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Environmental Degradation and Micro-pollutants in Light of Environmental Laws

June 2022

June 2022

DOI:10.1007/978-3-030-96523-5_4

In book: Hazardous Environmental Micro-pollutants, Health Impacts and Allied Treatment Technologies (pp.53-73)
Edition: First
Chapter: 4
Publisher: Springer

Authors:

Furqan Mahmud Butt

COMSATS University Islamabad; Quaid-i-Azam University

Umair Bin Nisar

COMSATS University Islamabad

Toqeer Ahmed

COMSATS University Islamabad

Environment is everything surrounding human beings. Biotic and abiotic contributors of environment affect natural, build, and social aspects of human beings. For healthy livelihood, human beings are dependent on environment. The increase in population, urbanization, and industrialization is having severe effect on world environment. Climate change further aggravates the situation. Despite several laws drafted for the awareness and reduction of environmental degradation, no profound results have been obtained. Environmental issues induce several negative externalities and contribute to market failure, thus affecting economic growth; this becomes a serious problem in developing and underdeveloped countries where there are no strong rules for reducing these negative externalities. Pakistan is ranked fifth among the most affected countries in terms of climate change despite the contribution of less than 01% in emissions. The air quality index of Pakistan is getting poor with every passing day; Lahore and Faisalabad were ranked as most polluted cities all over the world in terms of air quality index. The government of Pakistan has taken some time to realize environmental degradation and has initiated projects like billion tree tsunami and air quality laws to address climate change and environmental degradation.

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Emerging Contaminants and Associated Treatment Technologies

ToqeerAhmed

MuhammadZaffarHashmiEditors

Hazardous

Environmental

Micro-pollutants,

Health Impacts and

Allied Treatment

Technologies

Emerging Contaminants and Associated

Treatment Technologies

Series Editors

MuhammadZaffarHashmi, COMSATS University, Islamabad,Pakistan

VladimirStrezov, Macquarie University, Sydney,NSW,Australia

Emerging Contaminants and Associated Treatment Technologies focuses on

contaminant matrices (air, land, water, soil, sediment), the nature of pollutants

(emerging, well-known, persistent, e-waste, nanomaterials, etc.), health effects

(e.g., toxicology, occupational health, infectious diseases, cancer), treatment

technologies (bioremediation, sustainable waste management, low cost

technologies), and issues related to economic development and policy. The book

series includes current, comprehensive texts on critical national and regional

environmental issues of emerging contaminants useful to scientists in academia,

industry, planners, policy makers and governments from diverse disciplines. The

knowledge captured in this series will assist in understanding, maintaining and

improving the biosphere in which we live. The scope of the series includes

monographs, professional books and graduate textbooks, edited volumes and books

devoted to supporting education on environmental pollution at the graduate and

post-graduate levels.

More information about this series at https://link.springer.com/bookseries/16185

Toqeer Ahmed • Muhammad Zaffar Hashmi

Editors

Hazardous Environmental

Micro-pollutants,

Health Impacts and Allied

Treatment Technologies

ISSN 2524-6402 ISSN 2524-6410 (electronic)

Emerging Contaminants and Associated Treatment Technologies

ISBN 978-3-030-96522-8 ISBN 978-3-030-96523-5 (eBook)

https://doi.org/10.1007/978-3-030-96523-5

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Editors

Toqeer Ahmed

CCRD

COMSATS University Islamabad

Islamabad, Pakistan

Muhammad Zaffar Hashmi

Department of Chemistry

COMSATS University Islamabad

Islamabad, Pakistan

Preface

Environmental micropollutants are a diverse group in the form of microbes, organic

pollutants, and air/dust particles present in all media causing serious environmental

and health issues. Microbes in the form of bacteria, viruses, protozoan, and fungi

produce toxins in the environment and food, causing harm to the human beings.

Similarly, other micropollutants in the form of dust particles, allergens/pollens, and

spores, which are present in the environment, are threats to human health, affecting

both indoor and outdoor air quality. Micropollutants present in different form and in

different environments/media, such as soil, air, and water, may pose serious hazards

to people working in them. Organic pollutants in the form of polyaromatic hydro-

carbons, polychlorinated biphenyls, DDT, organochlorine pesticides, hormones,

and pesticides present in the soil and inorganic in the heavy metals causing serious

issues to human food chain. Mycotoxins produced by certain types of fungi and

bacteria contaminate different types of human and animal food and pose serious

threat to life.

Climate change is not only impacting livelihood but also changing life/disease

cycle, reproduction, and incidence of disease from pollutants along with huge

impact on precious resources, such as water and food, and the environment.

Similarly, infectious diseases caused by micropollutants are impacted by climate

change both in positive and negative ways. Different factors like socioeconomic,

urbanization, population density, land use, sanitation, and hygiene highly contribute

to spreading infectious diseases caused by micropollutants. So, it is important to

address all aspects of environmental micropollutants causing hazards to

human health.

In this book, basic concepts along with the advances in research related to envi-

ronmental micropollutants and treatment technologies to cope with the issues/haz-

ards have been discussed in detail. Different chapters of this book provide detail of

hazardous environmental micropollutants in different media like air, water, and soil

and methods to deal with the hazards caused. Policy- and economy-related issues

have been discussed in part. Antibiotics are undoubtedly one of the most effective

drugs being utilized for animal and human therapy. They are not only used for pre-

venting and treating different infectious diseases in animals and humans but also

used for agricultural and farming purposes. There is an increasing concern over the

past years about the effects of disposal and irrational use of antibiotics on both envi-

ronment and human health. Environmental media, which include air, soil, and water,

act both as a transmission medium and reservoir for antibiotic resistant bacteria.

This most important aspect has been covered in detail. Health hazards in the form

of toxic gases caused by burning of plastic waste and possible cohesive approaches

for the remediation of plastic waste are discussed. Mycotoxins and aerial fungal

spores and their human health impacts have been discussed. Other topics in this

book include allied treatment technologies for the remediation of environmental

micropollutants, which are discussed in depth.

Mostly knowledge provided in this book is updated and advanced level and

should be of interest to graduate level students, early career researchers and scien-

tists working in different domains and dealing with micropollutants and their toxic

impacts like, mycotoxins, organic and inorganic pollutants, infectious diseases etc.

We hope this book can be recommended for the students of environmental sciences

and as reference book for courses like environment and health, poverty and environ-

ment etc.

Islamabad, Pakistan ToqeerAhmed

MuhammadZaffarHashmi

Preface

vii

Contents

1 Environmental Micropollutants and Their Impact on

Human Health with Special Focus on Agriculture . . . . . . . . . . . . . . . 1

Bushra Gul, Muhammad Kamran Naseem, Waqar-un-Nisa Malik,

Ali Raza Gurmani, Ayaz Mehmood, and Mazhar Raque

2 Infectious Diseases, Challenges, and Their Impacts on

Human Health Under Changing Climate . . . . . . . . . . . . . . . . . . . . . . . 21

Toqeer Ahmed, Faridullah, and Rashida Kanwal

3 Marble Dust as an Environmental and Occupational Hazard . . . . . . 37

Salma Khalid, Mohsina Haq, and Zia-Ul-Ain Sabiha

4 Environmental Degradation and Micro- pollutants in Light of

Environmental Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

Furqan Mahmud Butt, Umair Bin Nisar, and Toqeer Ahmed

5 Impacts of Micro Pollutants on Human Health and

Enumerating the Environmental Refinement . . . . . . . . . . . . . . . . . . . 75

Muhammad Nawaz and Sheikh Saeed Ahmad

6 Emerging Organic Contaminants, Pharmaceuticals and

Personal Care Products (PPCPs): A Threat to Water Quality . . . . . . 105

Bashir Ahmad and Muhammad Imran

7 Environmental and Health Effects of Heavy Metals and

Their Treatment Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143

Hajira Haroon, Muhammad Rizwan, and Naveed Ahmed

8 Organophosphates’ Pollution Status and Their Remediation

Through Microbial Interaction in the Twenty-First Century . . . . . . . 177

Saliha Ahmad, Shazmin, Mazhar Raque, Fawad Ali,

Muhammad Farooq Hussain Munis, Syed Waqas Hassan,

Tariq Sultan, Tariq Javed, and Hassan Javed Chaudhary

viii

9 Toxic Organic Micropollutants and Associated Health Impacts . . . . 205

Muhammad Ijaz, Toqeer Ahmed, and Alishbah Iftikhar Ahmad

10 Impact of Aerial Fungal Spores on Human Health . . . . . . . . . . . . . . . 219

Sadia Alam, Maryam Nisar, Syeda Asma Bano, and Toqeer Ahmad

11 Health Risks Associated with Arsenic Contamination and Its

Biotransformation Mechanisms in Environment: A Review . . . . . . . 241

Muhammad Hamza, Sadia Alam, Muhammad Rizwan, and Alia Naz

12 Mycotoxins in Environment and Its Health Implications . . . . . . . . . . 289

Sadia Alam, Sobia Nisa, and Sajeela Daud

13 Antibiotics: Multipronged Threat to Our Environment . . . . . . . . . . . 319

Muhammad Zeeshan Hyder, Saniya Amjad, Muhammad Shaq,

Sadia Mehmood, Sajid Mehmood, Asim Mushtaq,

and Toqeer Ahmed

14 Remediation of Plastic Waste Through Cohesive Approaches . . . . . . 337

Bibi Saima Zeb, Qaisar Mahmood, Haleema Zeb Abbasi,

and Tahseen Zeb

15 Treatment Technologies for the Environmental Micro-pollutant . . . . 365

Ayesha Ayub and Sheikh Saeed Ahmad

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387

Contents

1© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022

T. Ahmed, M. Z. Hashmi (eds.), Hazardous Environmental Micro-pollutants,

Health Impacts and Allied Treatment Technologies, Emerging Contaminants and

Associated Treatment Technologies, https://doi.org/10.1007/978-3-030-96523-5_1

Chapter 1

Environmental Micropollutants andTheir

Impact onHuman Health withSpecial

Focus onAgriculture

BushraGul, MuhammadKamranNaseem, Waqar-un-NisaMalik,

AliRazaGurmani, AyazMehmood, andMazharRaque

Abstract Micropollutants (MPs) are key contaminants present in the soil, water,

and environment. They vary based on natural properties and classied as organic

(polychlorinated biphenyls, polyaromatic hydrocarbons, organochlorine pesticides,

DDT, hormones, EDC, pesticides) to inorganic (heavy metals). They enter the soil-

water- environment system through variable sources that include irrigation water to

agricultural system, disposal of expired pharmaceuticals, bio-solids or animal

excreta, sewerage wastewater, fertilizer application, industrialization, etc. They fur-

ther enter into the food system via a number of entry points such as groundwater,

agricultural soil, irrigated water, etc. and become part of the food chain.

Micropollutants largely impact the human health by triggering thyroid disorders,

neurodevelopmental dysfunctions in children, endocrine-associated malignancies,

and metabolic and bone abnormalities. Soil acts as an ultimate host for all such pol-

lutants where soil microbes degrade them biologically, addition of chemical inputs

can accelerate degradation, while use of physical approaches in remediating MPs is

costly. These MPs damage soil quality and soil microbial diversity, alter various soil

biogeochemical processes, and induce genetic changes in the microbial ecology.

Persistence of the MPs makes them more vulnerable for human health as they enter

the food chain. Phytoremediation is considered a proven technology to remediate

MPs in soil and multiple types of hyperaccumulator plants are used in remediation.

Developing nations do not yet have access to discharge limitations for new MPs into

the environment. This requires attention so that limitations may be set based on

scientic evidence.

B. Gul

Department of Biosciences, University of Wah, Wah Cantt, Punjab, Pakistan

M. K. Naseem · Waqar-un-Nisa Malik · A. R. Gurmani · A. Mehmood · M. Raque (*)

Department of Soil & Climate Sciences, Faculty of Basic and Applied Sciences,

The University of Haripur, Haripur, Khyber Pakhtunkhwa, Pakistan

e-mail: Mazhar.raque@uoh.edu.pk

1.1 Introduction

Micropollutants (MPs) are inorganic and organic substances that can adversely

impact the environment at very minute concentrations, in the range of micro-, nano-,

and pico-grams (μg/L (10−6 g/L); ng/L (10−9 g/L); pg/L (10−12 g/L)) (Chapman

1996). Micropollutants are ubiquitous and are often used to improve human life as

they are involved in daily life in the form of pharmaceutical and hygiene kits, pesti-

cides, plastics, endocrine-disrupting chemicals, etc. The general tendency toward

urbanization is the increasing number of untreated and treated wastewater, and MPs

stay in water. The extensiveness of MPs in aquatic systems is a major worry world-

wide. These MPs need disposal with minimum deterioration to the environment and

a new generation of MPs, usually called emerging MPs. Wastewater is the standard

source of these compounds, and this has generated difculties among researchers

and decision-makers dispensing with water use for household and production of

food. These comprise of (a) need to change thought of wastewater disposal, (b)

when water tables are intentionally recharged in order to rise volume of water

sources, (c) in soil-aquifer treatment systems, (d) reuse of water for consumption

and the reuse of wastewater for irrigation, and (e) where water levels are recharged

indirectly through this activity. Earlier advances in mass selective detection and

chromatographic separation techniques have approved the occurrence of organic

micropollutants (OMPs) in environmental matrices (surface water, water table, soil,

deposits, biota, and air-born particles), which enable a variety of concentrations to

be recognized for some of these contaminants (Hao etal. 2007). Micropollutants are

largely categorized into two types based on the nature of MP:

1. Heavy metals (specic density > 4.5kg/L), for example, cadmium (Cd), lead

(Pb), and copper (Cu), or “metal traces,” such as iron (Fe) and manganese (Mn),

and metalloids like arsenic (As) and vanadium (V). Heavy metals in various soil

organic amendments such as compost and vermicompost bound onto organic

matter and in convertible or adsorbed form. İn addition, typical chemical forms

are, in general, split between soluble and insoluble species in relation to the

condition of the metal in the starting materials and nature and chemistry of com-

posting process (Zucconi 1987).

2. Organic MPs (DDT, PCB, PAH, Hormones and EDC, PPCPs, and pesticides)

are comprised of a broad spectrum of compounds belonging to different chemi-

cal classes and used for many applications. Persistent organic pollutants (POPs)

are poisonous, consistent with nondegradability and strong hydrophobicity, can

compile in ora and fauna, and have the potential to wide-range move across

atmosphere (Cindoruk etal. 2020; Olatunji 2019). The presence and toxicologic

impact on environmental and human health of organic MPs have been broadly

examined in different environmental spheres (air, soil, and aquatic environment)

and food chains (Babut etal. 2019; Montuori etal. 2016; Poté etal. 2008). Three

main types of POPs are commonly stated in the environment for many years.

They are especially anthropogenically derived compounds involving polychlori-

nated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), and organochlorines

B. Gul et al.

pesticides (OCPs). Furthermore, according to the Stockholm Convention 2004

regulations, conservation of the environment and human health from POPs’ risk

is a high preference. For instance, through a variety of food matrices’ (e.g., veg-

etables, eggs, sh, meat, oils, and milk) usage, these contaminants were stated to

induce health impacts such as neurotoxicity, endocrine disruption, cancer, repro-

ductive disorders, leukemia, asthma, and health risks to fetal development

(Fernandes etal. 2019; Kim etal. 2017). The POPs are very determined in soil

and can affect crop quality and yield. Therefore, many studies stated the organic

MP degradation mechanism pathways (such as photocatalytic degradation) and

the remediation effectiveness of multielement contaminated soil to minimize

exposure, guarantee food safety, and protect human health (Weber etal. 2019; Ye

etal. 2020).

1.2 Sources ofMicropollutants

In natural and urbanized environments, water resources can be contaminated by

organic MPs through an extensive range of pathways, involving agricultural irriga-

tion using wastewater (Calderón-Preciado etal. 2011); inappropriate disposal of

expired pharmaceuticals (Tong etal. 2011); use of biosolids or animal excreta to

modify agricultural soils (Clarke and Smith 2011); exltration of wastewater in

sewerage systems (Wolf etal. 2012); and in some cases Arial deposition (Loos etal.

2007); in this perspective, it has been stated that wastewater is the major pathway of

organic MPs to enter into the environment (Kümmerer 2008) (Fig.1.1).

The rapid intensication of soil contaminants caused real concern for people liv-

ing around. Micropollutants attained more consideration in the last couple of

decades. They get released from multiple sources such as antibiotics, anti-

inammatories, disinfectants, heavy metals, rare earth elements, iodized contrast

media, spillage, leaching from dumps or landlls, endocrinedisrupting chemicals

(EDCs), personal care products, pharmaceuticals mainly through domestic sewer-

age systems, etc. (Hai etal. 2018; Verlicchi etal. 2010). They further enter into the

system through urban groundwater.

The dyeing industry is a major water-consuming and dye-utilizing economic sec-

tor (Spagni etal. 2012). It is evaluated that more than 50 billion tons of dyes are

utilized annually in the process of dyeing, of which ~20% is released directly into

aqueous efuent during the coloration process (Yurtsever etal. 2015) (Fig.1.2).

Landlls are considered a major source of emerging contaminants (ECs). The

leachate from the landlls carries organic MPs of anthropogenic origin (Table1.1).

The leachate may carry ltrate comprised of pharmaceutical, cleaning products,

disinfectants, avorings, etc. These ECs are persistent and have been found to with-

stand the natural attenuation process. Samples from differently aged landlls have

highly resistive ECs. Exhaust from vehicles pollutes soil with heavy metals. A sharp

rise in heavy metals concentration has been observed in soils of areas adjoining the

heavy trafc. The upper layers of soil prole are polluted with high concentrations

1 Environmental Micropollutants and Their Impact on Human Health with Special…

of heavy metals intake mostly by aerogenic sources (Yudina 2017). Studies revealed

that soil resists contamination of groundwater resources from contamination of As

and Pb. Analysis of soils affected by the Chernobyl atomic reactor accident showed

that Cs-137 could only penetrate for a few centimeters after 8 years. This shows that

soil also protects the groundwater out of air too. The application of biosolids has

been associated with the accumulation of MPs in soil. Application of biosolids from

wastewater raised MP levels by 10 times in soil (Andrade etal. 2010). In water-

scarce regions, wastewater is used for irrigation of agricultural elds. In developed

countries, wastewater is treated and applied to the soil. However, studies revealed

that even after treatment, recycled water carries many organic MPs. The level of

these compounds gradually increased in the soil posing threat to environmental sus-

tainability (Kinney etal. 2006).

1.3 Sources ofMPs inWastewater

The municipal wastewater comprises of numerous MPs due to anthropogenic activi-

ties. These MPs get added to municipal water through domestic and pharmaceutical

wastes. The origin of every MP can be traced from sources associated with human

activities directly or indirectly. The corrosion of metal surfaces leads to the addition

of heavy metals into wastewater. Similarly, use of plastic retardants, etc. also adds

Fig. 1.1 Representative sources and routes of MPs in the environment. (Adapted from Barbosa

etal. 2016)

B. Gul et al.

MPs to water. The urine and feces mostly contain MPs from pharmaceuticals, illicit

drugs, and hormones. Articial sweeteners are another important source of pollu-

tion in wastewater that enters through excretory products (Table1.2). Some MPs are

released into the wastewater directly. Surfactants, corrosion retardants, and personal

care products are part of the MPs that are added directly into the municipal water.

Fig. 1.2 Sources and pathways of MP (PPCPs) in the urban water cycle. (Adapted from Kim and

Zoh 2016)

Table 1.1 Anthropogenic sources of inorganic MPs

Cr Hg Sn Fe Cu Mn Zn Ni Cd Pb

Paperboard, pulp, peppermills, board mills,

paperboard, building paper, mills

× × × × × ×

Petrochemicals, organic chemicals × × × × × × ×

Inorganic chemicals, chlorine, alkalis × × × × × × ×

Fertilizers × × × × × × × × ×

Reneries of petroleum × × × × × × ×

Steel work foundries × × × × × × × × ×

Nonferrous metal work foundries × × × × × ×

Plating and nishing of aircraft and motor vehicles × × × × ×

Cement, at glass, asbestos products ×

Textile mill products ×

Leather nishing and tanning ×

Power plant of steam generation × ×

1 Environmental Micropollutants and Their Impact on Human Health with Special…

Besides these, synthetic chelating products and various industrial products are

added into the water directly. The runoff water is contaminated by diffusion of plas-

tic additives, ame retardants, and water-repellant compounds. The corrosion of

metal surfaces also leads to the addition of heavy metals into the wastewater. The

biocides and pesticides applied in the elds are leached into the runoff water during

rain. Aside from this, rainfall is tainted by heavy metals and other persistent organic

contaminants. In European countries, wastewater treatment plants (WWTPs) are

installed to treat sewage waste of urban areas. Monitoring of the released water

from WWTPs showed that it contains MPs. The treatment of water does not elimi-

nate the MPs completely and is a threat to the environment if remains unnoticed for

a longer period (Heeb etal. 2012).

1.4 Impacts ofMPs

The inuence of persistent organic pollutants (POPs) on human health may be high-

lighted in terms of exposure and the impacts of endocrine disruptors. Exposure to

endocrine disruptor chemicals (EDCs) is now recognized to have a larger role in the

causation of many more endocrine illnesses and disorders than previously assumed.

Female reproductive dysfunction, impacts on male reproductive health, adrenal dis-

eases, and the development of immune system difculties are examples. Thyroid-

related disorders, neurodevelopmental dysfunctions in children, endocrine-associated

malignancies, and metabolic and bone abnormalities are further examples (Grob

etal. 2015; Hughes etal. 1994; Humans 2010).

Table 1.2 Origin of MPs, their class, and mode of entry into the environment

Organic micropollutants

(OMPs) Class Mode of entry

Endocrine disruptive

chemicals, personal care

products,

pharmaceuticals,

Veterinary drugs, cardiovascular drugs

(-blockers), blood lipid regulators,

psychiatric drugs, analgesics, and

antibiotics

Farmland waste, accidental

spills, hospital disposal,

and discharge

Detergents, surfactants,

and per-uorinated

compounds.

Insect repellents, fragrances, steroids,

hormones antiseptics, UV lters,

synthetic musks, per-uorooctane

sulfonate, Per-uorooctanoic acid

Soil and groundwater,

industrial waste, laundries,

households, dispersants,

dilutants, and pesticides

Agriculture Flame

retardants

Herbicides, pesticides

Organophosphorus compounds,

organohalogen compounds

Household and agriculture

waste, industries, baby

products, electronics,

furniture, etc.

Additives Industrial, gasoline Municipal waste, disposed

engine oil

By-products of swimming

pool disinfectants

Haloacetic acids, trihalomethanes Chlorinated human

material such as saliva,

urine, skin, and hair

B. Gul et al.

Soil is the ultimate host for all chemicals released as a result of anthropogenic

activities. However, soil is enabled with a peculiar ability to maintain its natural

composition and resist potential changes. In this regard, soil microorganisms have a

pivotal role. They help to decompose contaminants and convert them into mobile

and available forms for plants. The impact of microorganisms on soil and the envi-

ronment can be ascertained through the relation of these compounds with soil and

water microorganisms. As soil and water depend upon microorganisms for degrada-

tion of xenobiotics and ultimate restoration in the natural state, their study is very

important. In this regard, soil microbial ecology helps to dene the impacts of MPs

on the environment and their possible degradation mechanism. The emerging MPs

are a potential threat to the biogeochemical cycle, element cycles as well as energy

ow of an ecosystem. Microorganisms, specially bacteria, have a variety of mecha-

nisms to interact with xenobiotics. However, there are some species of bacteria that

can be used for bioremediation of contaminated soils.

Microorganisms play similar roles in nutrient cycles in groundwater, and they

help to attenuate a variety of chemical processes in subsurface ecosystems, such as

MPs’ breakdown and immobilization, redox cycling, and nutrient transport (Griebler

and Lueders 2009). Several novel phylogenetic lineages have been discovered in

groundwater environments, indicating that groundwater has a bacterial community

capable of degrading xenobiotics and other MPs.

1.5 Xenobiotic Micropollutants

Xenobiotic: Both words are used interchangeably to refer to a man-made substance

that is not recognized by the enzyme systems of living organisms and is frequently

released into the environment at amounts that produce negative consequences. In

recent years, a large number of xenobiotic chemicals have been released into the

environment as a result of various industrial and/or agricultural activities. Pesticides,

fuels, solvents, alkanes, polycyclic aromatic hydrocarbons (PAHs), nitrogen, and

phosphorus compounds are examples of typical organic xenobiotics, whereas haz-

ardous heavy metals are the most common inorganic MPs. Xenobiotic chemicals

are substances that are present in living organisms or the environment but are not

generated by the organism. Most bacterial strains in soil cope with xenobiotics

through breakdown. Pesticide and pharmaceutical degradation characteristics are

found in microbes on plasmids and transposons. Horizontal gene transfer (HGT)–

also known as lateral gene transfer– or xenobiotic catabolic mobile genetic ele-

ments like plasmids allow them to acquire genetic information from comparable or

phylogenetically distinct populations in the community. It is commonly assumed

that MP-degrading enzymes are developed from isozymes in reaction to industrial

production and xenobiotic environmental discharge. Individual cells that are most

adapted to resisting or degrading the xenobiotic are selected, and their populations

grow in number in comparison to the rest of the microbial community. When a

xenobiotic, or organic substance in general, enters the soil, it might be exposed to

two fundamental processes (Cheng 1990):

1 Environmental Micropollutants and Their Impact on Human Health with Special…

1. Transfer procedures that move a material without changing its structure. They

include adsorption, crop retention, dissolved or sorbed runoff movements, diffu-

sion and vapor-phase diffusion, and sorption and desorption on soil colloid sur-

faces. Among these processes, the interactions at interfaces between organic and

inorganic soil colloids and xenobiotics through sorption/desorption mechanisms

are the most important. Adsorption processes allow an organic molecule to be

weakly or rmly linked with inorganic and organic colloids. Pure and polluted

clays, humic compounds, and humic–clay associations are the abiotic soil com-

ponents involved in the interaction with xenobiotics. Several of the processes

just outlined will be heavily inuenced by the existing interactions. They may

impact xenobiotic mobility, availability for plant or microbial absorption, trans-

formation by abiotic or biotic agents, and effect on soil activities.

2. Organic chemical degradation processes that change the chemical structure of

the organic substances. They happen as a result of chemical, biological, and

photochemical changes. Microorganisms, plants, and their enzymatic proteins,

whether intracellular or extracellular, are the biotic components engaged in the

biological breakdown of xenobiotics and, in general, in their interactions with

them (Fig.1.3).

1.6 Impact ofPharmaceutical MPs onSoil

The impact of pharmaceutical residues on soil ora and fauna is negatively related.

It is reported that phenol has negative impact on soil microorganisms. It denatures

the proteins formed by the bacteria (Zavarzin and Kolotilova 2001). Application of

animal manures produces bacteria in soil that generate antibiotics resistant to these

medicines. Later, these resistant genes get transferred to other bacterial strains

Fig. 1.3 Mutual interactions of xenobiotics with soil microorganisms and enzymes. (Adapted

from Gianfreda and Rao 2008)

B. Gul et al.

found in plants and become a potential threat to humans that consume such plants.

Genetic changes in bacteria appear on exposure to antibiotics. A study showed that

antibiotic tetracycline impacts bacteria at pH 6–7 more actively as compared to pH

8. In soil, tetracycline deteriorates more as it forms complexes with metals and

becomes more reactive towards bacteria. The biogeochemical cycles of many ele-

ments get disturbed by the action of pharmaceutical contamination of soil. Use of

antibiotics for humans, poultry, animals and contamination of soil disturb the natu-

ral cycles of sulfate reduction, methanogenesis, and nitrogen (Ding and He 2010).

Antibiotics such as glimepiride, glibenclamide, gliclazide, and metformin have

been studied for their fate in soil. Drugs with high concentration of polar organic

compounds had better sorption capacity. Hence, they were difcult to be bio-

transformed. They remain in the soil for a longer period and are potential threat to

environmental safety. Studies have shown that due to better mobility, metformin is

readily decomposed in the soiland has reduced half life. A comparison of sulfonyl-

urea herbicides and their derivative pharmaceutical drugs showed that herbicides

have less sorption ability and easier to degrade compared to sulfonylurea drugs

(Mrozik and Stefańska 2014). Penicillin is a widely used antibiotic and its effect on

cultured microorganisms has been studied. It has adverse impact on bacterial cell

wall synthesis. Tetracycline and streptomycin also have an adverse impact on bac-

teria. They disturb the ribosomal protein synthesis of bacteria (Zavarzin and

Kolotilova 2001) (Table1.3).

1.7 Impact ofMP Pesticides onSoil andSoil Organisms

Unjustied use of pesticides on crops and consequent deposition in soil poses threat

to soil fertility. These contaminants can adsorb onto soil particles and contaminate

soil for a longer period by deposition at the surface. In addition, crop pesticides can

also inuence soil microbes and disturb their physiological and metabolic pro-

cesses. In this way, indiscriminate use of these chemicals degrades soil and disturbs

the natural biogeochemical and elemental cycle in the environment (Savonen 1997).

1.7.1 Herbicides

• Triclopyr is a common herbicide used in landscape plants. It inhibits bacteria that

helps in the transformation of ammonia into nitrate (Pell etal. 1998)

• Glycine/Glyphosate is the world’s most frequently used herbicide (Dill et al.

2010). It functions by binding to enzymes and inhibits from the synthesis of

aromatic compounds that are essential for bacteria and fungi. It is polar and has

high sorption afnity in soil that makes it immobile. However, it is not persistent

and can be transformed to aminomethylphosporic acid. Glyphosate adversely

1 Environmental Micropollutants and Their Impact on Human Health with Special…

affects microbial population of soil. However, most microorganisms can tolerate

its impacts using many functions such as rapid detoxication.

• Chloroacetamide includes metolachlor and acetochlor, which have different

methods of detection (Table1.4). They are commonly used herbicides that func-

tion in soil through inhibition of elongase enzyme. These enzymes play various

important functions in bacteria and fungi (Rose etal. 2016)

• Sulfonylurea and Imidazolinone are used in cereal crops at relatively low con-

centrations. They act for inhibition of acetolactase synthase enzyme that is pres-

ent in microorganisms. Application and deposition of this herbicide are expected

to negatively impact microbes (Boldt and Jacobsen 1998).

Table 1.3 Micropollutants’ application and their peculiar characteristics

Micropollutants Applications Characteristics

Carbamazepine Anticonvulsant Potential ecotoxicity, water-persistent in

environment, degradation in sewage treatment

plant, low removal efciency on wastewater

treatment plants (WWTPs).

N,N-Diethyl-m

toluamide (DEET)

Insect repellent Persistent in environment, little data about

detection in aquatic environment, toxic for

freshwater invertebrates, birds, and sh

2-Methylthio-

benzothiazole

(MTBT)

Stabilizers or fungicide in

production of rubber

Sources include industrial plants, tire debris

Triphenyl

phosphate (TPP)

Hydraulic uid and ame

retardant

Possibly neurotoxic, bioaccumulation, toxic

effect to aquatic organisms

Tris(2-chlorethyl)

phosphate (TCEP)

Plasticizers and ame

retardants

Classied in the European Union as potential

human carcinogen, nonbiodegradable,

hazardous, toxic to aquatic organisms

Tris-(chlorpropyl)-

phosphate (TCPP)

Flame retardants Bioaccumulation potential, hazardous, readily

biodegradable

Fluoranthene Pyrene and uoranthene

like other PAHs form

during combustion

Among the PAHs, persistent organic MPs,

slow environmental degradation,

bioaccumulation potential, toxicity, priority

substances

Lidocaine Local anesthetic,

antiarrhythmic drug

Low potential for bioaccumulation

Caffeine Psychomotor stimulant High solubility in water, high stability under

varied environmental conditions

Tonalide, Fixolide,

(AHTN)

Polycyclic musk,

chemosensitizers

Bioaccumulation potential

Galaxolide 50,

Abbalide (HHCB)

Polycyclic musk,

chemosensitizers

Bioaccumulation potential

Triclosan Antibacterial and

antifungal agent

Bioaccumulation, aquatic toxicity

Pyrene Found in many

combustion products

Among the PAHs, persistent organic MPs,

toxicity, bioaccumulation

B. Gul et al.

• Triazines, phenylureas, and amides kill plant through disrupting photosystem ll.

However, they are only expected to kill photosynthesizing microbes and have no

such direct link with non-photosynthetic bacteria and fungi. Nevertheless, the

mobile nature of these herbicides is a potential threat for off-site damage of other

soil organisms.

• Phenoxycarboxylic acids are like the shape of auxins. They mimic the auxins and

disrupt important roles played by them. One of the most signicant roles of aux-

ins is the facilitation of plant microbial association. So, the application of such

herbicides can potentially affect association and disturb soil ecology.

Table 1.4 Group of chemical substances and analytical methods available

Group of substances Analytical methods available

Old organochlorines GC-MS LM-MS GC-ECD

Chlordane ×

PCBs × ×

Metoxychlor × ×

HCHs ×

Hexachlorobenzene ×

Heptachlor ×

Endrin ×

Endosulphan × ×

Dieldrin ×

DDTs ×

New pesticides

Alachlor × ×

Triuralin × ×

Simazine × ×

Isoproturon ×

Diuron ×

Dicofol × ×

Chlorpyrifos × ×

Atrazine × ×

Chlofenvinphos × ×

PAHs

Priority set and/or individual PAHS × ×

Old organochlorines

BRFs, PBDEs, HBCD, TBBP-A × ×

Pentachlorobenzene ×

hexachlorobutadiene ×

Endocrine disruptors

NP/NPEOs and related substances ×

Dibutyl and diethylhexyl phthalate ×

Octylphenol ×

PFOS ×

1 Environmental Micropollutants and Their Impact on Human Health with Special…

• Dinitroanilines such as triuralin and pendimethalin halt cell mitosis through

prevention of tubulin elongation. They hinder plant growth. However, not only

eukaryotes but prokaryotes also divide using tubulin proteins (Löwe and Amos

1998). Microbes depending on tubulin cannot divide after interaction with

Dinitroanilines.

1.8 Interaction ofMPs andSustainable Agriculture

Worldwide MPs are of great concern and they are present in various forms such as

heavy metals, gases, volatile organic compounds, loud sounds, over-dumped places,

excessive use of chemical fertilizers, pesticides, automobiles, and many oth-

ers forms.

These MPs are involved in acute environmental changes. Changes caused by

environmental MPs involve a variety of factors, such as: land degradation, water

scarcity, damage to plants, food famine, biodiversity, climatic changes, etc.

Agriculture is playing a noteworthy role from many decades in the economy and

survival of humans. It is considered the backbone for many countries. Agriculture is

a source of livelihood, revenue, economic development, foreign exchange, food

supply, fodder for animals, raw materials, etc. Micropollutants are emerging con-

taminants that contain anthropogenic as well as natural substances. These MPs are

leaving their impact on the environment as well as on agriculture. Continuous emis-

sions of gases such as chlorouorocarbon, carbon dioxide, lead, carbon monoxide,

etc. causes the continuous rise in climatic changes. Emissions of gases are depleting

the ozone layer and increase the temperature of the atmosphere. Excessive rise in

temperature damages growth and yield of crops. It is damaging the soil, specially

the areas with low annual rainfall. Excessive rise of temperature is another reason

for drought conditions. It affects soil conditions, causing land degradation, ero-

sion, etc.

Emission of sulphur and nitrogenous gases is the reason for acid rain, which

affects soil and damages crops. Industries such as pharmaceuticals, pesticides man-

ufacturers, etc. are emitting gases on combustion and dump their waste in water. The

MPs are the reason for water scarcity for useful purposes. It is impossible to use the

contaminated water for production of crops because it affects the yield of crops.

This contaminated water also affects the soil nutrients’ availability and microbial

activities. Excessive concentration of nitrate that results because of nitrogen and

oxygen is the reason of eutrophication. Its damages aquatic life and contaminates

water. Excessive nitrate concentration makes the water unavailable for agricultural

and household purposes.

MPs are an important issue to solve worldwide. It is affecting the land and atmo-

sphere leaving its impact on agriculture. It is affecting our efforts of sustainable

agriculture. These MPs are the reason for food scarcity in many areas, leading future

B. Gul et al.

generations to hunger, poverty, poor health, and economic losses. These problems

can be solved by minimizing the use of sprays, organic fertilizers, pesticides, etc.;

there is a need for awareness to avoid this problem.

1.9 Interaction ofMPs andMicrobial Activities inSoil

Microorganisms account for <0.5% of soil mass. These organisms are a major foot-

print for most soil properties and processes. About 60–80% of soil process and

metabolism activities occur due to microora. Microbial activities play a notewor-

thy part in the transformation of MPs. Microorganisms have the ability to control

MPs and release useful chemical compounds. Microorganisms play a key role in the

cycling of nutrients and their formation. Microbial activities are involved in a vari-

ety of processes, such as: nitrication, nitrogen xation, carbon mineralization,

nutrient availability, etc. Microorganisms commonly present in soil are bacteria,

fungi, actinomycetes, protozoa, algae, etc. These organisms in soil help to control

quality, depth, moisture, structure, and properties of soil. Most of the external fac-

tors, such as climate, topography, pollution, bedrock, etc., affect microbial activi-

ties. The interaction among multiple factors is responsible for variation in microbial

activities and soil. Microorganisms decompose MPs present in soil and transform it

to nutrients or organic compounds.

Pollutants are emerging contaminants involved in environmental changes. These

MPs are leaving their impact on the microbial activities. Micropollutants allow the

conversion of a large amount of nitrogen through the process of denitrication,

ammonication, etc. Conversion of nitrogen will lead to the emission of sulfur diox-

ide and sulfur compounds that will result in acid rain. Acid rain reduces nutrient

availability and soil processes. It results in soil erosion and ecological imbalance. It

affects the microbial activities because of erosion and changes in soil process.

Acidication impacts soil fertility and causes death of microorganisms responsible

for the microbial activities in soil. Increase of salinity in soil is linked with the MPs

present in soil. Deposition of nitrate and phosphorus because of irrigation and agri-

cultural process results in increased salt concentration in soil. Rise in salt concentra-

tion affects microorganisms’ growth and their activities which will result in growth

of crops and reduce groundwater quality. Soil MPs result in water pollution. When

chemicals such as heavy metals leach down the groundwater, it affects microbial

growth and their activities. For proper functioning of microorganisms, it is impor-

tant to provide favorable conditions. For proper microbial activities, it is important

to reduce MPs’ concentration from the soil.

1 Environmental Micropollutants and Their Impact on Human Health with Special…

1.10 Interaction ofMPs andHuman Health

Micropollutants are emerging contaminants that contain anthropogenic as well as

natural substances. These MPs are leaving their impact on the environment as well

as on human health. Humans always interact with environment on daily basis. This

interaction between humans and the environment results in pollution, global warm-

ing, deforestation, etc. These problems have a major impact on the human health.

Pollutants present in the atmosphere are causing human health problems such as:

• Increase the chance of respiratory diseases.

• Risk of developing asthma problems.

• Increase the respiratory inammation.

• Reduce lungs’ functioning.

• Damage reproductive system and endocrine system.

• Commonly show wheezing and coughing.

• Increase risk of heart failure.

• Increase the risk of developing cancer.

Pollutants present in water are causing human health problems such as:

• Cancer development

• Hormone’s disruption

• Rashes

• Hepatitis

• Damage reproductive system

• Damage immune system

• Damage respiratory system

• Cause heart problems

• Cause kidney failure

• Cause typhoid

• Cause polio and cholera

Pollutants present in soil are causing human health problems such as:

• Headache, vomiting

• Breakdown of central nervous system

• Cough, pain in chest

• High chances of developing of cancer

• Irritation of skin and eyes

• Damage to kidney

• Damage liver

• Muscular blockage

These all problems are caused by MPs present in the environment. These all

problems are reducing the lifespan of humans. It is important to resolve these prob-

lems to reduce the risk of human health.

B. Gul et al.

1.11 Strategies forManagement ofMPs

Micropollutants are of great concern worldwide. Changes caused by environmental

MPs involve variety of factors, such as: land degradation, water scarcity, damage to

plants, food famine, biodiversity, climatic changes, etc. Micropollutants also cause

a major impact on human health. Management practices are required to reduce the

risk of MP. There are different practices that are performed to reduce the risk of

micro-pollution such as forest buffer (trees, shrubs, grasses) should be planted

across the streams and banks of rivers. It will help to reduce pollution in water. It

will reduce the risk of temperature increase.

Hydrochars produced through hydrothermal carbonization (pistachio shells) are

a sustainable and efcient replacement to activated carbons for the removal of MPs

from wastewaters that are difcult to treat using traditional methods. For the inves-

tigation of caffeine/hydrochars aqueous systems, a combined experimental and

molecular simulation method is used. This case study is used to ne-tune a generic

framework for rationally customizing surface functional groups on hydrochars for

the selective adsorption of MPs from wastewaters (Román etal. 2018).

1.11.1 Air Pollutants

Air pollutants’ control strategies involve two categories:

• Control of emission

• Control of gaseous emission

There are many methods and instruments used to control the emission from air,

such as:

• Cyclone collector

• Wet scrubber

• Settling chamber

• Filtration devices

• Electrostatic precipitation

1.11.2 Water Pollutants

Water pollution may be controlled using a variety of methods and equipment,

including:

• Physical method

• Chemical method

• Biological method

1 Environmental Micropollutants and Their Impact on Human Health with Special…

Many methods and equipment are used to reduce water contamination through

physical processes, such as:

• Inltration

• Screening

• Sedimentation

• Flotation

Many methods and equipment are used to reduce water contamination through

chemical processes, such as:

• Chemical precipitation

• Adsorption

• Disinfection reaction

1.11.3 Solid Pollutants

There are many methods and techniques to control solid MPs such as:

• Landlling

• Incineration

• Composting

These all are modern and most used methods for the reduction of MPs. These

problems can be solved by minimizing the use of sprays, organic fertilizers, pesti-

cides, etc.; there is a need of awareness to avoid this problem.

1.12 Conclusion

Micropollutants are of great concern worldwide as they are sublethal to the environ-

ment and living organisms on the planet. A wide range of toxic effects of MPs affect

the organisms at cellular level. Changes caused by MPs involve a variety of factors,

such as land degradation, water scarcity, damage to plants, food security, biodiver-

sity, etc. Micropollutants also cause a major impact on human health. It is important

to reduce problem for the better survival of mankind. Reduction of pollution is

benecial in many ways such as prevention of MPs will minimize the greenhouse

gas emissions. Traditional bioremediation approaches such as phytoremediation,

biostimulation, and bioaugmentation might all play a signicant role. It leads to

sustainable environment for ages by remediating the agricultural soils and limiting

the MPs. In some situations, a mix of biological and chemical treatments may be

advantageous to achieve optimum remediation efciency. It reduces the nical cost

(waste management and cleanup cost) and environmental cost (health problems and

environmental damage). Reduction of environmental MPs is important for future

B. Gul et al.

generations, for their health and better life. Developing nations do not yet have

access to discharge limitations for new MPs into the environment. This requires

attention so that limitations may be set based on scientic evidence. To estimate the

related pathophysiological risk to humans and other creatures, it is critical to deter-

mine the toxic effects of MPs in organisms using specialized and suitable assays at

each level of biological organization. A comprehensive and cost-effective method

for detecting and analyzing MPs and their metabolites in environmental samples is

desperately needed. As a result, there is a need for a revised risk assessment meth-

odology that incorporates consolidated toxicity data generated from systematic

research in determining acceptable limits to safeguard human and ecological health.

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1 Environmental Micropollutants and Their Impact on Human Health with Special…

21© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022

T. Ahmed, M. Z. Hashmi (eds.), Hazardous Environmental Micro-pollutants,

Health Impacts and Allied Treatment Technologies, Emerging Contaminants and

Associated Treatment Technologies, https://doi.org/10.1007/978-3-030-96523-5_2

Chapter 2

Infectious Diseases, Challenges, andTheir

Impacts onHuman Health Under

Changing Climate

ToqeerAhmed, Faridullah, andRashidaKanwal

Abstract Climate variability like temperature changes, rainfall pattern changes,

heatwaves, drought etc. effects the infectious diseases in human beings has been

discovered in late nineteen century. Infectious diseases (IDs) like malaria, dengue

fever, chikungunya, yellow fever, seasonal inuenza, cholera, Asthma, TB, and

other respiratory diseases are caused by bacteria, viruses, protozoans, and other

parasites, but their mode of transmission, type, size, and impacts vary greatly. Some

of the IDs are epidemic, while others are pandemic and have long-lasting effects on

human beings and the economy of the world. These may be water- or food-related,

waterborne, vectorborne, or others. Lots of challenges are ahead for the scientists in

the twentieth and twenty-rst century to cope with the impacts of ID on health and

economy. In this chapter, linkages of ID with climate changes, challenges, impacts

on human health and economy, control and remediations of ID, role of modelling,

and future perspectives have been discussed in detail.

T. Ahmed (*)

Centre for Climate Research and Development (CCRD), COMSATS University Islamabad

(CUI), Islamabad, Pakistan

e-mail: Toqeer.ahmed@comsats.edu.pk

Faridullah

Department of Environmental Sciences, COMSATS University Islamabad (CUI),

Abbottabad, KP, Pakistan

e-mail: faridullah@cuiatd.edu.pk

R. Kanwal

Department of Biology, Army Public School and College, Rawalpindi, Pakistan

2.1 Introduction

Climate change (CC) impacts include sea-level rise, melting ice, heat waves,

droughts, oods, change in rainfall pattern and ecosystems, shift in seasons, etc.,

resulting in vulnerability of food and water along with the origin of infectious dis-

ease (IDs). IDs are impacted by change in climatic conditions, like change in rain-

fall pattern, temperature, humidity, heatwaves, etc. Shift in seasons impacts increase

or decrease in growth, host specicity, and mode of transmission of microbes.

Climate is changing due to rise in temperature as predicted by Intergovernmental

Panel on Climate Change (IPCC) that temperature will rise in the twenty-rst cen-

tury (IPCC 2014), and accordingly, it will not only impact the natural resources but

also affect human health-related infectious diseases like malaria, dengue fever, chi-

kungunya, yellow fever, Zika virus, West Nile, seasonal inuenza, cholera, Asthma,

TB, and other respiratory diseases caused by bacteria, viruses, and fungi. A suitable

environment is provided by the climatic conditions for their entry into the host,

growth, and completion of life cycle of the microbes. Accordingly, host selection for

specic environment, survival, reproduction, intensity, and geographical distribu-

tion varies due to climatic conditions, and by adopting preventive measures, health

impact can be controlled (Xiaoxu Wu 2016). Salmonellosis, cholera, and Giardiasis

outbreaks are common in monsoon and ooding, especially in warm and humid

conditions (Chretien 2014). Similarly, VBDs malaria, dengue fever, yellow fever,

etc. are increased during monsoon conditions and after rainfall especially under

humid conditions. Suitable temperature (25–35°C) and humidity 65–80% are the

optimum conditions for the breeding of mosquitoes and larval growth (Toqeer

Ahmed 2019). Socio-economic factors play important role in the spread of human

infections and vulnerability due to climate change. There is long-term direct rela-

tionship among socio-economic factors, climate change, and prevalence of disease

(Anwar 2019). The most common and emerging disease that appeared in 2019in

Wuhan city in China is COVID-19, which spread throughout the world and killed

thousands, and millions are affected by this pandemic, and it has been reported that

COVID 19 is dependent on meteorological parameters as low temperature and

humidity favour the transmission of disease (Jiangtao Liu 2020). This pandemic

disease impacts the ways of living, social contacts, and change in habits and envi-

ronment (Stefano Capolongo 2020). This highlighted the need to transform the cit-

ies into healthy environment. The IDs spread throughout the world and are impacted

by climate change (CC) without any restriction of boundaries, so there is a need to

mitigate these and governance and policies to control IDs and CC.The World Health

Organization reported that the changes in the pattern of infectious diseases are due

to climate change and need to learn the complex phenomenon through modelling

for the prediction of future impacts (WHO 2020) rather than observational studies.

This chapter describes how human infectious diseases are impacted by climate

change, challenges, and impact on human health, how to control IDs relate to cli-

mate change, and role of modelling on future impacts and perspectives. Predicted

impacts of climate change on IDs and their control are shown in Fig.2.1.

T. Ahmed et al.

2.2 Infectious Diseases (IDs) andClimate Changes (CC)

South Asian countries like India, Pakistan, Nepal, Bangladesh, Afghanistan, Sri

Lanka, etc. are most vulnerable to a signicant proportion of IDs due to CC and

other factors like socio-economic factors, urbanization, sanitation and hygiene, land

use, and population density (Bhandari, Climate change and infectious disease

research in Nepal: are the available prerequisites supportive enough to researchers?,

2020b). Climate change is impacting and increasing the severity of some diseases in

one part of the world and decreasing the impact in other parts like decrease in

malaria cases in the last decades and increase in viral diseases (Flahault 2016).

Another study reported that regression model showed that monthly diarrhoea cases

increased by 8.1% by the increase of 1°C average maximum temperature and 0.9%

by the increase in 10mm in rainfall (Bhandari 2020a). Similarly, Salmonella is

foodborne pathogens inuenced by temperature about 35% in European countries

(Kovats 2004). Epidemiological triangle (host, agent, and environment) has been

given to understand the behaviour of IDs and reported that without these aspects, a

disease cannot occur (Smith 2019). To address the actual facts on disease-specic

needs, more focused research is required to address the challenges under rapidly

changing climatic world (Redshaw 2013). There are a number of diseases which are

impacted by climatic parameters. Like Malaria, Yellow fever, Zika, COVID-19, and

Dengue fever are caused by viruses. Second, COVID 19 is affected by CC and vice

versa. Third, Cholera, TB, Asthma, and other respiratory disorders are caused by

bacteria. Fourth, Zoonotic diseases, which transfer from animals to human beings,

are caused by bacteria, viruses, and fungi, and Anthroponosis, which spreads from

human to human and animals. There are many other diseases like Japanese encepha-

litis, Rift Valley Fever, Chikungunya, leishmaniasis, and human African

Fig. 2.1 Predicted impact of CC on IDs and control

2 Infectious Diseases, Challenges, and Their Impacts on Human Health…

trypanosomiasis caused by viruses and are impacted by CC (Florence Fouque 2019;

Mordecai 2020). Fifth, waterborne diseases are impacted by climate change. High

temperature and precipitation are predicted to have more impact on IDs, especially

in the Arctic (Waits 2018). These diseases are posing serious threats and high risks

to human beings. CC further exaggerates the situation in some cases. The above

categories have been discussed in detail, that is how these are impacted by cli-

mate change.

2.2.1 Malaria, Yellow Fever, Dengue Fever, andVector-Borne

Diseases (VBDs)

A complex relationship has been found between CC and diseases caused by vectors.

As reported, CC contributes to the spread of VBDs like Dengue, Zika, and

Chikungunya, especially in developing countries (Filho 2008; Asad 2018). A warm

and moist environment favours the growth of vectors and their breeding (Naish

2014), but in other way high temperature and drought conditions stop the growth of

larvae and breeding of vectors or sometimes suppress the growth of vectors

(Florence Fouque 2019). A detailed review on impact of CC on dengue and malaria

through a systematic and modelling approach conrms the impact of CC on dengue

and malaria spread (Naish 2014; Christine Giesen 2020; Ngarakana-Gwasira 2016;

Martens (1997), p.1997). These climatic parameters impact the diseases indirectly.

CC will impact VBDs like malaria, yellow fever, and dengue fever, but how these

will depends on the factors like population, the immune system of the population,

deforestation, drainage, drug or insecticide resistance, demography, etc. as these

factors can impact the ecology of the vectors (Fernando 2020). Change in vector

and distribution in one region to another due to CC has been observed (Florence

Fouque 2019). CC can impact and increase the disease burden caused by vectors

especially in South and Sub-Saharan Africa (Mordecai 2020). Further, the impact of

CC on these diseases can affect social and economic losses. Chikungunya, West

Nile Virus, Zika, and Dengue are a diverse group of Arboviruses (Young 2018). A

strong and positive relation has been found in spread of Chikungunya and rainfall

(Shil 2018).

2.2.2 COVID 19 andClimate Change

There are two possibilities, either climate change is affecting the COVID and

spreading the pandemic disease or Covid is impacting the climate change. In the

rst case, it is not clear that climate change directly impacts the spread of COVID

19 disease, but it can affect indirectly like people living in poor air quality can be

more vulnerable to the worst symptoms of COVID and more people can die.

T. Ahmed et al.

Similarly, some studies reported that there is no direct evidence that increase in

temperature can stop the spread of COVID (Bernstein 2020; Bashir 2020; Iqbal

2020), but some others reported that temperature, wind speed, and humidity are

negatively correlated with the daily new cases and temperature (>20°C) positively

correlated with daily new cases (Yuan 2021).

In the second case, human mobility and transport are reduced due to the spread

of COVID pandemic throughout the world. As a result, the GHG emissions reduced

by 25% and quality of air improved and decreased particulate matter had been

observed (Sipra 2020; Jauregui 2020). Another study reported that the average tem-

perature, minimum temperature, and air quality can be helpful in suppressing the

disease (Bashir 2020). However, it is suggested that green environmental policies

can be helpful in reducing this pandemic disease (Bashir 2020). Among the lessons

learnt, acceptance of disease, preparedness like physical distancing, hygienic mea-

sures, mobility restrictions of ill persons, use of face masks, socio-economic restric-

tions, communication, and support, including early detection and warning, are the

key factors that helped in controlling the spread of disease (Yuri Bruinen de

Bruin 2020).

2.2.3 TB, Asthma, andOther Respiratory Disorder

Pollens and both indoor and outdoor allergens can cause respiratory issues. CC has

immediate and long-term impacts on the human respiratory system (Gerardi 2014).

Climate can increase pollens and allergens which are produced by moulds and

plants (Gennaro D’Amato 2014), but the degree of effect is not clear (Ayres 2009).

People who are sensitive to pollens and allergens are more vulnerable, like cardio-

pulmonary and asthma patients. Warming and increased unpredictability of weather

cause negative impacts on humans with respiratory disorders (Manish 2020). More

details on mould and aeroallergen have been given in separate chapters.

2.2.4 Zoonotic andAnthroponosis Diseases

Zoonotic diseases are the diseases which are transferred from animals to human,

like bird u, brucellosis, Ebola, Giardiasis, etc. or biting insects like Leishmaniasis;

malaria and dengue are caused by biting insects and climate change can cause shift

in animals and insects from one region to another (Cardenas 2008). Anthroponosis

is the disease which transfers from human to human, and Anthropozonosis is the

disease which transfers from animals to human under natural conditions like

Anthrax, Rabies, etc. A study reported the decrease in abundance of tsetse y in

Zambezi valley due to change in climate, especially increase in temperature

(Longbottom 2020). Recently reported Dracunculus medinensis is Zoonotic disease

in Chad spread in dry weather through waterborne route when ponds and rivers are

2 Infectious Diseases, Challenges, and Their Impacts on Human Health…

infected (Galán-Puchades 2020). Water and temperature are the major factors along

with geographical distribution that can inuence the Zoonotic heminths (Mas-Coma

2008). Brucellosis is caused by Brucella spp. transferred from animals to human

through infected meat and unpasteurized milk and other sources and is highly

affected by temperature. As reported, dry weather with increased temperature of

30°C can decrease the incidence of disease (Dadar 2020). Similarly, West Nile

Virus infections increased with an increase in temperature, while drought contrib-

utes 26% in prevalence (Smith 2020).

2.2.5 Waterborne Diseases

Aquatic pathogens of animal and human faecal origin may include bacteria, viruses,

and parasites. Also, some naturally occurring microbes can become pathogenic, e.g.

species of Vibrio (septicemia, diahorraea, and gastroenteritis), amoebae (encephali-

tis) Pseudomonas aeruginosa (infections of Ear and skin), and Legionella pneu-

mophila (Legionnaire’s disease) (WHO, Guidelines for drinking-water quality:

incorporating, 2008). Waterborne diseases include cholera, shigellosis, typhoid, etc.

Cholera is a bacterial disease and caused by Vibrio cholera. There is strong evidence

that cholera is affected by meteorological parameters (Fig.2.2) like high tempera-

ture and low precipitation can elevate the replication process of bacteria

(Asadgol 2019).

Cholera disease can also be caused during occupational (shing) and recreational

activities (Redshaw 2013). A systematic analysis on Vibrio spp. and Leptospira

spp., followed by E. coli, identied these microbes as commonly found pathogens

in the outbreaks of waterborne diseases after ooding, mostly in Asia (Alderman

2012; Ahern 2005). Flooding and heavy rainfall contribute to gastrointestinal ill-

nesses and contaminated water quality. There was a signicant rise in diarrhoeal

diseases among young children and the elderly after the 2007 Flooding in China

(Ding 2013). About 21,401 cases of diarrhoea were treated in the hospitals of

Bangladesh in August 2007, due to severe ooding (Nahar 2010). In 2010, diar-

rhoea was a principal reason of illness in Pakistan due to ooding accounting for

more than 17% of medical sessions in the worst affected area (WHO, Floods in

Pakistan-Health Cluster Bulletin No 12–16 August 2010 2010). Similarly, some

examples of rainfall impacts on waterborne diseases by poor water quality include

a case of waterborne outbreak of Campylobacter jejuni and Escherichia coli

O157:H7 in the Canadian town of Walkerton, which caused more than 2300 cases

of gastrointestinal illness, 65 hospitalizations, and 7 deaths. In this case, the drink-

ing water became polluted by livestock dung, following an intense rainfall

(O’Connor 2002); a substantial association between outbreaks of waterborne dis-

ease and excess rainfall. This study analysed 548 already reported outbreaks in the

United States from 1948 to 1994. The results showed that almost 51% of outbreaks

were preceded by heavy rainfall (Curriero 2001).

T. Ahmed et al.

More details on the infectious diseases related to climate change events are sum-

marized in Table2.1.

2.3 Remediation andControl ofID Related toCC

It is important to understand which ID is positively or negatively affected by

CC. Geographical distribution is important in understanding the impacts of CC on

IDs. In some regions, the incidence of IDs is lower by increasing meteorological

parameters, but in other regions, the prevalence and incidence of diseases are

increased by changing climate. Multidisciplinary and integrated approaches are

required to understand the mechanism, relationship with vector, host, and pathoge-

nicity, and deal with infections under changing climate (Mills 2010). Eco-

epidemiological methods can help in decreasing zoonotic diseases like Brucellosis

(Dadar 2020). Efciency in monitoring and generation of risk maps can be helpful

in controlling the VBDs (Fischer 2011). Preparation of a list of IDs which are

climate- sensitive, adaptation and mitigation strategies, emergency preparedness,

training of manpower, capacity building, developing testing kits, vaccines, develop-

ing models for projections, developing policies, and implementation of law and

enforcement are important in controlling the IDs (Semenza 2009; Filho 2008).

Improvements in sanitation, hygiene, and infrastructure are required to control IDs

along with awareness on how the IDs spread under changing climate (Filho 2008).

Use of remote sensing techniques for the detection of algal blooms for the improve-

ment of water quality is suggested. Similarly, for ID, molecular techniques to trail

contaminants are recommended (Rose 2001). Both operational research and human-

itarian aids are important including turning research into policies and their

Fig. 2.2 Monthly variation in the number of cholera cases and climate variables, 1998–2016

(Adapted from Asadgol 2019)

2 Infectious Diseases, Challenges, and Their Impacts on Human Health…

Table 2.1 Climate change events and their impacts on infectious disease

Climate

change event Type of disease Infectious disease Impacts References

Temperature Vector-borne

disease

Malaria Studies showed that

pathogens of malaria, i.e.

Plasmodium vivax and

Plasmodium falciparum,

develop below 15°C in

mosquitoes.

Snow (2003)

Dengue fever Increase in temperature

and humidity during rainy

season is associated with

increase in dengue virus

propagation in mosquitos,

contributing to the

outbreaks of dengue

haemorrhagic fever.

Zhang

(2008)

Zika virus Transmission of zika virus

increases at higher

temperature.

Winokur

(2020)

Leishmaniasis The distribution of

Phlebotomus papatasi in

Southwestern Asia is

dependent on temperature

and relative humidity

Karimi

(2014)

Lyme

borreliosis– LB

It is a tick-borne disease

and studies showed that

distribution of ticks in

Northern was associated

with very low temperature,

below −12°C.

Lindgren

(2006)

Waterborne

disease

Cholera Vibrio spp. showed an

increased growth rate

during the hot summers.

Colwell

(1996)

Skin infections, e.g.

cellulitis

Rainfall after long drought

increases the spread of

waterborne diseases.

Czachor

(1992)

Foodborne

diseases

Salmonellosis Rise in temperature in the

range between 7°C and

37°C increases the

reproduction rate of

salmonella bacteria.

D’Souza

(2004)

Campylobacteriosis It was observed that

warmer temperature

supports the growth of

Campylobacter spp. which

enhances the disease.

Kovats

(2005)

Airborne Allergy and asthma Allergy increases during

cold weather and pollen

season.

Damialis

(2019)

(continued)

T. Ahmed et al.

Table 2.1 (continued)

Climate

change event Type of disease Infectious disease Impacts References

Chickenpox Chickenpox increases at

tempterature 5–20°C.

Chen (2017)

Coronavirus Previous studies showed

that SARS-CoV-1 is

unstable at higher

temperature (above 38°C)

and higher humidity

(>95%).

Briz-Redón

(2020)

Tuberculosis Studies showed that spread

of tuberculosis increases at

low temperature, low

humidity, and low rainfall.

La Rosa G

(2013)

Zoonotic or

Anthroponosis

Ebola Studies showed that at

temperature above 27°C

transmission of Ebola

virus increases.

Kassie

Daouda

(2015)

Avian inuenza Cold temperature and low

relative humidity are

favourable to the spread of

inuenza virus.

Gilbert

(2008)

Giardiasis Studies showed that higher

temperature resulted in

increased death rate due to

Giardia.

Balderrama-

Carmona

(2017)

Flood Vector-borne

disease

Malaria Floods in Mozambique led

to spread of malaria,

typhoid, and cholera.

Epstein

(1999)

lymphatic lariasis There have been reported

increases in lymphatic

lariasis in different areas.

Nielsen

(2002)

Leptospirosis

diseases

Leptospirosis diseases

may also increase during

ooding in different areas.

Leal-

Castellanos

(2003)

Waterborne

disease

Cryptosporidium

infection.

Flood favours waterborne

disease transmission such

as Cryptosporidium

infection.

MacKenzie

(1994)

Drought Vector-borne

disease

hantavirus

pulmonary

syndrome (HPS)

Drought has been found to

be associated with

hantavirus pulmonary

syndrome (HPS).

Khasnis

(2005)

West Nile virus Increased West Nile virus

risks follow the drought.

Wang (2010)

(continued)

2 Infectious Diseases, Challenges, and Their Impacts on Human Health…

implantation are important (Small 2001). Global warming may have impacts on

water quality including WBDs/IDs, so more efcient tools or strategies are required

in the future, especially trained or skilled manpower (Levin 2002). Policies for

decarbonization should be devised to reduce global warming and CC impacts on

IDs and water quality. Inclusion of environmental perspectives into health assess-

ment and integrated approaches for surveillance are being suggested. Lack of qual-

ity data and its authenticity are important for processing of scientic models to

control IDs. Funding is the main requirement for all the data collection, modelling,

management, capacity building, and training purposes (Hess 2020). Establishment

of local early warning system for the prediction of health impacts by climate change

have been proposed (Wu 2016). Another study suggested the integrated surveillance

system, trans-border collaboration, and interdisciplinary research which can control

the disease burden caused by the IDs (Bhandari, Climate change and infectious

disease research in Nepal: are the available prerequisites supportive enough to

researchers?, 2020b). Due to less equipped and under-resourced laboratories in the

developing countries, they are more vulnerable to IDs. Hence, there is need to pro-

vide/generate funding for the high-performance equipment and qualied and trained

manpower to run the labs working for the diagnosis of the climate-sensitive dis-

eases. Similarly, international collaboration can boost the training of the manpower

and their deputation in the diagnostic laboratories is suggested. Similarly, another

study suggested the micro-stratication for malaria and other disease controlling

measures like use of mosquito nets, insect repellents, and fever checking not only at

borders, but also in the different districts and cities to control infectious diseases

including COVID-19, malaria, and other asymptomatic cases (Dhimal 2014).

Maintenance of health surveillance system and continuous efforts can provide sup-

port in achieving the goals.

Table 2.1 (continued)

Climate

change event Type of disease Infectious disease Impacts References

St. Louis

Encephalitis virus

The risk for transmission

of St. Louis Encephalitis

virus would increase,

during the droughts.

Shaman

(2002)

Chikungunya fever The Chikungunya fever

epidemic may be

associated with droughts.

Chretien

(2007)

Waterborne

disease

Diarrhoea Diarrhoeal diseases are

frequent during drought

especially in refugee

camps.

Epstein

(2001)

T. Ahmed et al.

2.4 Future Prospective andRole ofModelling onID

Modelling is important to understand the risk of infectious diseases in the future

under different climate scenarios. These models can be statistical, mathematical, or

climate change to understand the water quality and infectious diseases’ risks (Patz

2003). Empirical studies indicated that the global CC impacts on WBDs and VBDs

and is reported likely to increase with the increase in population and social inequali-

ties in developing countries and where the conditions are favourable (Fig. 2.3).

Different models are used to predict cases of dengue fever like ARIMA model

reported to be a good prediction model for a longer period as compared to other

models (Siriwan Wongkoon 2012; Luz 2008). Similarly, Articial Neural Networks

(ANNs) have been found effective to simulate the CC impacts on cholera to nd the

future trend of cholera outbreaks (Asadgol 2019). A study conducted to use the

spatial regression model to assess the distribution of IDs found that malaria, diar-

rhoea, and HAV infections are signicantly related to oods after controlling other

meteorological parameters (Gao 2016). Entomological models are used for the

assessment of mosquito abundance, growth status, and development, and the same

can be used for locusts.

Different models like MARA/ARMA model, container-inhabiting mosquito

simulation model (CIMSiM), CLIMEX model, Malaria-Potential-Occurrence-Zone

model, mathematical-biological model (simulation of malarial forecasts on the

basis of seasonal weather forecasts), classication and regression tree (CART), and

principal component analysis (PCA) for variability of cholera cases and dengue

simulation model are used for the control of malaria and dengue fever-related infec-

tious diseases (Patz 2003; Hoshen 2004; Islam 2009). A statistical model was used

and found effective to assess the impact of temperature and drought in the spread of

West Nile Virus disease. Similarly, scenario models are used to assess the scenario

under changing drought and temperature and suggested to apply for other diseases

(Smith 2020). The predicted population at risk by VBDs is shown in Fig.2.3.

2.5 Conclusion andRecommendations

Climate change brings both positive and negative impacts on the spread of IDs in

which geographic distribution and climate-specic conditions are important to

impact vector host relationship, life cycle, and specic disease. Hygienic condi-

tions, sanitation, and control of spread factors can help in controlling and decreasing

the impact and disease burden. It is important to study in detail the specic disease

in a specic geographic area and impacts of CC on the specic ID.It is not neces-

sary that disease in one area impacted by CC behaves in a similar way in other areas

and under different climates. Modelling studies can help in predicting the future

trends and impacts of IDs under similar conditions. Scenario and other models can

help in assessing the different scenarios under changing CC for the different IDs.

2 Infectious Diseases, Challenges, and Their Impacts on Human Health…

Capacity building and training in the lacking areas can help in improving the condi-

tions. The most important is the implementation of policies by using the peanut and

stick method, which can help in improving the existing conditions, especially in the

developing countries.

The following are the important recommendations:

1. Integrated approaches are important to address the IDs.

2. Preparedness in emergency is highly vital to tackle the IDs during disasters.

3. Mitigation strategies are necessary to cope with the IDs.

4. Eco-epidemiological approach to address spatiotemporal dynamics and infec-

tious diseases.

Fig. 2.3 Population at risk of VBDs in 1990 (a) and 2085 (b) by Regression Model. (Simon

Hales 2002)

T. Ahmed et al.

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Chapter 3

Marble Dust asanEnvironmental

andOccupational Hazard

SalmaKhalid, MohsinaHaq, andZia-Ul-AinSabiha

Abstract With the increase in urbanization over the last century, mankind is enjoy-

ing sophisticated modern architecture. The use of different types of naturally occur-

ring and synthetic materials is becoming very popular at industrial and domestic

levels. Marble being a natural metamorphic rock is commonly used by our society

because of its beautiful colors, easy maintenance, and lifelong durability. The other

side of the picture of marble use is very ugly because of the environmental and

health hazards that are caused by the marble industry.

Marble dust is produced by marble factories during the renement and process-

ing of raw marble into glass polished tiles, slabs, and tabletops. The dust produced

during this process is added as a pollutant to the environment or is inhaled in high

concentrations by the workers via the respiratory tract, thus making them more

prone to chronic pulmonary diseases. These particles being highly irritant and aller-

gic cause respiratory disease affecting both upper and lower respiratory tracts ulti-

mately leading to decreased respiratory functions. Different literature showed that

workers and residents living in areas adjacent to marble/granite factories are prone

to lung disease, e. g., silicosis.

Also, dry cough and shortness of breath are the commonest complains with

which these workers present. In spite of the latest advancements in medical eld,

only supportive treatment (antihistamine, Montelukast, and bronchodilators) can be

given to these patients if preventive measures are not taken on time.

S. Khalid (*)

Prime Institute of Public Health, Prime Foundation, Riphah International University,

Islamabad, Pakistan

M. Haq

Department of Pathology (Microbiology), Peshawar Medical College, Prime Foundation,

Riphah International University, Islamabad, Pakistan

Zia-Ul-Ain Sabiha

Department of Community Health Sciences, Peshawar Medical College, Prime Foundation,

Riphah International University, Islamabad, Pakistan

International Agency for Research on Cancer (IARC) classied marble dust,

heavy metals, and crystalline silica as carcinogens in 1997. International Labor

organization (1919) protects workers’ right and thus demands effective prevention

techniques, safe working places, and awareness programs regarding commonly

addressed health issue for the workers working in industries. If effective treatment

is not given to workers who have developed the above-mentioned health issues on

the right time, they might develop an end-stage lung disease (chronic lung disease/

lung cancer). Different epidemiological studies show that workers exposed to mar-

ble dust have an increased risk of developing chronic asthma, chronic bronchitis,

and impaired lung functions and even lung cancer.

Marble dust, other than having serious health issues, can have a considerable

economic impact as well; like decrease in working productivity, increase in health

expenditure per person, and increase in mortality and morbidity. Health being the

basic right of man, strict preventive measures should be taken for and by these

workers as they constitute a substantial number of chronically affected patients of

respiratory tract.

3.1 Introduction

With the increase in urbanization over the last century, mankind is enjoying sophis-

ticated modern architecture. The use of different types of naturally occurring and

synthetic materials is becoming very popular at industrial and domestic levels.

Marble being a natural metamorphic rock is commonly used by our society because

of its beautiful colors, easy maintenance, and lifelong durability. Today, half of the

world’s marble extraction is mostly from six countries; Italy, China, India, Spain,

Egypt, and Turkey. However, marble is produced by many other countries too

(Ciccu etal. 2005).

The other side of the picture of marble use is very ugly because of the environ-

mental and health hazards that are caused by the marble industry (Corinaldesi etal.

2010). Mechanical breakdown and other procedures of marble dealing have not

only considerable effects on the environment but also on workers’ health and safety

and the communities residing in nearby villages. Cumulative impacts include lack

of environmental protection, rehabilitation measures, community engagement, and

inappropriate and unsafe operational procedures (Bui et al. 2017; Gorman and

Dzombak 2018; Nuong et al. 2011). Well, in fact, the recognized truth is that the

marble industry provides much-needed opportunities for employment to the poorest

families of the nearby communities (Paracha 2009).

This particular industry in its present state is confronting different challenges

along with the devastating conditions of the worker like fatal injury including rock

fall, res, explosions, mobile equipment accidents, falls from height, gas explosion,

suffocation, and entrapment. Less common but recognized causes of fatal injury

include ooding of underground workings, wet-ll release from collapsed bulk-

heads, and air blast from block caving failure (Donoghue 2004). In addition to this,

S. Khalid et al.

workers are also exposed to toxic chemicals and dust that take a toll on their health

(Ashraf and Cawood 2017). There is no mechanism to provide compensation to ail-

ing or injured mine workers, to the families of those killed on the job, or to rural

communities affected by mining operations (Azad etal. 2013). Linked to these

issues, the International Labor Organization (ILO) estimated that about 2.3 million

people die due to occupational accidents and occupational diseases, 317 million

suffer from serious nonfatal occupational injuries, and 160 million suffer from

occupational illnesses and most of them belong to rural areas in less developed

countries (Takala etal. 2014).

Mechanical breakdown like grinding, cutting, drilling, crushing, explosion, or

strong friction results in emission of dust. All over the world, the marble industry is

considered a high waste-producing industry. It is estimated that round about 70% of

the precious marble is wasted as marble dust during the procedures of mining and

polishing. This wasted marble is dumped in roads, rivers, and agricultural elds and

causes environmental pollution and generation of marble dust (El-Gammal etal.

2011; Gazi et al. 2012). This polluted environment directly or indirectly affects

health by polluting the air quality (Nakao etal. 2018). The dust that penetrates

inside the lungs is particulate matter (PM), and usually 15–20% of cases of common

chronic obstructive pulmonary disease (COPD) are linked with prolonged occupa-

tional exposure to dust, vapors, gases, and fumes over a long period of time (Azizah

2019; Borup et al. 2017; Faisal and Susanto 2017; Sudrajad and Azizah 2016)

(Fig.3.1).

The particulate matter (PM2,5) enters the alveoli and causes inammation and

reduces lung function. The maximum harmful exposure to particulate matter is

measured (10 mg/m3) for 8h. The dust particulates are divided into two categories,

namely PM10 and PM2.5 (Khoiroh 2020) (Table 3.1). Dust clouds in a working place

Fig. 3.1 Exposure of workers to marble dust as occupational hazard

3 Marble Dust asanEnvironmental andOccupational Hazard

reduce visibility and deposited dust may cause slipperiness, increase the risk of

accidents, and lead to degradation of materials and environmental pollution due to

its deposition on various structures, machinery, and equipment (Park 2005).

In addition, ne dust covers the ground and prevents rainwater from percolating

into the soil. Marble dust also destroys plants by covering their leaves and reducing

exposure to sunlight which indirectly affect the health (Noreen etal. 2019).

To avoid the occupational factors and conditions hazardous to the health and

safety of workers, such as occupational diseases and workplace accidents, the pro-

tection and promotion of the health of workers are necessary. Nowadays, it is con-

sidered an occupational health multidisciplinary and comprehensive approach that

includes general health, the worker’s physical, mental, and social well-being, and

personal development (Humans and Cancer 2006).

3.1.1 Potential Hazards fromMarble Quarrying toWaste

Marble dust is produced from marble quarrying by cutting of rocks to marble facto-

ries during renement and processing of raw marble into glass polished tiles, slabs,

and tabletops. The dust produced during this process is added as a pollutant to the

environment or is inhaled in high concentrations by the workers via the respiratory

tract, thus making them more prone to chronic pulmonary diseases (Rajgor and

Pitroda 2013). These particles being highly irritant and allergic cause respiratory

disease affecting both upper and lower respiratory tracts ultimately leading to

decreased respiratory functions (Chen etal. 2012). Different literature showed that

workers and residents living in areas adjacent to marble/granite factories are prone

to lung disease, e.g., silicosis (Nij etal. 2003). People with silicosis have a higher

risk of developing tuberculosis (Álvarez etal. 2015). Similarly, various epidemio-

logical studies indicate that workers exposed to marble dust have an increased risk

Table 3.1 Exposure to dust concentration and rate of intake in different media

Variable

Exposure concentration in

different parameters Rate of intake

Concentration in media Mg/l (Water) l/hour, l/day

mg/m3 (Air) Mg/inhaled per minute or

per hour

Mg/100cm2 (Contaminated

surface)

Mg/kg body weight ingested

per day or per meal

Quantity available for

absorption (Potential dose)

Mg inhaled, total

Mg inhaled/kg body weight

Mg ingested total

Mg ingested per kg body

weight

Mg-on skin total

Mg/cm2 skin area

S. Khalid et al.

of occupational asthma, impairment of lung function, chronic bronchitis, renal

impairment, and nasal inammation (Angotzi etal. 2005; Armaeni and Widajati

2016; Leikin etal. 2009; Morton and Dunnette 1994; Pulungan 2018). Workers are

exposed to marble dust, heavy metals, and crystalline silica, which are classied as

known carcinogens by the International Agency for Research on Cancer (IARC) in

1997 (Golbabaei etal. 2004; Scarselli etal. 2008; Yaghi and Abdul-Wahab 2003;

Yassin etal. 2005). Marble dust is abrasive in nature and causes allergies to the skin

(Scleroderma) and eye irritation. Workers with these diseases can go undiagnosed

and untreated, and worst of all, effective preventive measures are not taken because

of a lack of awareness of the problem. Also, dry cough and shortness of breath are

the commonest complains these workers present. In spite of the latest advancements

in medical eld, only supportive treatment (antihistamine, Montelukast and bron-

chodilators) can be given to these patients if preventive measures are not taken

on time.

3.1.2 Exposure toMarble Dust Concentration

Different processes involved in marble quarrying to marble workshop produce mar-

ble dust cloud into the atmosphere. Occupationally, these workers are exposed to

high content of dust in their workplace during their routine working hours (Bickis

1998), which is known as "primary airborne dust" (WHO 1999). This dust com-

prises of particle sizes in the range of 1–400μm, and particles larger than 100 μm

easily settle down near the source. All these dust particles are divided into three size

ranges, i.e., larger than 20μm are termed large particles and 20–1μm and less than

1μm as ne and ultrane particles, respectively (Leonard 1979). The particle size

of a dust cloud may be different from that of the powder originated from its source.

The determinants include the amount (mass), distribution of particle size, falling

height from parental rock, material ow and moisture content and air movement in

the workplace, etc. (Bickis 1998). Exposure of an individual to the workplace and

their integration with the exposed media, dust concentration, and in relation to time

can be calculated by the following equation.

3.1.3 Calculation ofExposure

Ej Cj t







Where

Ej=exposure of the individual

ʃ=integrated with exposure media

3 Marble Dust asanEnvironmental andOccupational Hazard

C=concentration of marble dust

d=exposure dose (mg/kg/day)

t=for a time period (Detels etal. 2011)

The main crystalline composition of minerals present in marble dust includes

magnesium calcium bis (carbonate) (MgCa (CO3)2) and calcium magnesium alumi-

num catena- alumosilicate (Demirel 2010).

3.1.4 Inhalable andRespirable Marble Dust

The US Environmental Protection Agency (EPA) dened respirable dust as particu-

late matter less than 10μm in diameter. Respirable dust enters into the lungs and

causes pneumoconiosis in workers on prolonged exposure. In the working place, the

quality of air must be maintained by keeping the concentration of respirable dust

2mg/m3 (Speight 2020) (Table3.1). Marble dust other than having serious health

issues can have a considerable economic impact as well, like decrease in working

productivity, increase in health expenditure per person, and increase in mortality

and morbidity. Health being the basic right of man, strict preventive measures

should be taken for and by these workers as they constitute a substantial number of

chronically affected patients of the respiratory tract.

3.2 Health Hazards atWorkplace andintheSurrounding

Exposure to dust has always remained a known cause of occupational lung diseases.

Different regulatory authorities have always tried to produce and maintain occupa-

tional guidelines and standards to minimize the exposure of workers to such inhal-

able particles that can ultimately result in end-stage lung conditions.

There are different routes through which workers are exposed to these occupa-

tional hazards. These routes are percutaneous routes, respiratory routes, and oral

routes (Davidson and Davidson 1984; Gray and Harrison 2004; WHO 1999).

The most common health hazards at workplace and in the surroundings are as

follows:

3.2.1 Silicosis

Overexposure to free crystalline silica’s dust leads to a brotic lung disease that is

called silicosis. This is a serious lung condition, and if not treated on time, it can

prove to be fatal. It is a slow but irreversible, progressive, and fatal condition of the

S. Khalid et al.

lungs. The severity of the disease depends upon the exposure time and the amount

of free crystalline silica that is inhaled and eventually gets deposited in the alveolar

region (exchange of pure oxygen takes place).

Depending upon the duration of exposure, silicosis is divided into two major

types, acute silicosis and chronic silicosis.

3.2.1.1 Acute Silicosis

Acute silicosis occurs after a few months to a maximum two years of exposure to

silica’s high concentration. The patient experiences difculties in breathing (dys-

pnea), which later on may become very severe. This respiratory insufciency is the

result of brosis and emphysema which ultimately causes cor pulmonale and leads

to death.

3.2.1.2 Chronic Silicosis

In chronic silicosis, symptoms show up after a decade after the person is exposed to

low or moderate amounts of silica. The symptoms might be mild at rst, and then

with the passage of time, they will slowly worsen (Davidson and Davidson 1984;

Gray and Harrison 2004; Richards 2003; WHO 1999).

3.2.2 Chronic Obstructive Pulmonary Disease (COPD)

Chronic obstructive pulmonary disease is characterized by poor airow and long-

standing breathing disorder. COPD mostly presents with dyspnea, shortness of

breath, and productive cough. COPD is a progressive disorder and it worsens with

the passage of time slowly affecting the quality of life. A person who suffers from

COPD ultimately becomes so crippled that he/she cannot carry out his/her daily

routine work easily because of difculty in breathing. Emphysema and chronic

bronchitis are now collectively named under the heading “COPD”

In developing countries, COPD is also the result of occupational health hazards.

Prolonged exposure causes an inammatory response in the lungs that leads to the

narrowing of air passages and ultimately affecting the normal architecture of lung

parenchymal tissue. This leads to poor exchange of gases inside the lung tissue, thus

affecting the breathing of a person. Workplace exposure is believed to be the cause

in 10–20% of the cases. Some industries producing high levels of dust like coal

mines, cotton textile, silica, and berglass can lead to COPD (Davidson and

Davidson 1984; Gray and Harrison 2004; Richards 2003; WHO 1999).

3 Marble Dust asanEnvironmental andOccupational Hazard

3.2.3 Pneumoconiosis

Pneumoconiosis is dened as “the accumulation of dust in the lungs and the tissue’s

reaction to its presence”. It is basically caused by the dust inhaled in the workplace;

that is why it is called occupational lung disease. The severity of Pneumoconiosis

depends on the amount of dust particles inhaled. The most common type of it is

called “miner lung”. Other forms of pneumoconiosis depend on inhalation of exces-

sive amounts of iron oxide resulting in siderosis, inhalation of tiny particles causing

stannosis, inhalation of beryllium causing berylliosis, talc, graphite, and mica

(Davidson and Davidson 1984; Gray and Harrison 2004; Richards 2003; WHO 1999).

3.2.4 Lung Carcinoma

Many dust particles such as silica, asbestos, wood dust, and radioactive particles are

known as carcinogens, leading to lung cancer, mesothelioma, nasal cancers, and

blood carcinomas. Some particles, like those of silica, asbestos, and radioactive

particles, get deposited in the lungs, causing cancer of the lung tissue. Carcinomas

due to asbestos (mesothelioma) have been linked to occupations such as that of

building maintenance, ships maintenance, etc.

The establishment of carcinoma depends upon the exposure time of workers to

certain chemicals. The minimum the time between exposures, the minimum is the

chance of development of Ca if proper preventive measures are taken (Davidson and

Davidson 1984; Gray and Harrison 2004; Richards 2003; WHO 1999).

3.2.5 Skin Disorders

Skin being the largest organ of the body helps us to protect the inside of our body

from the harsh environmental factors. Occupational skin disorders are caused when

there is direct contact of a worker with one or more hazardous substances. Workers

can come in contact with such substances via handling tools, dipping/immersion of

objects or substances in chemicals, etc. These procedures lead to disruption of the

normal barrier function of the skin.

The commonest occupational skin disorders include contact dermatitis, folliculi-

tis, skin infections, and skin cancers.

The most common side effects are seen in hands and arms as they are most fre-

quently in contact with chemicals in working areas. The commonest of all the

above-mentioned conditions is contact dermatitis, which clinically appears as

inammation of skin, redness, dryness, blistering, scalding-like appearance, and

starts to bleeds.

S. Khalid et al.

Infection of hair follicles means folliculitis. This condition is common in those

workers who are exposed to minerals and soluble oils. Skin cancers are common in

workers who deal in UV radiation industries, nuclear power plants, and industries

dealing with tar products (Davidson and Davidson 1984; Gray and Harrison 2004;

Richards 2003; WHO 1999).

3.2.6 Ophthalmic Disorders

Occupational ophthalmic diseases have a long latent period. Most of them cannot be

treated, but all of them are preventable. Occupational eye illness can be divided into:

chemical injuries; radiation injuries; electrical injuries; heat injuries; etc.

In industries, workers deal with different kinds of chemicals, especially liquids

and gases. These are of major concern causing injuries to eyes, for example, if liquid

chemicals splash into a worker’s eyes giving him acidic/basic burns, it ultimately

leads to the scarring of cornea if not treated on time. Same way, fumes, gases, and

vapors can also damage the eyes.

Different forms of radiations, for example, UV radiations, infrared radiations,

and high source visible light, can also damage the sensitive area of the eye that is

called Retina. In industries like glassblowing and steel making, workers are exposed

to high intensity of light which can cause irreparable damage.

Electrical cataracts have been reported to be a cause of electrical injuries.

Corneal tissue scaring and corneal damage are common in workers who deal

with heat as a source of energy in industries (Davidson and Davidson 1984; Gray

and Harrison 2004; Richards 2003; WHO 1999).

3.2.7 Occupational Renal Disorders

There are certain industries that have direct impact on renal functions of the workers

working in them, for example, industries of mercury, cadmium, lead, and silica.

These industries produce nephro toxins (those chemicals that affect renal functions

via direct toxic action).

The most common occupational renal disorders are acute renal dysfunction and

chronic renal insufciency.

Acute renal dysfunction is of sudden onset and develops hours to days after the

exposure to a specic toxin. It causes the necrosis of tubules and is also called acute

tubular necrosis ATN. It is characterized by decreased output of urine (less than

500ml/day). On microscopic examination of urine, there are renal tubular cells,

cellular casts, and little or no proteins.

3 Marble Dust asanEnvironmental andOccupational Hazard

Chronic renal insufciency develops slowly over time. Symptoms develop

slowly and include nausea, vomiting, loss of appetite, stomatitis, nocturia, and sei-

zures. However, nal diagnosis is based on renal biopsy (Davidson and Davidson

1984; Gray and Harrison 2004; Richards 2003; WHO 1999).

3.3 Health Hazards DuetoInappropriate Management

The poor working conditions, not only at mines but also at workshops, increase the

work-related issues and also make a big chunk of the population vulnerable to occu-

pational diseases and disorders and also increase government budget on health-

related issues (Jiskani etal. 2020).

Worldwide, the prevailing key issues in the marble sector are:

• Use of old techniques/machinery

• Financial constraints

• Institution mismanagement

• Lack of experts and technical knowledge

• Lack of workers’ safety measures, etc.

The prevailing issues call for a great attention of the government as well as the

stakeholders towards health protection of the workers, provision of better working

environment, (Jiskani etal. 2019) workers training, and implementation of strict

guidelines.

3.4 Hazard Prevention andControl

Hazard prevention and safety measures should be taken into account in the work-

place either in the quarry or in the marble workshops with increased emphasis on

risk management. The risk management not only benets in a healthier and happier

workforce and increased productivity but also protects the health of the workers and

promotes the economic well-being of the country. It requires the involvement and

cooperation of management and administrative support, workforce with technical

knowledge and experience, occupational health professionals, allocation of suitable

nancial resources, and political will. A multidisciplinary approach should design,

implement, and maintain dust emission and control strategies to prevent health haz-

ards and occupational disease at a workplace. The impact of these concerns over the

whole eld of occupational health and safety has been considered in an ILO publi-

cation (Brune 1997). Several measures for the prevention of health hazards and

occupational diseases are grouped under three main headings: medical, engineer-

ing, and legislative.

S. Khalid et al.

3.4.1 Medical Measures

It is the basic requirement of occupational health. The implementation of medical

measures includes periodical examination and clinical evaluation should be carried

out at least once a year. In addition to workers’ health history and physical examina-

tion, specic laboratory tests must be carried out every one or two years, such as

spirometry and chest radiography in quarrymen exposed to dust as well as those

exposed to noise in marble processing. In preplacement examination, the fresh can-

didate may totally be rejected or may be given a job on the basis of a thorough

physical, biological, and radiological examinations. Special test for endemic dis-

ease and medical history of worker having anemia, hyper tension, kidney disease,

family history like asthma, skin bladder disorders, occupational history, and social

history (exposure if any other) must be considered before induction. First aid ser-

vices must be provided at work in case of accident or any causality. There should be

provision of medical as well as immunization services and health insurance schemes

for workers and their families. Periodic inspection of working environment should

be carried out for checking temperature, lighting, ventilation, humidity, noise, air

pollution, and sanitation. Occupational physician should be familiar with the raw

material processes and products manufactured and dust produced at workplace and

adverse health consequences. Also, it is important to maintain the workers’ health

and disability record too. Arrange health education and counselling programs for

workers to reinforce them to use PPE (masks, gloves, and goggles) in workplace to

protect their respiratory airways and lungs (Angotzi etal. 2005; Park 2005).

3.4.2 Engineering Measures

The other most signicant measures for reducing health hazards in the marble

industry are appropriate engineering procedures, because worldwide, this industry

is known as the most labor-intensive industry. There should be adequate building

design for industry, good housekeeping to boost the morale of the worker, and gen-

eral ventilation and for dust, which settle down on the machinery, oor, racks, and

beams should be promptly removed by vacuum cleaner or by wetting agent. The wet

method should be tried to combat dust with regular water spray as moisture in pro-

cesses of grinding, sieving, and mixing. Hood should be used for suction of dust,

fumes, and gases into the collecting units. Mask, apron, gloves, respirator, and other

protective equipment should be regularly used and general hygiene should be main-

tained. The workers should be educated about the type of respirator to use and when

and how to use. For protection against noise pollution and other workplace factors,

air plugs, ear muffs, helmets, safety shoes, gumboots, barrier creams, screen, and

goggles should be reinforced and the worker should be trained for the appropriate

use of the protective devices. The good machined plant will play a positive role in

reducing the hazards of the contact with the harmful substances to the fullest

3 Marble Dust asanEnvironmental andOccupational Hazard

possible extent. Dermatitis can be prevented if hand mixing is replaced by good

mechanical devices. Grinding machine can be completely enclosed and combined

with exhaust ventilation. Further research and periodical environmental surveys

should be carried to determine whether the dust and other gases escaping in the

atmosphere are within the permissible limits or not (Park 2005).

3.4.3 Legislation

Many countries around the world have comprehensive occupational health legisla-

tions, like the “Occupational Safety and Health Act (1970) legislation in the United

States. In 1974, a regulation was enacted in the United Kingdom, “Health and

Safety at Work Act,” and further, the European Union adopted a policy in 1989 on

the “Fundamental Social Rights of the Workers”. The main goal of occupational

health legislation is to ensure a safe and healthy working environment along with

strong emphasis on primary prevention of health hazards. Proper implementation of

legislation develops and promotes a positive social culture and enhances smooth

operations and increases the productivity of the working environment. Different

countries have different occupational safety and health practices such as legislation,

guideline, enforcement, and incentives. Some nations adopted a pooling system and

some have health and safety insurance system for their workers. For instance, some

member states in the European Union promote Occupational Safety and Health

(OSH) programs by providing grants and subsidies and tax system incentives for

compliance (Elsler 2007; Esler etal. 2010). But signicant variations were observed

in compliance of occupational safety and health between countries, economic fac-

tors, and sizes of enterprise because the number of fatalities is more in the develop-

ing countries as compared to developed countries (World Bank 1995).

3.5 Conclusion

International Agency for Research on Cancer (IARC) classied marble dust, heavy

metals, and crystalline silica as carcinogens in 1997. International Labor organiza-

tion (1919) protects workers’ right and thus demands effective prevention tech-

niques, safe working places, and awareness programs regarding commonly

addressed health issues for the workers working in industries. If effective treatment

is not given to workers who have developed the above-mentioned health issues at

the right time, they might develop an end-stage lung disease (chronic lung disease/

lung cancer). Different epidemiological studies show that workers exposed to mar-

ble dust have an increased risk of developing chronic asthma, chronic bronchitis,

and impaired lung functions and even lung cancer. Marble dust other than having

serious health issues can have a considerable economic impact as well; like decrease

in working productivity, increase in health expenditure per person, and increase in

S. Khalid et al.

mortality and morbidity. Health being the basic right of man, strict preventive mea-

sures should be taken for and by these workers as they constitute a substantial num-

ber of chronically affected patients of the respiratory tract.

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53© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022

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Chapter 4

Environmental Degradation

andMicro- pollutants inLight

ofEnvironmental Laws

FurqanMahmudButt, UmairBinNisar, andToqeerAhmed

Abstract Environment is everything surrounding human beings. Biotic and abiotic

contributors of environment affect natural, build, and social aspects of human

beings. For healthy livelihood, human beings are dependent on environment. The

increase in population, urbanization, and industrialization is having severe effect on

world environment. Climate change further aggravates the situation. Despite several

laws drafted for the awareness and reduction of environmental degradation, no pro-

found results have been obtained. Environmental issues induce several negative

externalities and contribute to market failure, thus affecting economic growth; this

becomes a serious problem in developing and underdeveloped countries where

there are no strong rules for reducing these negative externalities. Pakistan is ranked

fth among the most affected countries in terms of climate change despite the con-

tribution of less than 01% in emissions. The air quality index of Pakistan is getting

poor with every passing day; Lahore and Faisalabad were ranked as most polluted

cities all over the world in terms of air quality index. The government of Pakistan

has taken some time to realize environmental degradation and has initiated projects

like billion tree tsunami and air quality laws to address climate change and environ-

mental degradation.

F. M. Butt

Department of Meteorology, COMSATS University Islamabad, Islamabad, Pakistan

e-mail: furqan.mahmud@comsats.edu.pk

U. B. Nisar (*) · T. Ahmed

Center for Climate Research and Development, COMSATS University Islamabad,

Islamabad, Pakistan

e-mail: umair.nisar@comsats.edu.pk; toqeer.ahmed@comsats.edu.pk

4.1 Pollution andEnvironment

Pollution is addition of harmful chemicals/contaminants into the atmosphere which

can cause severe damage to health and the environment(Nathanson 2015), whereas

the environment is everything that surrounds us and comprises both biotic and abi-

otic components. These components represent both living and nonliving things in

ecosystems. These components represent a relationship between producers, con-

sumers, and decomposers that relay on uctuations of temperature air and sunlight.

With increase in population, urbanization, and industrial developments, the environ-

ment is severely affected (Nisar etal. 2018); most of the pollution induced in the

environment is the result of automobiles, industrial sector, and solid wastes (Ekins

2010). World population has drastically increased over the years and if it continu-

ously exceeds at the same pace, it will cause severe loss to environment (Hamrick

2004), as population increase demands utilization of more resources thus resulting

in overburden on natural resources and increase in environmental degradation

(Behrens etal. 2007). World Health Organization (WHO) has estimated that about

4.2 million children die due to ground-level air pollution, causing heart disease,

lung cancer, stroke, and acute respiratory infections (WHO 2018). Pollution is

unequally induced by some prominent countries in the world, but price is paid by

every living organism on earth. Despite the steps taken after Paris accord (2016), the

CO2 emissions are continuously increasing, which are causing an increase in tem-

peratures. With China being the largest CO2 emitter, it accounts for more than one-

quarter of emissions, followed by the USA with 15% emissions, the European

Union (EU-28) with 10%, followed by India and Russia with 7% and 5%, respec-

tively (Lelieveld etal. 2019). A regular passenger car emits around 4.6 metric tons

of pollutants each year (Masiol etal. 2014). The average gasoline vehicle on the

road has a fuel efciency of about 22 miles per gallon, with an average annual travel

distance of about 11,500 miles (this statement does not apply to developing nations,

where average vehicle fuel usage is between 10 and 15 miles per km). At this pro-

portion, every gallon of fuel burned produces about 8,887 grammes of CO2 (Pachauri

etal. 2014). Annual total CO2 emissions by world region are shown in Fig.4.1.

Increase in population has severe effect on waste generation which plays a vital

role in waste generation. The world annually generates 2.01 billion tons of munici-

pal solid waste, out of which 33% is not managed in environmentally friendly man-

ner. Waste generation by single individual worldwide is about 0.74 kg per day

ranging from 0.11 to 4.54 kg. The future projection portrays the generation of

wastes could go up to 3.40 billion tons annually, which shows a drastic increase

from 2.01 billion tons today (Kaza et al. 2018). Share of global population and

municipal solid waste for G20 countries has been shown in Fig.4.2.

The situation gets worse in developing countries, especially in the SAARC coun-

tries where population is increasing rapidly and resources are overutilized, and as a

result, pollution is severely affecting the environment (Hasnat etal. 2018).

The global cost of air pollution caused by fossil fuels in South Asia is $8 billion

a day (Liu et al. 2015), or roughly 3.3% of the entire world’s economic output

F. M. Butt et al.

(CREA and Greenpeace Southeast Asia report). Pakistan is one of the leading coun-

tries in Southeast Asia; despite the environmental laws, the implementation faces a

big problem.

Presently, several environment-related laws such as pesticide control, motor

vehicles emission’s regulation, and control of industrial pollution through Pakistan

Environment Protection Ordinance 1983 exist. However, these laws are not being

implemented fully and effectively.

Fig. 4.1 Annual total CO2 emissions by world region. (Ritchie and Roser 2017)

Fig. 4.2 Showing share of global population and municipal solid waste for G20 countries. (Ritchie

and Roser 2017)

4 Environmental Degradation andMicro-pollutants inLight ofEnvironmental Laws

4.2 Micro-pollutants andEnvironment

The phrase “micro-pollutants” refers to various chemicals found in trace concentra-

tions in the water-soil-air matrix, ranging from micrograms to picograms per liter,

and emphasizes the substances’ small concentrations range. Micro-pollutants

include pharmaceuticals, cosmetics, synthetic musk, industrial chemical substances,

pests, and disinfectants. Agricultural and nonagricultural sources release these pol-

lutants into the water supply (Antakyali etal. 2015). Micro-pollutants are anthropo-

genic contaminants that appear in the marine ecosystem well above a (potential)

normal background level because of human activities, but at trace levels -(Stamm

etal. 2016). As a result, micro contaminants are characterized by their anthropo-

genic origin and low concentration presence, and thousands of chemicals fall into

this group (Schwarzenbach etal. 2006). Ice covers more than 70% of the earth’s

surface, with 97.2% contained in oceans, 2.15% in ice sheets and glaciers, with just

0.65% fresh water available for use. Water is used in agriculture, industries, house-

holds, and in every aspect of life (Lutgens etal. 2006).

Around onefth of the planet’s population lack access to clean drinking water,

and two-fths suffer from unsanitary living conditions (WWAP 2003). Waterborne

pathogens kill over 2 million people per year, the majority of whom are children

under the age of ve. The growing chemical contamination of surface and ground-

waters, which has relatively unknown long-term consequences on marine life and

human health, could easily contribute to a similar or even larger crisis. More than a

third of the world’s clean freshwater is used for farming, commercial, and domestic

uses, and most of these operations pollute the water with a variety of synthetic and

geogenic compounds. As a result, it should come as no surprise that chemical con-

tamination of aquatic environments has become a signicant public issue in almost

every nation (Schwarzenbach etal. 2006).

The municipal drainage scheme and dispersed sources such as irrigation provide

input to the aquatic ecosystem. Persistent substances can move through the waste-

water treatment plant (WWTP) without being broken down. In addition, input of

easily degradable pollutants happens by out-of-date WWTPs and ood water or

mixed sewage overows on a regular basis. Micro-pollutants may accumulate along

the strip or in lakes if many WWTPs drain into the same water body. Micro-

pollutants from urban runoff can contaminate groundwater used for drinking water

through inltration of polluted surface water (Gälli etal. 2009). Industry and com-

munities use approximately 10% of the commonly available water, resulting in a

current of wastewater that drains or makes its way into rivers, wetlands, reservoirs,

or coastal seas (WWAP 2003).

Various chemical compounds of different proportions can be found in these

wastewaters. Around 300 million tons of articial chemicals used in commercial

and consumer goods end up in natural waters every year (Schwarzenbach etal.

2006). Agricultural sector, which consumes 140 million tons of fertilizer as well as

several million tons of chemicals per year, contributes to additional problems related

to water pollution (FAO 2006). For example, in the European Union, there are over

F. M. Butt et al.

100,000 identied chemical compounds, among which 30,000–70,000 are used on

a regular basis (EINECS, European Inventory of Existing Chemical Substances).

Another signicant cause of water pollution is the consumption of 0.4 million tons

of oil and diesel components because of accidental spills. The inltration of salty

water into reservoirs due to aquifer overexploitation; the human-driven mobiliza-

tion of naturally occurring geogenic hazardous chemicals, such as heavy metals and

metalloids; and the biological development of pesticides and malodorous com-

pounds are all notable causes of pollution (Schwarzenbach etal. 2006).

To date, there is a scarcity of a successful and long-term global plan to combat

this pervasive and still unnoticed contamination of marine ecosystems. In highly

developed nations, source controls and technological infrastructure, such as waste-

water treatment plants, serve as partial hurdles, but signicant obstacles remain

(Schwarzenbach etal. 2006). The source, action, and management of the limited

number of macro-pollutants found at μg/liter to mg/liter concentrations, such as

acids, salts, nutrients, and natural organic matter, are relatively well-understood:

Increased primary productivity, oxygen loss, and harmful algal blooms will all

result from high nutrient loads. Predicting environmental responses, optimizing

treatment technologies, and developing coordinated policies at the size of river

basins are all problems in such situations (Mengis etal. 1997; Jackson etal. 2001).

Several investigations in Europe and North America have recently conrmed the

detection of these “micro-pollutants” in wastewater, surface water, ground water,

and drinking water (Ternes 1998; Daughton and Ternes 1999; Daughton and Jones-

Lepp 2001; Heberer 2002; Kolpin etal. 2002; Calamari etal. 2003; Frick and Zaugg

2003; Boxall etal. 2004; Metcalfe etal. 2004; Ternes etal. 2004; Glassmeyer etal.

2005; Sedlak et al. 2005; Loraine and Pettigrove 2006). The quantities of these

substances in surface waters were as low as a few micrograms per liter. Pollutants

were found in ground water and drinking water at levels as low as one microgram

per liter. Eventually, there are fears that other pharmaceuticals intended for specic

biological causes could be harmful for the environment as well (Ternes etal2004).

For the contraceptive 17α-ethinylestradiol (EE2) and the antiphlogistic diclofenac,

respectively, estrogenic effects and renal alterations at environmental concentration

levels have already been published (Routledge etal. 1998; Triebskorn etal. 2004).

It has been highlighted and conrmed that residues from these micro-pollutants are

likely to cause renal failure in vultures, resulting in a drastic reduction of the vulture

population in Pakistan (by more than 95%) (Oaks etal. 2004).

Water, as we all know, is necessary for human socioeconomic activities. However,

owing to overexploitation of water resources and deforestation, stresses on the water

system have increased, posing a threat to human health and long-term socioeco-

nomic stability (Vörösmarty etal. 2010; Shevah 2014). This dire situation necessi-

tates elucidating the relationships between the water ecosystem and socioeconomic

processes, as well as using appropriate water environment management instruments

to deter water environmental destruction and promote socioeconomic growth that is

consistent with the water environment’s viability. As a result, complete awareness

of the social, economic, and environmental settings is needed for both water quality

management and the supply and demand balancing of water supplies (Yang et al.

4 Environmental Degradation andMicro-pollutants inLight ofEnvironmental Laws

2015). Evaluating the inuence of micro-pollutants in water bodies is a daunting

challenge that necessitates enhanced analytical and modelling techniques to inves-

tigate the distribution, bioavailability, and biological effects of single compounds

and chemical mixtures. Current and emerging methods for classifying chemicals

based on their ability to affect humans and the atmosphere must also be rened.

Micro-pollutant mitigation methods, as well as techniques to mitigate their penetra-

tion into the water systems, need to be further developed. The development of

“green” chemistry, which involves the creation of more environmentally sustainable

manufacturing processes and materials, is a complementary solution (Schwarzenbach

etal. 2006).

4.3 Landscape ofEnvironmental Laws forPollution

Remediation andMicro-pollutants

Environmental law is a generalized term that encompasses various laws that support

the environment (Sands and Peel 2006). It can be dened as a collection of different

common laws and pacts that govern how humans will interact with Mother Nature

(Hempel 1996). The purpose of making such laws is to protect the environment and

devise some rules for utilizing the natural resources (Palmer 1992) Most of these

laws restrict pollution, stress on the sensible use of natural resources, and protect

forestation and animal population (Wiggins etal. 2004). The vast eld of environ-

mental laws includes topics in legal settings; for example, regulation of standards of

emission in Germany, green great wall initiative in China, and the bottle return law

in the United States are among the several other laws that focus on environmental

protection. Environmental laws are relatively new and lawmakers started document-

ing these laws in the twentieth century (Palmer 2002). History reveals the imple-

mentation of laws to safeguard environmental issues regarding human health as a

societal part; in 80 AD, a legislation was passed by the senate of Rome to protect

water supply for drinking and bathing. In the fourteenth century, the British banned

burning of coal and dumping waste into waterways (Evans 1997). Benjamin

Franklin organized many trips to correct disposal of trash when William Penn, the

Quaker leader of the English colony of Pennsylvania, issued an order to conserve

one acre of woodland for every 5 acres of land acquired for habitation. The British

government established rules to limit the harmful consequences of coal burning and

chemical manufacturing on humans and the environment in the mid-nineteenth cen-

tury, when environmental pollution was at its worst (owing to the industrial revolu-

tion) (Fenger 2009). Twelve European nations signed an agreement for the

preservation of agriculturally valuable birds around twenty-rst century (Ferrero-

García 2013). The United States, Japan, Russia, and the United Kingdom signed a

treaty in 1911 to preserve and conserve fur seals. This treaty, which was ratied by

the United States and the United Kingdom (on behalf of Canada) in 1916, cleared

the way for the protection of migrating birds. It was later extended to Mexico in

F. M. Butt et al.

1936 (Dorsey 2009). The conference for the conservation of ora and fauna in

Africa in the form of nature reserves was adopted by Belgium, Egypt, Italy, Portugal,

South Africa, Sudan, and the United Kingdom in 1930, signaling a shift in the

framework towards ora and fauna sustainability in their original environment.

Spain and France, while signing the agreement, never ratied it (Adams 2013).

The environmental movement began to gain traction in the West in 1960, both

politically and philosophically. Or, to put it another way, many events/incidents led

to the understanding of the necessity for environmental preservation. The stage was

set by Rachel Carson’s publication of Silent Spring (Carson1962), which studied

chlorinated hydrocarbon insecticides and the damage they produced (Gavrilescu

etal. 2015). This work led to the realization of actual environmental hazards on

broader scale. After this realization, majority of environmental developments took

place at that time. Lawmakers began to pass environmental laws in the twentieth

century. United States government passed several environmental laws that chal-

lenged the status quo dominated by industrialists, including solid waste disposal, air

and water pollution, and endangered species protection. The nal step was the

establishment of an environmental protection agency to oversee the implementation

of these laws (Kolln and Prakash 2002). This environmental legislation expanded

the national government’s role, as these issues had previously been deemed to be the

responsibility of local governments.

There has been rapid industrialization in Japan, especially after world war-II

(Tsurumi 2015). As a result of this industrialization, industrial wastes were released

indiscriminately into the human food cycle. The tragedy in Minamata, where a sig-

nicant number of people were poisoned by mercury after eating a sh tainted with

industrial toxins, sparked the movement (Harada 1995). This resulted in consider-

ation by the Japanese government in the early 1960s to formulate a comprehensive

pollution control policy; the efforts materialized in 1967 when Japan created the

rst law for Environmental Pollution Control (Sumikura 1998).

After realization by leading countries in the world, several other countries started

joining in the issue by devising or joining pacts for several environmentally friendly

laws. The Ramsar Convention, which focuses on Wetlands of International

Importance, particularly as Waterfowl Habitat, was signed by thirty-four countries

in 1971. This agreement went into effect in 1975, and it presently has over 100 sig-

natories (Gardner and Davidson 2011). The accord required participating countries

to establish one protected wetland area so that the importance of wetlands in pre-

serving natural balance could be recognized. As countries became more aware of

environmental issues, they began to work together to address them. The United

Nations conference in 1972 led to the formation of the United Nations Environment

Program (UNEP) (Ivanova 2007). Despite its little inuence in implying the sanc-

tions on different countries, it serves as a baseline for many consortiums to follow.

Two commissions directly raised under the inuence of UNEP were established in

1972 (marine life) and 1973 (endangered species of ora and fauna), respectively

(Coggins 1974).

European countries were slow responders in managing environmental legisla-

tions until the Stockholm conference. In 1972, European countries started realizing

4 Environmental Degradation andMicro-pollutants inLight ofEnvironmental Laws

that industrial growth should be balanced with environmental issues (Coggins

1974). In the same year, the European Commission published its rst environmental

implementation strategy, and European governments began to make environmental

policy a priority (Wallace etal. 2020). Quoting the example of Germany, the public

perception about environmental legislations changed drastically in the 1980s, which

became evident when they elected the Green Partyin Germany as a representative

in the national parliament in 1983 due to its strict environmental campaign; at the

end of the twentieth century, this party got its share in government and developed

Germany extensive policies (Otto and Steinhardt 2014). Later on, with integration

with Netherlands and Denmark (green troika), it took environmental laws to the

next level (Liefferink and Andersen 1998). The Chernobyl incident marked the

development in transboundary effects of environmental degradation as the countries

that were facing the downwind effects of the incident had to devise some laws and

reduce the consumption of daily intakes of food (Howland 1987). This incident

generated two international agreements. The rst convention was on sharing of

information on priority basis of an incident. The second convention focused on

assistance to prevent the loss of life and environment due to nuclear incidents. These

two conventions were drastically drafted and implemented in 1986 (IAEA 2016).

Another convention on nuclear prevention was applied in 1994 that compelled the

signatories to develop basic procedures to safely manage the nuclear assets.

The interesting thing regarding the unreliability of datasets associated with

impacts of human activities is often a problem. It has always been a challenge to

write laws that handle human involvements; these rules were frequently adaptable

enough to meet scientic and technical advances.

Convention in Vienna on the Depletion of the Ozone Layer was another step

toward solving worldwide environmental problems (Bodansky 2001). In 1995, the

breakthrough in global environmental development was the UN conference on envi-

ronmental development, known as “Earth Summit,” in which 178 countries adopted

this law (Grub etal. 2019). The environmental laws after 1995 were seen in global

perspective. Another important development during this year (1995) was the devel-

opment of Intergovernmental Panel on Climate Change (IPCC) jointly by the UNEP

and the world meteorological organization (WMO) ( Metz etal. 2001). IPCC was a

global initiative to study the human inuence on global temperature changes. The

work of IPCC was criticized by communities for using insufcient datasets as

reports ring the bell about severe climate changes due to emissions. Kyoto protocol

came as an answer to the IPCC report critics and assigned the signatories emission

targets for sustainable development (Meyer 1999). This protocol introduced a bril-

liant concept of emissions trading that was intended for controlled emissions

throughout the world. This protocol allowed the developed countries to sell their

emission reduction units, which they have earned by controlling the emission well

below the authorized limits. In addition, those developed countries can also earn

these reduction units by supporting the developing countries in terms of supplying

the technology for the reduction of emissions. It is a wonderful rectication proto-

col, but since its adoption, it faced strong opposition, especially from developed

countries such as the United States (Hovi etal. 2012).

F. M. Butt et al.

With development in analytical methods involving detection of concentrations

from micro to nanograms in water samples, new pollution directories for the world

have been opened (Allan etal. 2006). Unfortunately, now new legislations/laws are

being devised to tackle the micro-pollutants that are causing a serious threat to the

human populations. The main reason for increase in micro-pollutants is the growing

population and industrialization. Several research projects in European countries

(Riskwa2, Strategie, COHOBAI etc.) are identied and addressed reduction mea-

sure for substance pollution in water (Amann etal. 2011). The major contribution

was by German Environment Agency(also known as Umweltbundesamt), which in

collaboration with other international partners (Rhine protection commission) has

devised several strategies and decisions on this matter. The developments have

occurred in the form of competence centers and equipping 19 treatment plants with

fourth treatment stage (NA 2000)

Switzerland has introduced several additional measures in wastewater treatment

since 2016in addition to the introduction of several laws (Czekalski etal. 2014).

European water frame directive (WFD) also stressed and provided directives on the

reduction and prevention of micro-pollutants. These legislations focus on ecosys-

tems biodiversity and availability of drinking water by using natural treatment

methods. Micro-pollutants have become a growing world problem and are often

linked with climate change (Delpla et al. 2009). Ever-growing climatological

changes throughout the world have triggered higher concentrations of micro-

pollutants in rivers, oceans, and subsurface aquifer system. It is the need of time to

address these issues considering growing climate changes. The laws associated with

micro-pollutants are at early stage. Most commendable work is done by European

Union (EU) with legislations focusing on the treatment at source of micro- pollutants.

The micro-pollutants from pharmaceutical industry and plastic industry are stressed

to be treated at the source before dumping them in water. German water protection

policy has set up benchmarks in addressing the issues associated with micro-

pollutants that have small concentrations and can end up in water bodies, which

later become part of the food chain, thus having adverse effects on health

(Metz 2011).

Actors participating in development policy and development in the rest of the

world have discussed how to deal with the problem. To decrease the use of danger-

ous pollutants at the source, proposed legislative measures might target consumers,

farmers, or industry (Press 2020). An alternative policy approach addresses the end

of pipe agreement that focuses on the treatment of sewage before introducing it to

the water body (Triebskorn etal. 2019). The three principles (source control, pol-

luter pays, and end of pipe treatment) legislated in the EU, if implemented in true

sense, can set an example for rectication of micro-pollutants, but despite strong

environmental laws’ implementation, EU has lot more to do in devising laws for

addressing micro-pollutants. The same stands for the rest of the world, where major-

ity of countries don’t have details regarding micro-pollutants’ effects on their envi-

ronment; thus, a strong legislation about awareness and eradication is desired all

over the world.

4 Environmental Degradation andMicro-pollutants inLight ofEnvironmental Laws

4.4 Micro-pollutants: AThreat toGrowing Economy

ofPakistan

Pakistan, like other developing countries around the world, is experiencing severe

water scarcity and pollution. The country’s available water supplies are almost

depleted. The rising toxicity of Pakistan’s drinking water supplies, as well as the

implications on human health and the environment, is a major cause of concern

(Azizullah etal. 2011).

Since ground aquifers provide water to most of Pakistan’s population (roughly

70%), surface water is also a signicant source of water for irrigation, drinking, and

domestic uses (Aziz 2005). The most basic source of supply in most Pakistani cities

is groundwater, which includes a variety of pathogens, including many infectious,

bacterial, and protozoan agents, resulting in 2.5 million deaths per year from

endemic diarrheal disease (Daud et al. 2017). Every year, an estimated 250,000

children die because of waterborne diseases. Diseases such as diarrhea, typhoid,

intestinal worms, and hepatitis are caused by insufcient quantities or consistency

of water, as well as a shortage of sanitation facilities. The annual risk of drinking

contaminated water is projected to be Rs 114 billion. Similarly, patients with water-

borne diseases occupy 20–40% of all hospital beds in Pakistan (Khalid and Khaver

2019). The consequences of the lack of clean drinking water and sanitation facilities

are observed not only on public health, but also on the economy. Pakistan spends Rs

365 billion a year on environmental depletion. A third of this amount is spent on

health-related costs because of insufcient water supplies and sanitation

(Mughal 2016).

Contaminated water is the most common cause of water contamination, which

has a negative impact on Pakistan’s economy and has a negative impact on Pakistani

people’s living standards (Ahmad etal. 2019). According to an estimate of the gross

economic burden of inadequate sanitation, it was calculated to be 343.7 billion PKR

(US$5.7 billion). This is the equivalent of 3.94% of Pakistan’s GDP. The direct

nancial burden, which is equal to 0.8% of GDP, is 69.52 billion Pakistani rupees

(US$1.15 billion). Most overall economic costs were attributed to health-related

issues. They accounted for 87.16% of all quantied economic expenses, or 3.43%

of gross domestic product. The gross economic burden on health is projected to be

299.55 billion PKR (US$4.93 billion), with nancial losses accounting for 48.76

billion PKR (US$801.53 million). The economic burden of inadequate sanitation

due to water is projected to be 15.98 billion PKR (US$262.68 million), or 0.18% of

GDP.This accounts for 4.65% of the overall damage, with nancial losses of 15.51

billion PKR (US$254.85 million) accounting for 15.51 billion PKR (US$254.85

million). Other welfare losses, such as consumer needs (which include comfort and

acceptability, privacy and ease, stability, avoidance of conict, status and popular-

ity, and time loss), are estimated to be 22.77 billion PKR (US$374.4 million), or

6.63% of overall impacts and 0.26% of GDP.Most of the expense comes from lost

time due to household access to free defecation sites (16.5 billion PKR [US$271.6

million]), which accounts for 73% of all welfare costs or 5% of all costs (Nishat 2013).

F. M. Butt et al.

According to a preliminary estimate, Pakistan is losing 25% of its possible crop

production (Abedullah 2006). The contribution of environmental problems to

Pakistan’s economy is estimated to be about 1.8 billion dollars. This expenditure

was attributed to the costs that citizens and the country expend on welfare, as well

as the lack of productivity that happens as a result of labor and individual absentee-

ism from factories, workplaces, and schools due to poor health (Brandon and

Ramankutty 1994). In January of 2000, the Ministry of Environment released a

report stating that Pakistan spends about 17 million dollars per year on pollution-

related issues, especially expenses related to clean-up activities, but that 84 million

US dollars are needed to fully resolve Pakistan’s environmental problems (Ahmad

etal. 2019). This reduction in pollution would also contribute to the long-term sur-

vival of Pakistan’s natural resources. The additional benets that will most likely be

provided by preserving existing capital have not yet been factored into the above

calculations (Abedullah 2006).

4.5 Environmental Policy andEconomic Relation

inPakistan

Every action done by the government, corporation, or other public or private entity

to identify the impact of human activities on the environment, including actions

aimed at preventing or reducing negative consequences on environments, is referred

to as environmental policy (Bueren 2019). Air and water contamination, landll

control, habitat conservation, biodiversity preservation, nature conservation, habi-

tats, and endangered animals are some of the topics that are addressed by environ-

mental policies (Eccleston and March 2011). For example, environmental policies

may be tackled by the introduction of a global eco-energy policy to resolve global

warming and climate change concerns (Banovac etal. 2017). The policies include

economic planning as well as the control of harmful substances such as pesticides

and various types of industrial waste. This approach should be used to intentionally

manipulate human behavior to minimize harmful repercussions for the biophysical

climate and natural resources, as well as to guarantee that environmental changes do

not have unfavorable consequences for humans (Jordan 2005).

Pakistan’s Environmental Policy is focused on a collaborative approach to

achieving long-term sustainability goals through constitutionally, administratively,

and professionally strong organizations. On December 6, 1997, the Pakistan

Environmental Protection Act was enacted to provide for environmental protection,

restoration, recovery, and enhancement, as well as pollution prevention and control

and the promotion of sustainable development (Ministry of EnvironmentGovernment

of Pakistan 2005).

The National Environment Policy establishes an overarching mechanism for

tackling Pakistan’s environmental challenges, including degradation of freshwater

sources and coastal waterways, air pollution, inadequate waste management,

4 Environmental Degradation andMicro-pollutants inLight ofEnvironmental Laws

erosion, habitat depletion, desertication, natural disasters, and climate change. It

also offers recommendations on how to resolve cross-sectoral issues, as well as the

root causes of environmental pollution and international commitments (Ministry of

Environment2005). Economic policies that ensure optimal resource use are a pre-

requisite, but not adequate, for establishing effective environmental incentives.

Environmental strategies are often required to resolve industry failures that result in

environmental concerns. Command and control policies and opportunity or market-

based policies are two types of policies that can be used to x environmental con-

cerns. Government-imposed environmental quality requirements on emissions,

technology type, or input usage are examples of command-and-control policies.

Prices are used in incentive- or market-based programs to attempt to affect waste

and resource utilization. Despite the benets of market-based interventions,

Pakistan, like many other countries, has largely relied on regulation policies.

However, these initiatives have frequently struggled to produce outcomes because

regulating agencies lack the nancial and technological tools to successfully enforce

them (Faruqee and Kemal 1996). In April of 1997, Pakistan has adopted market-

oriented policy reform, which would support both economic development and the

climate if it is enforced and extended rapidly. Non-distortionary economic policies

that encourage economic development by optimizing resource distribution often

generate adequate conditions for environmental conservation, according to experi-

ence in other countries. Of necessity, sound economic policies are insufcient.

Environmental policies that x industry failures are also expected. Economic policy

failures also lead to environmental issues, such as forest, rangeland, and rainfed and

irrigated agriculture. Subsidies for irrigation water, for example, allow farmers to

overuse water, worsening the irrigated agriculture’s waterlogging and salinity

issues. Deforestation and depletion of Pakistan’s forestland have been compounded

by a loss of property rights in communal forests and a failure to provide local people

with resources to engage in forest-management decisions (Faruqee 1997).

4.6 Steps Taken by Government toTackle Micro-pollution

Plastic pollution is caused by the deposition of plastic trash in the ecosystem. The

Greek term “plastikos” indicates “ability to be changed or molded into numerous

forms/shapes.” (Mukheed and Khan 2020). Plastic waste with a diameter of less

than 5mm is referred to as microplastics (Betts 2008), which are either immediately

released into the atmosphere or created when larger plastic debris degrades.

Microplastics are graded as primary or secondary microplastics based on how they

are produced. Microplastics, such as microbeads in cosmetics, are manufactured on

a microscale. The breakdown of macroplastic produces secondary microplastics

(Horton etal. 2017).

The sources of microplastics in aquatic and coastal environments have already

been addressed. (Duis and Coors 2016). Sewage leakage, microbers from textiles,

contaminants emitted from paints, and tires are all signicant causes of

F. M. Butt et al.

micro-pollution (Browne et al. 2011; Klein et al. 2015; Coppock et al. 2017).

Microplastics have been discovered in a variety of aquatic ecosystems, such as

wastewater treatment wastes, industrial runoff, and wastewater discharge following

heavy rain occurrences (Anderson etal. 2016).

Microplastics have become a regular part of the global ecosystem, posing a sig-

nicant danger to marine and coastal environments (Cai etal. 2017; Bordós etal.

2019; Koongolla etal. 2018). The presence, distribution, and impact of microplas-

tics have been extensively researched in aquatic environments, but less focus has

been paid to freshwater systems, and as a result, research on microplastic pollution

of rivers and lakes is scarce when compared to oceans (Zhang etal. 2016; Sruthy

and Ramasamy 2017). Because of their smaller size range, microplastics are eaten

by invertebrates, sh, and marine animals because they are identical to food sources

(Thushari etal. 2017).

Many nations have banned the commercial usage of microplastics like micro-

beads owing to their harmful consequences. The Microbead-Free Water Act, for

instance, was passed in the United States in 2015, prohibiting the use of microbeads

(NOAA 2018). Canada approved legislation limiting the use of microbeads in 2017

(Lam etal. 2018). In 2016, the Australian Microbead Working Group was formed

with the goal of negotiating voluntary agreements with the cosmetics sector to erad-

icate microbeads from rinse-off cosmetics (EPAN 2016; Lam et al. 2018). Since

these laws were just newly enacted, the result is still unknown. Taiwan’s Waste

Disposal Act, which is administered by the Environmental Protection Agency, bans

the use of microbeads (Central News Agency 2018). In Pakistan, there is no clear

legislation on microplastic contamination. In Islamabad and the capitals of other

provinces of Pakistan, regulations governing the use of plastic items such as poly-

ethylene bags are made, in which the use of plastic bags is banned (Pakistan

Environmental Protection Agency 2019). These rules prohibiting the use of plastics

would act as a starting point for the creation of further legislation to combat plastic

waste. Implementing a ban on the use of plastic materials would further mitigate

microplastic waste by preventing unsafe disposal (Irfan etal. 2020).

In South Asia, Pakistan has the highest proportion of mismanaged plastic.

Bangladesh, France, and Rwanda are among the countries that have outlawed the

use of plastic bags. Plastic bags are prohibited in Pakistan’s Capital Territory,

Islamabad, as well as several other towns such as Lahore and Hunza, according to a

Statutory Regulatory Order (SRO). Currently, there is no federal or regional regula-

tory system in place to address the issues of single-use plastics and plastic trash

treatment in general (Mukheed and Khan 2020). Plastics are less expensive, more

dependable, and more widely available in the country; in a struggling economy, a

blanket prohibition will lead to the loss of many employments or a drop in consumer

footfall if no other bag is available. Though PET bottles and other high-value plas-

tics are scavenged, most of the single-use nonbiodegradable plastic ends up in

uncovered waste sinks, landlls, or public sewers, clogging sewage treatment sys-

tems (Mukheed and Khan 2020). The root of the issue has been identied as the

current municipal waste management scheme, which prioritizes picking waste from

4 Environmental Degradation andMicro-pollutants inLight ofEnvironmental Laws

collection point and properly disposing of it in city outskirts without ltering,

resource conservation, or recycling, as well as failing to require communities to take

responsibility (Mukheed and Khan 2020). We all know that waste management

rms cannot address this complicated challenge on their own; they need compre-

hensive policy, technology, and funding from both public and private stakeholders.

Every year, 30 million tons of solid waste are generated in Pakistan, with plastics

accounting for 9% of that total. A total of 55 billion plastic bags are manufactured

here each year. These single-use nonbiodegradable bags typically end up in open

waste dumps, landlls, or urban sewers, clogging waste collection systems and the

service costs. Existing municipal waste management strategies exacerbate the prob-

lem by focusing solely on collecting garbage from community bins and dumping it

on the outskirts of cities without segregation, resource reuse, or recycling, as well as

failure to encourage people to act properly (Qari and Shaffat 2015; Rajak etal.

2019; Dawei and Stigter 2010).

In 2017, Pakistan introduced oxo-biodegradable technologies as a tool to combat

plastic waste. After their useful life, oxy-biodegradable plastics completely biode-

grade in the environment, leaving no adverse effects on the environment. As a result,

all the problems related to plastic pollution will be addressed. After close analysis

of both alternative solutions and empirical facts, the legislation was formulated

(Daily Times Pakistan 2020). In 2019, the Islamabad Capital Territory adopted a

new model, prohibiting the use of plastic bags and encouraging the use of biode-

gradable bags. The Ministry of Climate Change took the initiative (MoCC). The

MoCC is trying to ensure that the prohibition is fully implemented by enforcing

harsh penalties and hefty nes on anyone who break it. Polypropylene bags are

nonbiodegradable; as major commercial polymers, polyethylene and polypropylene

are extremely resistant to biodegradation, i.e., degradation by microorganisms

(Mukheed and Khan 2020). Authorities have overlooked an important fact: polyeth-

ylene is not the only pollutant in the world. Plastic contamination is also caused by

polypropylene and other single-use plastics. Nonwoven PP, BOPP, CPP, Metalized

lms, WPP, and shrink wraps are often found in single-use materials that are dis-

carded in the eld. The negative consequences of plastic waste accumulation are

rapidly growing. As a result, removing them from the ecosystem is important (Daily

Times Pakistan 2020). Plastic waste accumulation has a growing number of nega-

tive consequences. Therefore, it is important that they be excluded from the com-

munity. Fabric-like nonwoven polypropylene bags are made entirely of

polypropylene, a plastic. These polypropylene bags in the industry are mistakenly

labelled as biodegradable because they disintegrate into pieces, resulting in micro-

plastics. Microplastics enter the food chain, posing a threat to the lives of thousands

of land and sea mammals. Microplastics can’t be collected or seen by the naked eye

because of their small size. As a result, rather than xing the plastic waste issue,

these bags will exacerbate it (Mukheed and Khan 2020).

F. M. Butt et al.

4.7 Conclusion

Many organic materials, such as medicines, pathogens, chemical contaminants, etc.,

are found in wastewater as these contaminants are seldom eliminated during waste-

water treatment; they are released into aquatic ecosystems, which are sometimes

utilized to produce water for drinking.

Up till now, the effectiveness of biological and oxidative sewerage and water

purication processes has been based mostly on the dispersion of target chemicals,

even though it is well-known that the conversion of organic pollutants can result in

products with equivalent or even higher toxicities. To comprehend and analyze the

reactive and biological treatment methods, it is critical to unravel the degradation/

oxidation routes and determine the products formed.

Many of Pakistan’s environmental issues may be traced back to economic poli-

cies that have had unforeseen and indirect environmental consequences. The

Environmental Protection Act of 1997 is a signicant piece of environmental legis-

lation in Pakistan’s legal history. This policy was created with the goals of environ-

mental preservation, protection, rehabilitation, and betterment, pollution prevention

and control, and the implementation of sustainable development. The National

Environmental Action Plan (NEAP), which was approved in February 2001 to fol-

low the NCS program, intends to achieve four goals: clean air, clean drinking water,

wastewater treatment, and sustainable development. Another important policy in

Pakistan’s history is the Pakistan’s National Environmental Policy (2005–2015),

which aims to improve the quality of life of Pakistan’s citizens via environmental

protection, preservation, and development, as well as effective cooperation among

government entities, civil society, the private sector, and other partners.

Environmental authorities have not done a good job of monitoring and regulating

natural resource usage and pollution.

To summarize, the government should not rely solely on regulation in the future,

but rather progressively adopt market-based measures, which can be more

successful.

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4 Environmental Degradation andMicro-pollutants inLight ofEnvironmental Laws

75© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022

T. Ahmed, M. Z. Hashmi (eds.), Hazardous Environmental Micro-pollutants,

Health Impacts and Allied Treatment Technologies, Emerging Contaminants and

Associated Treatment Technologies, https://doi.org/10.1007/978-3-030-96523-5_5

Chapter 5

Impacts ofMicro Pollutants onHuman

Health andEnumerating

theEnvironmental Renement

MuhammadNawaz andSheikhSaeedAhmad

Abstract Micro pollutants are chemical substances which are generated through

natural as well as human activities. The anthropogenic sources of micro pollutants

are so far greater than natural processes. These micro pollutants are present in

diverse forms, e.g., pharmaceuticals, heavy metals, personal care products, and

endocrine disrupting chemicals. The nature of their toxicity also ranges from mild

to very chronic for the human health as well environmental dysfunctions. This chap-

ter also deals mainly with the amount of the micro pollutants released, their main

sources, toxicity ranges, and the way these pollutants produce ill impacts on the

human health. It has been observed that all micro pollutants having any source can

produce their adverse impacts on the health of humans, and these impacts include

DNA mutation to organ modication, with the outbreak of certain diseases of which

liver, lung, and kidney diseases are prominent. The possible pathway of these pol-

lutants has been observed in the form of drinking or wastewater which enter in to

human body through irrigating the fruits or foods and by drinking the water having

such pollutants. The objective of this study is also to employ all possible options by

which these pollutants could be eliminated completely from the environment. There

are certain options which can be used for their reduction very simple to last tech-

niques. This study also stresses to minimize all possible sources of these micro

pollutants rather than to use possible option for their elimination once they enter in

to the environment.

M. Nawaz

Department of Environmental Sciences, Bahauddin Zakariya University, Multan, Pakistan

e-mail: mnawaz@bzu.edu.pk

S. S. Ahmad (*)

Department of Environmental Sciences, Fatima Jinnah Women University,

Rawalpindi, Pakistan

e-mail: drsaeed@fjwu.edu.pk

5.1 Introduction

Micro pollutants are chemical substances which are always found in very low con-

centration, ranging from mgL−1 to ngL−1 in the environment and cause serious threat

to the ecosystem. Micro pollutants occur in all aspects of the environment, atmo-

sphere, soil, and water, but mostly they work effectively in the aquatic environment

and pose direct impacts on the health of the environment. Wastewater from indus-

tries and domestic contains plenty of micro pollutants which are released into the

aquatic ecosystem, causing disturbance in the ecosystem functioning. These micro

pollutants are generated both by human activities and anthropogenically in the envi-

ronment and disrupt the smooth working of the ecosystem (Wanda et al. 2017;

Bunke etal. 2019). Due to micro pollutants, water pollution has become a great

issue since 1990 due to uncontrolled discharge of these substances into the main

water channels which serve for drinking as well as for agriculture purposes. Since

the last two decades, global issues related to water and atmospheric pollution have

emerged quickly because of ecosystem-unfriendly human activities,resulting in

adverse effects on the environment. Multiple anthropogenic activities of mankind in

the form of urbanization, transport, unwanted use of agriculture fertilizers, and

industrial generation have enhanced the pollution of water as well as air, like fast

production of greenhouse gases, carbon dioxide, particulate matter, nitrogen oxide

species, chemicals, leachates, oil spills and nutrients in the soil, water, and atmo-

sphere (Pablos etal. 2015; Grandclement etal. 2017; Rizzo etal. 2019). It has been

estimated that from 1930 to 2000, the amount of chemicals produced by human

activities has increased by one million to four hundred million tons per year; simi-

larly during 2002–2011, among all produced chemicals, 50% are very harmful com-

pounds which cause serious health impacts (Gavrilescu etal. 2015). According to a

study by Barbosa etal. (2016) and Talib and Randhir (2017), 70% of the produced

chemicals by human activities have prominent impacts on the water quality. It has

been also observed that in Europe about 0.1 million chemicals have been registered,

among them approximately 70, 000 are being used daily which mostly end up in the

aquatic ecosystem after their use. It has also been estimated that about 300 million

tons of micro pollutants are discharged into the water in the form of consumer prod-

ucts and industrial efuents annually, in which 970 have been identied as emerging

micro pollutants. Due to having serious consequences, the EU commission has put

some micro pollutants in the watchlist, which include 17-alphaethinylestradiol,

17-betaestradiol, estrone, diclofenac, 2,6-di-tert-butyl-4-methylphenol2-

ethylhexyl- 4-methoxycinnamate, macrolide antibiotics, methiocarb, neonicoti-

noids, oxadiazon, and triallate (Bunke etal. 2019). This chapter also focuses on the

generation, transportation, and impacts of such micro pollutants which need to be

eliminated from the environment by using some strategies.

M. Nawaz and S. S. Ahmad

5.1.1 Classes ofMicro Pollutants

Micro pollutants are a certain group of chemicals which are generated naturally or

by anthropogenic activities such as mining, ill agricultural practices, industrial dis-

charge, and pharmaceutical synthesis. There are several types of micro pollutants

depending upon the nature of sources and consumer ends. According to Jia-Qian

etal. (2013), the major groups of micro pollutants are as follows:

(a) Pesticides

(b) Pharmaceuticals

(d) Personal care products (PCPs)

(e) Biocides

(f) Heavy metals

5.1.1.1 Pesticides

All kinds of animals in the form of plants, animals, or microorganisms which can

destroy the food, luxuries, or health status of living things are termed as pests, while

chemicals which can prevent, repel, or destroy the action of these pests are termed

as pesticides (Dunn 2012). This group of pesticides consists of several compounds

which are in the form of insecticides, rodenticides, fungicides, herbicides, acari-

cides, molluscicides, and nematocides. Sometimes these pesticides work in the

form of microorganisms like fungi or bacteria, also may be in the form of compo-

nents of living organisms like endotoxin or whole organism for killing the pest, for

example, wasps (Trichogramma evanescens), which are used as predatory organ-

isms for controlling the pest in agriculture (Parastar etal. 2018). The use of pesti-

cides has been increased tremendously worldwide since the last few decades, which

has changed the farming practices resulting in environmental problems. It has been

observed that during 2008–2012, about 45% of expenses on herbicides have been

used among all pesticides including 14% on insecticides, 10% on fungicides, and

23% fumigants. These pesticides enter the soil through runoff, leaching, careless

disposal, and container washing which have caused ecosystem dysfunction (Luo

etal. 2016).

5.1.1.2 Pharmaceuticals

Several authors have dened the term pharmaceuticals as the group of chemicals

which can be administered for the purpose of curing diseases of all animals and

humankind, which includes veterinary medicines and some growth enhancer in

plants as well. Frequently used pharmaceuticals include analgesics/anti-

inammatories, antibiotic, cardiovascular pharmaceuticals (b-blockers/diuretics),

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

psychostimulants, estrogens and hormonal compounds, and antiepileptic drug

(Bueno etal. 2012; Nicholas-Bateman 2012; Li etal. 2013). These drugs are being

synthesized in greater amounts all over the world due to high consumption per cap-

ita, and it has been estimated that Asian countries, especially India and Pakistan, are

consuming huge quantities of these chemicals annually. In this regard, India is

among the top ve countries that are generating pharmaceuticals, with expenses of

about 45 USD billion annually, which are expected to rise 60 USD million by 2022

and the export of these drugs will rise from 30% to 60%. (KPMG International

2006; Kallummal and Bugalya 2012; Ebele etal. 2017). It can be said that every

third tablet being used at global level is synthesized in India, but interestingly it is.

In other words, every third pill taken in the world is manufactured in India, but it has

been observed that 80% of the drugs are being consumed inside India. Despite the

high rate of consumption of these drugs, the waste handling is not so much up to the

mark (Subedi etal. 2015).

5.1.1.3 Endocrine-Disrupting Chemicals

Endocrine-disrupting chemicals have been dened by many agencies during late

1990s which have the opinion that these are some sort of exogenous drugs that after

their release and transportation can disrupt the regulation, maintenance, homeosta-

sis, and developmental process, which is being performed by some natural hor-

mones present in the body. These endocrine-disrupting chemicals can eliminate

functioning hormones in the body by binding with them or change the metabolism

which creates the malfunctioning of these hormones. (Mocarelli etal. 2008; Damjan

etal. 2011). According to the denition of Yilmaz etal. (2020), endocrine- disrupting

chemicals are an exogenous group of compounds; probably more than 1000 which

disrupt the biological functions of hormones in the body. These are sometimes

grouped in the forms of heavy metals, pesticides, fungicides, pharmaceuticals, and

industrial efuents and cause a worldwide problem for the environment and human

health. Like other chemicals, the quantity of endocrine-disrupting hormones is also

increasing day by day, and due to contamination, the physiology of living organisms

has been disturbed. These chemicals are produced naturally as well as synthetically

and many micro pollutants being produced in the environment act as endocrine-

disrupting hormones which include pesticides, dioxins, polycyclic aromatic hydro-

carbons, polychlorinated biphenyls, phthalates, bisphenol A alkylphenols, and

heavy metals like arsenic, cadmium, lead, and mercury which have shown negative

impacts on the regularity and balance of endocrine (Gago-Ferrero et al. 2012).

According to observations of Yoon etal. (2010) and Jeong etal. (2017), endocrine-

disrupting hormones work as blockers of estrogen and thyroid gland which produce

abnormality in the endocrine systems. About one thousand compounds have been

identied which act as endocrine-disrupting chemicals and can be found in samples

of urine, milk, serum, and placenta by biomonitoring studies.

M. Nawaz and S. S. Ahmad

5.1.1.4 Personal Care Products

Personal care products are those chemical substances which are used in our day-to-

day life and range from medicines to shampoo, conditioner, lotion, and tooth pastes.

These products, along with pharmaceuticals, have got much attention due to pro-

ducing toxic impacts on human health as they contain various groups of compounds

and one more interesting phenomenon concerned with them is that they are only

conned to aquatic habitat by their ending up as consumer product (Radjenovic

etal. 2009; Kasprzyk-Hordern etal. 2009). These products are used for improving

hygiene and health, but even their low concentration can produce toxicity in the

ecosystem. These products are also considered as endocrine-disrupting hormones

(Tolls etal. 2009; Paulsen 2015). The problem of production of such products has

been increased since last decades, and according to Tanwar etal. (2014), the Global

Beauty Market has been categorized into ve portions on the basis of synthesis of

these products which are hair care, skin care, fragrance, colors, and toiletries items.

The rate of discharge or decomposition is much faster than other pharmaceuticals as

these are applied externally while drugs are used internally, so due to this property,

these are a heavy burden on the water bodies. European countries like Italy,

Germany, and Spain are the main producers of such products and represent about

70% of the total world cosmetic production.

According to Ebele etal. (2017) and Montes-Grajales etal. (2017), from 1998 to

2010, the sale of beauty items increased from 166.1 billion to 382.3 billion USD,

which included a higher amount of skin growth substances. The review study of

Montes-Grajales etal. (2017) reported that about 72 products have been identied

which act as micro pollutants whose concentration varies from 0.09 ng/L to

7.82 ng/L.

5.1.1.5 Biocides

According to Parsons etal. (2019), biocides are chemical substances which are used

for the preservation of addible goods durably, insects’ control, and disinfection of

surfaces. Nowadays, many antimicrobial applications are being used at house and

commercial level, for example, detergents, seats of toilets, etc. About more than 200

active biocides are being used commercially for daily life. Exposure to products

containing biocides is increasing at a high rate due to widespread use of daily life

products, and after exposure, these biocides cause numerous problems when they

come in contact with human skin, sometimes by way of inhalation inhalation. Many

environmental impacts have been observed by using these biocides, but their effect

increases many folds when more than one biocides are the component of a single

daily life product. The general concerns noted by Pinto (2010) are the follows: rst,

these biocides make association with the target sites very similar to antibiotics

which then cause mutation and resistant nally; second, due to difference in the

activity of these biocides, antimicrobial efciency is suppressed which causes the

failure of antibodies of living organisms.

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

5.1.1.6 Heavy Metals

Heavy metals are those substances or elements that have their specic density more

than 5g/cm3 and atomic weight above 40. These above 35 metals occur naturally in

the environment and 22 metals among them are considered as heavy metals. These

substances normally consist of higher electrical conductivity which loses their elec-

tron very easily to form cation (Li etal. 2017). These metals are found in each

component of the ecosystem, including earth, aquatic parts, and mostly body parts

of plants and animals. Metals like copper, iron, gold, nickel, silver, zinc, etc. are

considered as heavy metals because of having high atomic number as well as

adverse effects on living organisms. Some metals are very essential for the physio-

logical function of living organisms and their deciency leads towards diseases.

These essential elements include zinc, copper, cobalt, magnesium, and iron sele-

nium and are produced naturally as well as anthropogenically in the environment

(Zambelli etal. 2016; Rahimzadeh etal. (2017), but when crossing their threshold

limit, many biochemical disorders have been observed in the body of living organ-

isms (Zhao etal. 2017). Contaminant metals in the form of lead, mercury, arsenic,

and cadmium affect the food chain in the ecosystem because after entry in the eco-

system, they increase their concentration by the process of bioaccumulation and

biomagnication (Alam etal. 2019). Industrial revolution and some environmental

events like cyclones and volcanic eruptions are causing the release of such toxic

metals in the ecosystem, and it has been observed that about two million tons of

industrial and agricultural waste are being released into the aquatic environment

every year. About 1.5 billion people are getting contaminated water worldwide

because toxic metals after their release accumulate in the water as persistent organic

pollutants for a longer period of time and consequently produce toxic impacts on the

human health through food chain (Abdi etal. 2018; Adam etal. 2019).

5.1.2 Major Sources andPathways

According to the opinion of Pal etal. (2010), Bo et al. (2016), and Magi and Di

Carro (2016), micro pollutants present in any form (pesticides, pharmaceuticals,

personal cleaner product, or endocrine-disrupting products) always end up in the

aquatic environment and produce real threats to the ecosystem. Figure5.1 shows the

back and forth movement of micro pollutants in three layers of water, e.g., surface

water, ground water, and then in the form of drinking water, which reaches the

human body (Barbosa etal. 2016). It has always been found that these micro pollut-

ants are present in surface water, ground water, and drinking water as well. Figure5.2

shows the transportation of some micro pollutants with some other nanoparticles in

the soil and ultimately ending up in the water. Water consists of many residues of

these pollutants, which reach the human body through the food chain. Choi etal.

(2008) investigated the concentration of different micro pollutants including acet-

aminophen, carbamazepine, cimetidine, diltiazem, and sulfamethoxazole in the

M. Nawaz and S. S. Ahmad

wastewater of Korea and Wales, which was found about 10ug/L which is the high-

est concentration ever found in the water. Kasprzyk-Hordern et al. (2009) found

similar concentrations of gabapentin, tramadol, and acetaminophen in the wastewa-

ter produced from hospitals of the UK.These chemicals are ingested orally, and

after utilization, these are secreted from the human body in the form of urine or

feces. It has been observed by Vulliet and Cren-Olivé (2011) that ground water is

less polluted as compared to that of surface water because it may be due to surface

ow of water can disseminate the micro pollutants and far less reach of contami-

nants occur in the ground water. This ground water is only polluted when there is

inltration of pollutants from agriculture, sewer tanks, or through seepage of septic

tanks (Lapworth etal. 2012). Soil can also play a signicant role in groundwater

pollution because it acts as a pathway for transportation of micro pollutants through

the water which ows through it (Stepien etal. 2013). During the interaction of soil

and water, the biochemical properties of soil and micro pollutants enhance the trans-

fer of pollutants to ground water.

Some recent investigations (Loos etal. 2013) showed that micro pollutants pri-

marily reach the aquatic ecosystem after their generation and it depends upon the

mode of action of pollutants as well as binding sites of soil and water. Figure5.2

shows the transportation of these micro pollutants clearly, and major pathways seem

to be in the form of agricultural, urban runoff, municipal, industrial wastewater

discharge, sludge disposal, and accidental spills (Dale etal. 2015). The micro pol-

lutants along with nanoparticles remain in movement from the source (where

Fig. 5.1 Representative sources and routes of micro pollutants in the aquatic environments.

(Barbosa etal. 2016)

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

generated) to their sink (degraded and accumulated). Micro pollutants in the form

of heavy metals which are produced naturally are present in the environment.

Garcia-Esquinas etal. (2013) reported that heavy metals being the major portion of

micro pollutants are present in the biotic as well as abiotic portion of the environ-

ment. According to Krishna and Mohan (2016), heavy metals are always present in

the ecosystem, but their exposure to humans mainly depends upon the many anthro-

pogenic activities of man. The heavy metals present in the earth ores are recovered

through mining, and toxic metals like zinc, arsenic, nickel, and lead are present in

oxides or suldes form. During the mining of such suldes or oxides, toxic metals

are released and spread throughout the environment by air, water, or soil. Sauve

(2014) observed similar transportation of heavy metals which are released from

industries and move through the environment as efuents or may move to soil as

runoff, erosion, or acid rain. Furthermore, it has been also noted that heavy metals

are also released as part of industrial products like paint, pesticides, cosmetics, and

herbicides which cause deterioration of the ecosystem. The possible entry of heavy

metals in human body may also occur through contaminated food items, sea foods,

Fig. 5.2 Movement of micro pollutants along with other nanoparticles in the soil and aquatic

ecosystem. (Dale etal. 2015)

M. Nawaz and S. S. Ahmad

drinking water, or through breathing, and most probably exposure through mining

(Kim etal. 2015; Ali and Khan 2018). These heavy metals always move in cyclic

form in the environment, as if synthesized in industry, from the atmosphere to the

soil, and then directly or indirectly into the human body. For this, heavy metals can

move through several routes; for example, heavy metals like cadmium, lead, mag-

nesium, and arsenic enter into the human body through the mouth along with food,

fruits, vegetables, or water. Some chemicals also move into the human body through

inhalation from the atmosphere, while some are absorbed through contacting the

skin (Guo etal. 2019). After entry, these heavy metals are distributed in the body

through the blood to the tissues and nally affect the target sites, like the liver, kid-

ney, or lungs (Jawed etal. 2020).

Micro pollutants in the form of pharmaceuticals, personal care products, and

endocrine-disrupting chemicals move to human body through aquatic water. These

chemicals can be of two types by their sources which are point source as well as

nonpoint source (Lapworth etal. 2012). According to the studies of Li (2014), the

point sources are identied as industrial, hospitals, and sewage water, while the

nonpoint source is not visible and very much difcult to locate, e.g., runoff, etc.

Figure 5.3 shows the pattern of movement of pharmaceuticals and other related

chemicals through different sources and pathways and it clearly shows that end up

of these chemicals is always in the aquatic environment. It has been observed that

about 70% of drugs are transported by households, while 20% come from livestock,

5% from hospitals waste, and 5% are not known by their source. The reports of

Besse etal. (2012) and Qin etal. (2012), conrm the presence of trances of partially

metabolized medicine in different water sources like in surface water, ground water,

drinking water as well as wastewater. Similarly, Falconer etal. (2006) and Huang

Fig. 5.3 Sources and pathways of pharmaceuticals and personal care products in the environment.

(Kurwadkar etal. 2015)

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

etal. (2012) also conrmed the spills of chemicals like endocrine-disrupting and

personal cleaner in the aquatic ecosystem. The entire pharmaceutically active com-

pound can be found in the humans and animals, including the mixture of whole as

well as half metabolized chemicals, which look more polar and hydrophilic. These

chemicals can enter or move into the body of organisms by food, vitamins, or

desired drugs, while can exit in the form of urine, feces, or bleeding. These pharma-

ceuticals when enter into the ecosystem cause adverse effects on the biochemical

activities of other living organisms. According to Debnath and Khan (2017), the

pathway of pesticides into the human body is also through inhalation, oral, or by

skin, and after exposure, pesticides cause injuries or poison which need immediate

treatment.

5.2 Impacts ofMicro Pollutants onHuman Health

Several authors have documented the impacts of different micro pollutants on

human health as shown in Table.5.1. The particulate matter and organic and inor-

ganic pollutants which are released from different sources have chronic effect on

human health as they have a high rate of transfer in the blood after their exposure.

Luong etal. (2017) and Huy et al. (2017) noted the close interaction between the

emissions of certain pollutants from industries and agriculture sector with the num-

ber of patients having chronic respiratory disorders in the hospitals of Vietnam.

Similarly, Nhung etal. (2018) studied the status of ambient air of Vietnam with

other Asian countries comparatively and found higher concentrations of polychlori-

nated biphenyls in the ambient air of Vietnam. In the case of some personal care

products (PCPs), the oral entry of heavy metals is also one of the best examples of

generation of toxicity after their application in the form of cosmetics when applied

around the mouth or contact of hands to mouth having negative effects. This phe-

nomenon is likely to be more frequent than the inhalation of these cosmetics. Heavy

metals having higher concentrations in cosmetic products have been shown to have

greater impacts on the human body. Lead has been found responsible for causing

neurotoxins associated with the problems of learning, speaking, and behavioral

aspects. Similarly, it has also been associated with certain problems of men and

women. According to Lau etal. (2018), lead can affect fertility in human beings and

bring changes in the hormones, irregularities in the menstrual cycle, and late onset

of puberty in girls. Similarly, pregnant women are prone to more complications

because lead can enter through the placenta and causes brain problem in infants.

Cadmium can also enter the body through the application of cosmetics in the form

of hair creams and absorbed in the body through contact with skin. It has been found

stored in the kidney and liver, ultimately causing the cancer of these organs.

Ingestion of high concentration of cadmium causes stomach problems in the form

of vomiting and diarrhea, while lower but long-term exposure of lead can deform

the bones and damage the liver and kidney. Chromium and mercury found in the

daily used products have also adverse impacts in the form of skin allergy, ulceration,

M. Nawaz and S. S. Ahmad

Table 5.1 Multiple impacts of micro pollutants on human health

Micro pollutant Impacts Pathway Author

Endocrine disruptors Reduce fertility in male Move through

plasma

Li etal. (2012)

Personal cleaner products Stop the growth of

infants

Transported in the

human milk

Yin etal. (2012)

Persistent and mobile organic

compounds

Food toxicity Absorbed and

transported by

water

Reemtsma etal.

(2016)

Persistent organic pollutants

(POPs)

Respiratory problems,

asthma, and bronchitis

As air particulate

matters,

Phung etal.

(2016) and

Nhung etal.

(2018)

Arsenic, 1,4-dioxane, and

vinyl chloride

Carcinogens, cause

cancer

found in wastewater Nogueira etal.

(2015)

Pesticides sprayers Antioxidant status, and

altered activities of

cellular enzymes such

as catalase, ligase

Runoff, lost via

spray drift, off

target deposition,

Transported

towards soil and

water

Wafa etal.

(2013)

Pesticides like atrazine

organophosphorus,

carbamates, organochlorines

Disturbance in the

hormonal system

Through water and

skin contact

Bergman etal.

(2014)

PCPs (metallic elements) Abnormal hormonal

control causing

reproductive

impairments, decreased

fecundity, increased

incidence of breast and

testosterone cancers,

and persistent

antibiotic resistance.

Present in water,

transferred to the

body by contact

with skin or

inhalation, and also

can move to body

via food.

Endocrine-disrupting

chemicals (Biphenyl A,

Polychlorinated biphenyles,

Dioxin)

Effects on infant’s

growth, decrease in the

semen quantity,

testosterone level

decline

Through livestock

feces, agricultural

waste and through

contaminated fruits

and vegetables

Travison etal.

(2007)

All micro pollutants Cause of cancer, brain

damage, liver

problems, and

reproductive problems.

Transportation

through water,

food, contacts, and

inhalation

Ha etal. (2007),

Diamanti-

Kandarakis etal.

(2009), and

Swaminathan

etal. (2013)

Micro pollutants (Plastic

goods for packing, containing

epoxy resin, Polychlorinated

biphenyl, etc.)

Breast cancer, decrease

in the androgen,

feminizing like side

effects in men

Transported via

water and food due

to contamination

Rogers etal.

(2013)

(continued)

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

Table 5.1 (continued)

Micro pollutant Impacts Pathway Author

Pharmaceuticals and PCPs

(Carbamazepine Diclofenac

Naproxen Gembrozil

Bisphenol-A)

Male & female

reproductive problems,

kidney disorders,

Immune syndrome,

thyroid disorders,

Cancer, bone problems,

and metabolic

syndrome.

Oral administration

and drinking water

Alma etal.

(2019) and IARC

(2019)

Arsenic, Zinc, Selenium,

Mercury, Copper (from

plating, miming, and

agriculture)

Cancer in the human

body, DNA mutation,

Syndrome, stomach

ulcer.

Entry through food

and water

Bessbousse etal.

(2008)

Chromium from leather and

plating industries

Cancer, bronchitis,

Skin inammation

Through drinking

and irrigated water

Bilal and Iqbal

(2019)

Mercury and zinc from

mining.

Leukemia, Anemia,

kidney, and skin

problems

Fish is also one of

the sources of Hg to

human body

Engwa etal.

(2019) and

Bolisetty etal.

(2019)

Trace elements of Pb and Cd High concentrations of

Pb and Cd cause blood

cancer, liver necrosis,

skin, and reproductive

problem

Water and

contaminated food

Guo etal. (2019)

Biocides

(Tetrachlorsalicylanilide and

Fentichlor)

DNA degeneration,

Inhibition of cell

growth. Respiratory

syndrome.

Through

vegetables, water,

and food.

Diphenylalkanes,

polycarbonate plastic

Tissues damage,

Decline biological

activities, Endocrine

disruption.

Inhalation, water

and food

Meeker and

Ferguson (2011)

Herbicides (Nonylphenol and

Octylphenol)

Postnatal disorder, NP,

and OP have been

detected in human

Transported

through human

breast milk,

seafood, and eggs.

Ademollo etal.

(2008) and

Calafat etal.

(2008)

Pesticides like DDT and

Phenols

Disorder of male

reproductive system

and hormonal

imbalance

By absorption

through irrigated

water and vegetable

consumption

Mnif etal.

(2011)

Endocrine disruptive

chemicals(Di-2

ethylhexylphthalate (DEHP)

Preterm births.

Pregnancy failure

Food and water Chang etal.

(2017)

Pesticides (organochlorines,

metabolites)

Risk of type 2 diabetes

and its comorbidities

Through fruits and

vegetables

Azandjeme etal.

(2013)

Occupational herbicides like

imazethapyr, a heterocyclic

aromatic amine herbicide

Cause of bladder

cancer and colon

cancer

Through drinking

water and

contaminated foods

Koutros etal.

(2009)

(continued)

M. Nawaz and S. S. Ahmad

nervous toxicity, immune syndrome, and reproductive issues in men and women.

The studies of Murphy et al., McKelvey et al., and Lingamdinne et al. show that

antimony, cadmium, mercury, and chromium are also present in the makeup pow-

der, hair cream, shampoo, conditioner, and lipstick which cause the certain human

disorders when their concentration reaches to threshold limits. Some of the metals

like arsenic have synergetic effect when combined with the other metals or oxides.

Singh et al. found that arsenic has its ecological and individual health impacts when

it is in the form of salts, oxides, or suldes of copper and iron because it is exten-

sively carcinogenic in nature. Arsenic is also frequently detected in drinking water,

which it can enter through pesticides containing arsenical salts, and lethally impact

human and environmental health. Mazumder also observed its common use as sui-

cidal substance by many people by causing the poison due to acute toxicity. Similar

effects have been also noted in the case of lead, which can form chelates or com-

plexes with other metallic substances, and its absorption is very easy compared to

the rest of the heavy metals. Pesticides have also chronic effects on human health

especially in people working in the agriculture elds, living nearby pesticides indus-

tries, and have close contact with pesticides, as shown in the Fig.5.4. These pesti-

cides affect human behavior and fertility and cause depression, anxiety, and nervous

disorders. These pesticides are also available widely and sometimes available to

everyone which looks supportive in attempting suicides as many cases have been

observed in many Asian countries and Central America. Mostly, drugs when found

in lower concentrations pose no impacts on human beings, but as their concentration

reaches the threshold level, many neurological disorders have been found on them

Zoeller etal. (2012). According to the reports of SEER (2003) and Fisher (2004),

tumors mostly occur in the age of 20–35 which primarily originate from the germ

cells; also the rate of testicular cancer has increased since the last decade, which has

been found due to exposure to the environmental pollutants, which are in the form

of endocrine-disrupting chemicals. These chemicals have also been found in

increasing obesity in the people of Europe and Asia. Chemicals like vinyl chloride,

benzidine, benzene, and polycyclic aromatic hydrocarbons have been found in

increasing prostate cancer and diabetes in the human body (Azandjeme etal. 2013).

PCBs have been associated with nervous disorders, lower IQ, problems in thinking,

and writing in humans. These PCBs with other persistent organic compounds like

polybrominated biphenyl ethers have also been found in impairing towards the neu-

rotransmitter activity and synaptic disorders. Brominated ame retardants,

Table 5.1 (continued)

Micro pollutant Impacts Pathway Author

Pesticides, e.g., parquet,

rotenone, and maneb),

insecticides, e.g.,

organophosphate, fungicides

(e.g., fenhexamid, and

cyprodinil).

Parkinson disease,

younger age death,

cancer, and neurotic

disorders

Food stuffs of

vegetables,

absorption by water

Chorfa etal.

(2016)

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

Tributyltin (TBT), and triphenyltin (TPT) are also the main causes of problems in

thyroid hormones levels, puberty, and metabolisms disorders. Having strong asso-

ciation with some other endocrine- disrupting chemicals, it has been found that

reproductive disorders like 50% decrease in the sperm count, lower fertility, early

puberty, and genital malformations have been increased due to chemical abundance

and exposures. Such estrogenic chemicals have also been observed to cause uterine

broids, ovarian dysfunction, and subfertility in humans (Patisaul etal. 2013; Biro

etal. 2013; Buck Louis etal. 2014).

5.3 Possible Options forEnvironmental Renement

There is a serious problem concerned with the toxicity of micro pollutants in the

environment generated due to human activity by different ways. These pollutants

have created a threat for the ecosystem functioning and human health, so there is

urgent need to eliminate such toxic elements from the environment. The possible

ways being utilized for minimizing the effects of these pollutants have been

list below.

Fig. 5.4 Human health–related adverse effects of pesticides on different living being systems.

(Bilal etal. 2019)

M. Nawaz and S. S. Ahmad

5.3.1 Elimination by Physicochemical Application

It has been found that for the removal of personal care products (PCPs), there is a

need for some comprehensive treatment methods for their removal, and simple

coagulation or occulation is not sufcient (Ternes and Joss 2006). In this regard,

carbon in both forms, granular or powdered, is the best option for the removal of

contaminants like nonpolar compounds or endocrine-disrupting compounds by the

process of adsorption (Snyder etal. 2006; Bolong etal. 2009). Activated carbon

through the process of adsorption can remove the micro pollutants up to 90% as

Snyder etal. (2006) performed the process of adsorption for 66 PCPs and found that

only nine had efciency less than 50%, while all others were removed successfully

at the ve contacts hours by using 5mg/L PAC.For this process, it is also necessary

to dispose off PAC (powered activated carbon) and GAC (granular activated carbon)

very carefully through landlling or like other solid management systems because

these spent PAC and GAC need a high amount of energy for degeneration and pose

a risk to environmental health, because if these are left untreated, then it can be

more dangerous than micro pollutants.

5.3.2 Use ofBiological Treatments

Clara etal. (2005), Kimura etal. (2007), and Radjenovic etal. (2009) studied the

process of removal of contaminants from the environment by using two types of

technologies in the forms of conventional activated sludge process (CAS) and mem-

brane biological reactor (MBR) with the help of nitrifying bacteria for degradation

and sludge retention time for efcient removal. They observed that longer retention

rate for about fteen days provided the nitrifying bacteria with more diverse physi-

ological, metabolic, and in return, increased the process of mineralization.

Oppenheimer etal. (2007) also investigated that for some compounds (ibuprofen,

methyl paraben, galaxolide, triclosan, caffeine), there is no difference for removal

degree by conventional activated sludge and membrane biological reactor efcien-

cies. It has been also observed that for the removal of some other compounds from

wastewater like mefenamic acid, indomethacin, diclofenac, and gembrozil, the

MBR method works well than CAS which has been recorded 30–50%, but some

compounds like carbamazepine persist and cannot be removed by using both meth-

ods (Radjenovic etal. 2009). Batt etal. (2006) and Miège etal. (2008) also observed

the efciency of nitrifying bacteria and found that these bacteria have a very impor-

tant role in the process of decomposition of some highly toxic pharmaceuticals in

wastewater treatment plants which use higher retention rate time. They also found

that by using nitrogen with these biological systems, the removal efciency of PCPs

is more enhanced than other treatments, like the bio lter method.

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

5.3.3 Removal by Reverse Osmosis (RO)

Many authors have described the authenticity of working of Reverse Osmosis for

the removal of very toxic compounds, including personal care products (PCPs) and

endocrine-disrupting compounds from wastewater (Snyder etal. 2003; Oppenheimer

etal. 2007). It has been also conrmed by the studies of Braghetta and Brownawell

(2002) that removal efciency of RO is greater than 90%, while lower efciency has

been also noted for the diclofenac which is 55.2–60% and ketoprofen 64.3%.

Similarly, WERF (2005) found the removal rates more than 90% or even better in

case of naturally occurring and some synthetic compounds. It was also noted by

Oppenheimer etal. (2007) that RO can remove all such compounds occurring natu-

rally or synthetically, which are not possible to be removed by SRTs even for

30days.

5.3.4 Application ofNano Filtration

This nano ltration method is very cheap, common, and almost in the access of

every worker. This method consists of three steps which are followed by the next

step one an other. These steps are in the combination of adsorption, sieving, and

electrostatic repulsion and are mostly used for pharmaceuticals. The removals’ ef-

ciency also differs from compound to compounds depending on the structure and

reactivity. Mostly, the efciency of compounds is different depending on the solu-

bility, polarity, and membrane structure. This method of ltration is also very good

and 90% removal efciency has been achieved by this from wastewater (Yoon etal.

2006; Watkinson etal. (2007); Bolong etal. 2009).

5.3.5 Implication ofOzonation Oxidation Processes

These processes are mostly used for the removal of pharmaceuticals present in the

water. Many researchers including Huber et al. (2005), Andreozzi etal. (2005),

Ternes and Joss (2006), and Zimmermann etal. (2008) have found that medicines

such as antibiotics, carbamazepine, and some other pharmaceuticals have the ten-

dency to be reactive with molecular ozone, while some pharmaceuticals like inam-

matory compounds, diclofenac and indomethacin, are very stable and cannot be

degraded easily through the process of ozonation. This ozonation process is inu-

enced by many factors in the process of degradation of such pharmaceuticals, such

as quantity of oxidants, quality of wastewater, and mode of operation. Solubility of

compounds present in the water also matters in case of their degradation because

particulate matters present in high concentration show high removal trend after

reaction with ozone. Huber etal. (2005), Pauwels and Verstraete (2006), and Bouju

M. Nawaz and S. S. Ahmad

etal. (2008) showed that soluble compounds always react with ozone readily and

can oxidize hundred times more faster than insoluble ones because of having restric-

tion of diffusion rate, but removal rate is decreased with the consumption of more

oxidants due to high contents of particulates. So this technique can work best with

the low concentrations of compounds present in wastewater.

5.3.6 Mechanism ofDisinfection

The process of removal of toxic compounds through the process of ozonation some-

times performs partial decomposition in the case of some personal care products

(PCPs) due to high concentration of waste material. Huber etal. (2005) observed

that in the case of removal of PCPs, the oxidation process does partial disinfection

because compounds present in the wastewater are normally shielded with ozone or

hydroxyl ions. It has been also estimated that a concentration of 5–10mg O3/L with

a contact time of 15–20min is enough for the degradation of long chain of 2–3 unit

long compounds of PCPs. Ternes and Joss (2006) found that chlorine with its com-

pounds for the contact time of 30min by adding 10mg/L of ClO2 removed most of

bacteria and virus, while it is also very important to use the disinfecting compounds

in adequate quantity because Emmanuel etal. (2004) found that when NaClO is

used as a disinfecting agent with a dose of 1–8mg/L, it can reduce the amount of

bacteria very fast, but it has very serious consequences in terms of causing toxicity

for aquatic organisms by polluting their habitats.

5.3.7 Construction ofWetlands forNatural Polishing

Constructed wetlands can be very effective in the removal of pharmaceuticals by the

process of photolysis, phytoremediation, bioremediation, and soil uptake (White

etal. 2006; Matamoros etal. 2008). This involves the process through the vertical

and horizontal surfaces having benets of consisting aerobic, anaerobic, and anoxic

conditions with proximity to plant rhizosphere for the degradation of pharmaceuti-

cals compounds. Some pharmaceutical compounds like ibuprofen can be best

reduced by the aerobic process, while clobric acid and diclofenac can be best

removed by the anaerobic; similarly, halogenated compounds can be removed effec-

tively in the toxic environment (Lin and Reinhard 2005). Matamoros etal. (2008),

Bartels and von Tumpling (2008), and Zhou etal. (2009) found through experimen-

tal work that aerobic conditions are much efcient in removing the contaminants

than anaerobic conditions, while surface ow system can eliminate some POPs and

PCPs very actively from aquatic habitats. Similarly, high retention time rate

enhances more degradation of toxic elements in the water.

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

5.3.8 Use ofMembrane Bioreactor (MBR) Technique

This technology emerged recently emerged for water recycling, transforming waste

water into high-quality efuents for various usages at a large-scale. The Membrane

Bioreactors (MBRs) techniques have been available since the last two decades at

commercial use and have been well-recognized for handling various contaminants

such as pathogens, suspended solids, and nutrients. This can also work better than

conventional activated sludge process (CAS) technology (Melin et al. 2006;

Atkinson 2006). But this has some barriers in the case of treating trace elements like

endocrine-disrupting chemicals (EDCs), pesticides, and pharmaceutically active

compounds (De Wever etal. 2007). Tadkaew etal. (2010) studied the mechanisms

of removal of these trace elements and observed that some trace elements like ibu-

profen and bezabrate can be removed completely, while compounds like carbam-

azepine and diclofenac cannot be removed at all. So this membrane bioreactor BMR

can work best for selective removal of toxic compounds.

5.3.9 Elimination Through Ozone andBioltration Method

Ozone (O3) is the most frequently used technique for the process of disinfection and

as oxidants. This involves the transformation of organic compounds through reac-

tion with ozone by reacting with O3 and hydroxyl ions, which result in the destruc-

tion of compounds by decay of ozone in the waste water. The reaction of O3 and

hydroxyl radicals with organic compounds is very selective, while second order rate

of reaction also plays a signicant role in the degradation of compounds because the

order of reaction changes after every 10 orders of reaction. In the case of OH, it is

also a very less selective oxidant because its reactions with most of the compounds

need the diffusion-controlled mechanism (von Gunten 2003). The advanced oxida-

tion processes (AOPs) also depend upon the enhancement of the formation of OH

radicles. In this case, the combination of O3/H2O2 increases the conversion of O3 to

OH and reduces the reaction time needed for the micro pollutants. The combined

use of ozone/hydrogen peroxide (O3/) accelerates the conversion of O3. Legrini

etal. and Lee and von Gunten found that a combination of ultraviolet radiations

(UV) and H2O2 results in the production of OH which can act as an AOP as well. It

can also work for the transformation of micro pollutants by the direct process of

photolysis and by reacting with OH.In the case of this technology, it has been also

observed that OH acts as a powerful oxidant which scavenges dissolved organic

matter, carbonates, and bicarbonates. The OH can also react actively with nitrates,

but in this case, this behaves very poorly.

M. Nawaz and S. S. Ahmad

5.3.10 Removal Through Nitrifying Activated Sludge (NAS)

There is a serious effect of releasing of emerging pollutants like pharmaceutical and

personal care products (PPCPs) from sewage treatment plants, which can affect the

environment signicantly, because these plants have been not upgraded with new

technologies (Vieno etal. 2007; Smook etal. 2008; Radjenovic etal. 2009). For this

reason, it is very essential to use the recent techniques for handling such emerging

pollutants (Wick etal. 2009; Xu etal. 2010). In this regard, activated sludge process

has played a signicant role in the removal of such micro pollutants from the waste

water with special emphasis on the biological degradation (Barret etal. 2010), but

sufcient results have not been obtained by this treatment process due to certain

factors. Nitrifying activated sludge (NAS) has been identied as one important tech-

nique for the decomposition of such compounds. Zhou and Oleszkiewicz (2010)

and Hernández-Leal etal. (2011) found that 17a-ethinylestradiol can be degraded

well by using this process. This has been also tested by other researchers (Suarez

etal. 2010) by using nitrifying bacteria. This technique involves the elevated elimi-

nation of micro pollutants with NAS and has been attributed to the process of bio-

degradation with sorption mechanism (Tran etal. 2009).

5.3.11 Use ofBioaugment KMnO4 andOxidation

The frequent increase of micro pollutants and cyanobacteria into the drinking water

has created a problem worldwide as it directly threatens human health as the pollut-

ants cannot be removed completely by using any technique. In this regard, some

latest techniques by using KMnO4 pre-oxidation have demonstrated very good

results for the removal of such toxicants in the drinking water, but still are not useful

in removing the toxicants completely because traces of cyanobacteria still remain in

the water which can be toxic for its use. For this purpose, KMnO4 pre-oxidation in

collaboration with bioaugmentation in the form of sand ltration method has been

found good in removing cyanobacteria along with other micro pollutants from the

drinking water. KMnO4 with bioaugmentation, being a very traditional chemical

for oxidation, has been found very useful in removing the pollutants such as muta-

gens, microbial pollutants, and precursors of chloroform in drinking water. This is

also very effective in the process of coagulation and removal of algal blooms in the

water (Chen etal. 2009). Some authors (Ou etal. 2012) have reported that there is

10–30% increase with the use of 0–40mg/L of aluminum salt as coagulants and

pre-oxidation with 1.7 mg/L of KMnO4, but this is a drawback because this oxida-

tion process can leave toxic traces, which can make the water unhealthy. For this

purpose, KMnO4 pre-oxidation combined with bioaugmentation process has been

used with 2-hydroxy-4- methoxybenzophenone-5-sulfonic acid, which is a very

chronic pollutant with one species of cyanobacteria (Microcystis aeruginosa) and

has been found to be a model for removal of micro pollutant. In this case, biogenic

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

manganese oxide (BMO) can also further purify the quality of drinking water by

removing the cyanobacteria toxics (Zhang etal. 2017).

5.3.12 Through Enzymatic Bioremediation

Use of enzymes have been as widely accepted by producing the frequent results

since many years and also with the development of immobilized oxidative enzymes

have their multiple applications. Currently, these immobilized oxidative enzymes

have produced a pathway towards green environment production by using their cer-

tain amounts for removal of very toxic micro pollutants which can be a challenge

for human health. Gonzalez-Gil etal. (2018) have found that among these enzymes,

laccases and horseradish peroxidase have been frequently used since the last ve

years, producing good results as these have enough capacity to withstand the reac-

tion mixture and easy to separate. However, still there is need to develop new bio-

remediated techniques with the help of these enzymes as there is great diversity of

micro pollutants.

5.3.13 By Advanced Anaerobic Digestion Systems

Current research work on the micro pollutants’ removal by many techniques has

found the useful aspects of manure toxicants’ removal with the production biogas

through advanced anaerobic digestion systems. This system can also work better for

more treatments, including pasteurization, which can enhance the process of

removal of pathogens along with micro pollutants. These micro pollutants in the

form of antimicrobial compounds, manure contaminants, and other pharmaceuticals

can be removed better through the use of activated carbon by the process of adsorp-

tion. The activated carbon can increase the production of methane gas with the

removal of various antibiotic compounds such as lincomycin, ciprooxacin, and

erythromycin in the anaerobic digestion with the addition of chicken manure and

food waste particles (Zhang and Cai 2019). The use of biochar precursors in this

case also has been found to be good for the degradation of contaminants along with

activated carbon. Duan etal. have also found that biochar has enough ability to

produce the surface area for making the microbial colonies which can degrade the

contaminants produced in the soil. Similarly, Basso etal. (2013) and Tang etal.

(2013) reported the effect of using activated carbon in the form of biochar which

contained removal ability for polychlorinated compounds. The studies of Zhang and

Cai (2019) have also reported the importance of advanced anaerobic systems by

using activated carbon with the combination of biochar for the removal of very toxic

heavy metals present in the soil. It has been also found that there was an increase of

87–95% with the addition of activated carbon in the form of biochar. This system

M. Nawaz and S. S. Ahmad

has been also found very cheap, accessible, and very easy to handle and precursors

have no further harmful impacts on the environment.

5.3.14 Use ofMicrobial Genes forDegradation

In addition to some physical and chemical techniques being used for the removal of

micro pollutants in the wastewater which can produce better results, microbial deg-

radation for organic and inorganic micro pollutants is also one of the best options

for their removal (Carey and Migliaccio 2009). According to another study

(Gonzalez-Gil et al. 2018), microorganisms can enhance the removal of certain

kinds of harmful nutrients such as extra organic carbon, nitrogen, and phosphorus

from the waste streams. Among the removal of organic micro pollutants, only some

of them can be removed, while others are partially removed through the possible

pathways including biosorption and bioaccumulation, but most successful is the

biodegradation which is done by the use of some microorganisms or their parts.

This process involves three steps as follows:

1. Microorganisms use these micro pollutants as a source of carbon and energy,

e.g., toluene (Woods etal. 2011) and some pesticides, by converting them to CO2

or sometimes convert these into solid biomass. In the case of heavy metals which

contain no carbon, these microorganisms can also convert them by using elec-

tron receptors through precipitation (Fischer and Majewsky 2014).

2. Microorganisms can also decrease the toxicity of these micro pollutants by trans-

forming their molecular structure such as antibiotics by the process of hydroly-

sis. It is worth notable that all resistant antibiotic genes do not encode the protein

that degrades the antibiotics, but many efux pumps can provide resistance

against the contaminants without changing their structure (Yelin and

Kishony 2018).

3. Microorganisms can also change the micro pollutants by the process of come-

tabolism such as pesticides, bisphenol, and pharmaceuticals (Fischer and

Majewsky 2014)). This process occurs when micro pollutants pass through small

structural changes like acetylation, methylation, and hydroxylation by using

other growth substrates. This process occurs by the consumption of these sub-

strates by the enzymes which work on them. These enzymes cannot be regulated

in the presence of micro pollutants but can work better in the presence of these

substrates. It has been also observed that ammonia oxidizing archae can trans-

form pharmaceuticals by oxidizing these compounds (Men etal. 2016).

Some authors (Gonzalez-Gil etal. 2017; Guo etal. 2017; Jiao etal. 2017) have

reported that many enzymes can encode the microbial gene sequence, which are

then useful in removing the micro pollutants such as antibiotics and b-lactamase.

5 Impacts of Micro Pollutants on Human Health and Enumerating the Environmental…

5.3.15 Coagulation/Sedimentation

Coagulation or sedimentation is a very simple and older technique for the removal

of colloidal particles; although it can remove the micro pollutant completely, results

have been found sufcient for removing the different pollutants. Stackelberg etal.

(2007) reported 15% of the micro pollutants in the form of pharmaceuticals through

the process of coagulation. Similar ndings have also been found by Vieno etal.

(2007) that micro pollutants like organic materials, heavy metals, and some pharma-

ceuticals can be signicantly removed by the process of coagulation. The reports of

Ternes etal. (2002) and Adams etal. (2002) also indicated the removal of pharma-

ceuticals by about 30%, and during this process, Fe+3 were removed. In this pro-

cess, coagulation with adsorption in the form of clay particles through electrostatic

interaction between micro pollutants and coagulants was found successful under

sunlight (Nikolaou et al. 2007). It has also been found by Huerta-Fontela et al.

(2011) that the removal efciencies of coagulation vary from 9% to 100% depend-

ing upon the conditions and nature of pollutants. It was found that removal tendency

of pharmaceuticals was 70%, while 40–60% was found in case of PCPs.

5.4 Conclusion andRecommendations

Through this study, it is concluded that micro pollutants are present in different

forms including organic to inorganic and have different sources in which human

activities are playing a pivotal role in their generation and reaching to target sites.

Among the sources, human activities are contributing largely than natural processes

in the form of industries, pharmaceuticals industries, and irregular fertilizers use.

These micro pollutants are found in the form of heavy metals, pharmaceuticals, and

endocrine-disrupting chemicals. These micro pollutants after their release mainly

travel through the water cycle and then reach the human body directly or indirectly

and produce adverse impacts. Many researchers have observed their harmful

impacts on the human body when exposed directly or indirectly to such micro pol-

lutants. These impacts are mild to chronic and irreversible depending upon the

nature of pollutants. Although these pollutants are being released from different

sources, these mostly end up in the water, thus converting to waste water. Water

having such toxicants reaches to human body directly or indirectly through the food

chain and causes different problems. These can also produce changes from chromo-

somal to modication in different organs through different diseases which are

sometimes irreversible depending upon the nature of pollutants. There is a dire need

for the removal of such contaminants from the environment produced by any source

through using different techniques. This chapter has focused on the availing of some

possible tools based on old to very recent methods for their removal from the envi-

ronment for the sake of saving human health. There are numerous technologies

which can be used based on physical, chemical, and biological aspects. Through

M. Nawaz and S. S. Ahmad

this study, it can be recommended that it is very necessary to reduce the possible

sources mainly based on human activities and also to stop unnecessary use of chem-

icals fertilizers to the crops without any recommendation by the experts. It is also

very important to minimize all possible sources rather than to remove them from the

environment once these enter the environment.

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Chapter 6

Emerging Organic Contaminants,

Pharmaceuticals andPersonal Care

Products (PPCPs): AThreat toWater

Quality

BashirAhmad andMuhammadImran

Abstract Underground water contamination is a big challenge of this century.

Emerging organic contaminants (EOC), personal care products (PCPs), industrial

products, pesticides, pharmaceuticals, engineered nanomaterials, veterinary prod-

ucts, and food additives may pose threat to human health, and ecosystem. The

ground watercontaminationwhich is the main source of drinking water, is an area

of greater concern for the present and future of human civics. This chapter encom-

passes the possible emission sources in groundwater, contaminated surface water,

and the fate of EOC, PCPs, and pharmaceuticals. The advancements in analytical

techniques and precise equipment, quantitative detection of these contaminants is

now possible and more compounds can be speckled now. Probably it is not possible

to remove these pollutants from underground water reservoirs; however; detection

of contaminants, their control at source, awareness campaigns and regulatory frame-

work are possible approaches to compete this alarming challenge.

6.1 Organic Contaminants

A distinct array of synthetic organic composites is widely utilized for industrial

practices, human and animal healthcare, food making, and preservation worldwide.

The interest in contaminants’ occurrence in the aquatic ecosystem, their impact on

the environment, and possible toxicity even at low concentrations are noted in recent

B. Ahmad (*) · M. Imran

Biotechnology Division, Department of Biological Sciences, International Islamic University,

Islamabad, Pakistan

e-mail: Bashir.ahmad@iiu.edu.pk; muhammad.phdbt108@iiu.edu.pk

106

few last decades (Halling-Sørensen etal. 1998; Stan etal. 1994; Kümmerer 2009;

Daughton and Ternes 1999; Schwarzenbach etal. 2006; Stan and Linkerhagner 1992).

Underground water contamination is an increasing concern, relatively poorly

identied when compared with freshwater sources (Pal etal. 2010). Organic con-

taminants were beforehand not measured or recognized critical in groundwater as

far as circulation or xation was concerned, but now they are widely detected and

known as emerging contaminants (EC) which are unfriendly biologically and for

public health. Manufactured new chemicals or thiermodications or exiting chemi-

cal disposal could create new ECs. The ECs’ signicance and presence in the envi-

ronment are only revealednow (Daughton 2004).

The organic micro-contaminants in an aqueous atmosphere detection was impo-

siblebut recently, analytical procedures improvementresolve this issue (Petrovic

and Barcelo 2006; Lindsey et al. 2001). Richardson and Ternes analyzed recent

emerging micro-contaminants (Richardson and Ternes 2011).

The term degradates is widely used for different compounds (as well as

theirmetabolites and transformation commodities)such as product of personal care

products (PCPs); pharmaceuticals, pesticides, engineered nanomaterials, industrial

products, food additives, and veterinary products (Huschek etal. 2004; Hilton etal.

2003; Fent etal. 2006; Besse and Garric 2008; Crane etal. 2006; Celiz etal. 2009).

The ECs in atmosphere wastewater and surface water are easily characterized

and have greater diversity as compared to groundwater. The burdenofcontaminants

in waste and surface water is high. The surface water sources areused for public

water supply, in whichECcould be analyze (Pal etal. 2010; Houtman 2010),the

incidence and fate of ECs founded trace contaminants (Murray etal. 2010). The

Lapworth etal.’s (2012) systematic analysis raised the issue of worldwide ECs in

the groundwater and thierwidespread in groundwater sources, (Lapwort etal. 2012).

Environmentally signicant concentration of ECs is 102–104 ng/L; several

endocrine- disrupting ingredients have been identied in groundwaters. Many ECs

have the maximum priority materials for treatment and management in terms of

human health effects and potential environmental effects. Many ECs are unregu-

lated which has current analytical institutional challenges (Kavanaugh 2003).

A wide-ranging diversity of PPCPs are detected in the aqueous atmosphere

worldwide, stimulants, analgesics, cosmetics, disinfectants, antimicrobials, anti-

pyretics, fragrances, antibiotics, steroids, and antidepressants, commonly used on

daily basis for several purposes (Daughton and Ternes 1999).

The PPCPs can arrive in the aqueous atmosphere directly or indirectly via fertil-

izing, livestock breeding, landll leachate, and sewage discharge, resulting in unde-

sirable impacts on creatures and ecosystems (Grice and Goldsmith 2000; Corbel

etal. 2009; Ricart etal. 2010).

The regulated pollutant number will produce slowly in the coming decades. The

anthropogenetic microorganic contaminants observed in the river are needed under

the framework of various state rules and regulations (EC.Groundwater Directive

2006; EPA 2006).

B. Ahmad and M. Imran

107

The overall aim is to improve and protect the water source quality. From the

European perspective, groundwater condition is presently legalized in compliance

with Water Framework Directive (WFD) and Groundwater Directive (GD). The

drinking water is controlled by the Drinking Water Directive, while pesticides are

controlled by Plant Protection and Biocides Directives. GD and WFD were estab-

lished to protect groundwater and water-dependent ecosystems. These required

standard protocols for ECs that achieved its unawareness on many micro-

contaminant chemicals’ poisonous behavior, impact, and limited surveillance data

and limited values are not possible to yet establish.

The European Drinking Water Directive (EDWD) sets some parameters for the

organic micropollutants which consist of chlorinated solvents, aromatic hydrocar-

bons, and disinfection products. The signicance of ingredients recognized in the

WFD daughter directive included Di(2-Ethylhexyl) phthalate, octyl, and nonylphe-

nols, benzene, specied polyaromatic hydrocarbons (PAH), and various chlorinated

hydrocarbons (Water Framework Directive 2000, 2006).

The European Commission’s objective is to set boundaries for 16 new substances

underneath WFD containing synthetic contraceptives, anti-inammatory medicine,

and peruoro octane sulfonate (PFOS) (EC.EQSD 2008; EC.Review of priority

substances 2011).

A similar condition arises worldwide. Regulatory structures are required to con-

trol prospective micropollutant resources and to monitor the organic pollutants in

the aquatic atmosphere. A large number of organic substances were not subjected to

the current level of a rule. The US Environment Protection Agency sets legal stan-

dards for 125 micropollutants in drinking water; 31 might be considered as micro-

organic contaminants excluding pesticides; no pharmaceuticals or PCPs

contaminants were included. The US EPA announced the latest pollutant candidate

list (CCL-3) 2009 that contained three pharmaceuticals, eight hormones, PFOS, and

peruorooctanoic acid (PFOA) (USEPA 2009; Petrovic and Barceló 2006).

6.1.1 Emerging Groundwater Contaminants (EGC) Types

It is much more identied about the groundwater pesticides when related with other

substances like pharmaceuticals (poorly characterized). The risks for human health

for several compounds are also recorded, their capacity to travel in the aqueous

atmosphere is not fully investigated, and ecological persistence is unfamiliar.

Considering their behavior, resources, mobility, physical and chemical characteris-

tics throughout the aqueous atmosphere, and related risks, the following types of

micro-contaminants are considered emerging in groundwater (Fig.6.1).

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

108

Types of Emerging Groundwater Contaminants

Pesticides PharmaceuticalsLife-style

Compounds

Personal

Care

Compounds

Industrial

Additives

Food AdditivesWater

Treatment

products

Flame/Fire

Retardants

Surfactants Hormones

and

Sterols

Ionic

Liquids

1). veterinary and human

antibiotics

2). prescription drug

3). nonprescription drugs

4). iodinated X-ray contrast

media

Caffeine, nicotine

and its metabolite

1). N,N-diethyl-

meta-toluamide

(DEET)

2). parabens –alkyl

esters of p-

hydroxybenzoic

acid

3). triclosan

4). tonalide and

galoxalide

5). benzophenones

and

methoxycinnamates

1,4-dioxane, a 1,1,1,-trichloroethane

Benzotriazole

Dioxins

Triethyl citrate

Butylated

Hydroxyanisole

and

Hydroxytoluene

camphor, 1,8-

cineole

(eucalyptol),

citral,

citronellal, cis-

3-hexenol,

heliotropin,

phenyl ethyl

alcohol,

triacetin, and

terpineol.

N-nitrosodimethylamine

(NDMA)

Polybrominated diphenyl ether

octyl- and 7 nonyl-phenol, cetrimonium, chloride

estrone, estriol,

17α- and 17β-

estradiol,

nandrolone,

ethinylestradiol, and

diethylstilbestrol

pyridinium, pyrrolidinium, or morpholinium moieties)

quaternary ammonium salts

Fig. 6.1 Different types of emerging groundwater contaminants (EGC)

B. Ahmad and M. Imran

109

6.1.2 Pesticides

Pesticides are found in trace concentrations in groundwater and are known as highly

recognized contaminants. In the 1990s, simazine, atrazine, and a variety of other

herbicides were discovered in the groundwater across the world (Bauld 1996; Close

1996; Kolpin etal. 1998; Tappe etal. 2002; Zanella etal. 2011; Spliid and Køppen

1998; Water 2011). New parent compounds were dectected afterimproved analyti-

cal techniques e.g., metaldehyde (UK) (Source: http://www.water.org.uk/home/

policy/positions/metaldehyde- brieng), and known as merging contaminant. If we

study 20 year ago was obvious that pesticide degradates need to be taken into con-

sideration (Galassi etal. 1996; Kolpin etal. 2000).

Several studies demonstrated that pesticide metabolites could be found in

groundwater in higher concentrations, while the parent compounds of agronomic

and amenity detection limits are low (Kolpin etal. 2004; Lapworth and Gooddy

2006). Naturally, the degradates are biologically active compounds that could be

toxic. The pesticide registration procedure is common, but the monitoring process

is notadequately observed.

6.2 Pharmaceuticals

Pharmaceutical substances in the aquatic ecosystem have been recognized and also

have concerns (Richardson and Bowron 1985). The primary routes of these com-

pounds into the environment are: (a) unused products disposal; (b) agriculture prac-

tices; and (c) humans excretion (Barnes et al. 2008). A wide spectrum of

pharmaceutical goods have been found in groundwater-surface and discarded in

wastewater (Nikolaou, Meric and Fatta 2007; Pérez and Barcelo 2007; Vulliet and

Cren-Olive 2011; Miller and Meek 2006). These include the following:

1. Human and veterinary antimicrobials: Lincomycin, tetracycline, sulfamethoxa-

zole, clobric acid, and ciprooxacin.

2. Doctor-prescribed medications: Salbutamol, codeine, diclofenac, and

carbamazepine.

3. Nonprescription medications: Salicylic acid, ibuprofen, and acetaminophen or

paracetamol.

4. Iodinated X-beam contrast media: Iopromide and iopamidol.

The prospective risks for surface water are noted from Tamiu and chemotherapy

drugs (cyclophosphamide or 5-uorouracil, ifosfamide) and illicit medications

(amphetamines and cocaine) (Singer et al. 2007; Moldovan 2006; Zuccato etal.

2000; Johnson etal. 2008; Buerge etal. 2006; Kasprzyk etal. 2008) (Table6.1).

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

110

6.3 Lifestyle Compound

The groundwater is affected by sewage waste like caffeine, nicotine, and its metabo-

lite cotinine (Godfrey etal. 2007; Teijon etal. 2010; Seiler etal. 1999). Saccharine,

acesulfame, sucralose, and cyclamate are found in high concentrations in ground-

water, which is affected through sewage inltration ponds. Buerge etal. (2009)

demonstrated acesulfame is a commonly detectable containment in the aquatic

atmosphere due to its common use, persistence, and mobility.

1. N, N-diethyl-meta-toluamide DEET

2. Parabens-alkyl esters of p-hydroxybenzoic destructive

3. Bactericide and antifungal agents, such as triclosan

4. Polycyclic musks, such as tonalide and galoxalide

5. UV lters/sunscreen, such as benzophenones and methoxycinnamates.

Triclosan and methyl triclosan were detected in the surface water in Switzerland,

which reected persistent metabolite (Van Stempvoort et al. 2011; Buerge et al.

2009; Lindström et al. 2002). Tonalide (AHTN), HHCB-lactone, and galoxalide

(HHCB) were found in wastewater (Horii etal. 2007) and compounds used as a

marker for wastewater surface (Fromme etal. 2001; Buerge etal. 2003a).

The synthetic musk compounds were discovered in aquatic sediment, surface

water, digestion in sh, biota samples in bioaccumulation, and environmental, sew-

age, and sewage sludge; human hazard assessment (Table6.3) was debated (Heberer

Table 6.1 Summary and statistics’ analysis to maximum concentrations (ng/L) of ECs discovered

in 4 studies (Kavanaugh 2003)

Class Compound Use± N Lowest Average Highest

Pharmaceutical Ibuprofen+ Anti-inammatory** 14 0.6 1491 12,000

Sulfamethoxazole Antibiotic 15 5.7 252 1110

Paracetamol+ Analgesic 8 15 15,142 120,000

Diclofenac Anti-inammatory 11 2.5 121 590

Clobric acid+* Lipid regulator 8 4 1113 7300

Lincomycin Antibiotic 5 100 188 320

Ketoprofen Anti-inammatory 6 3 611 2886

Triclosan Antibiotic 6 7 509 2110

Iopamidol X-ray contrast media 5 130 760 2400

DEET Insect repellent 4 454 2251 6500

Propyphenazone Analgesic 5 15 553 1250

Sulfamethazine Veterinary medicine 5 120 298 616

Salicylic acid+* Analgesic 4 43 418 1225

Phenazone Analgesic 4 25 1503 3950

Carbamazepine Antiepileptic 23 1.64 5312 99,194

Primidone Barbiturate 4 110 3380 12,000

N=number of studies, ±primary use, *degrade, **also an analgesic, +known or potential EDS

B. Ahmad and M. Imran

111

2002). Most of these compounds are being used as sunscreen lipophilic conjugated

aromatic compounds found in an aqueous atmosphere (Jeon etal. 2006).

6.4 Industrial Condiments andTheir By-products

Industrial compounds are released in the atmosphere in wide range, which are prob-

lematic and alarming for the world. These compounds are polyaromatic hydrocar-

bons and fuel oxygenate methyl tertiary-butyl ether, plasticizers or resins bisphenols,

adipates, chlorinated solvents, and phthalates (Jeon etal. 2006; Garrett etal. 1986;

Verliefde etal. 2007; Moran etal. 2005, 2007). Mostly industrial compounds are not

emerging contaminants and have limits in drinking water. But some degradation

products are known as emerging contaminants (ECs).

Industrial emerging contaminants (ECs) are:

1. Benzotriazole derivatives

2. 1,4-dioxane, a 1,1,1, -trichloroethane

3. Dioxins, e.g., antimicrobial additive (triclosan) (Abe 1999; Giger etal. 2006;

Voutsa etal. 2006; Stuart and Lapworth 2013; Mezcua etal. 2004).

6.5 Food Additives

Some nutritional supplements are known as oxidizing agents or endocrine disrupt-

ers (Jobling etal. 1995). Triethyl citrate is a food additive which stabilizes foams,

pharmaceutical coatings, and plasticizer. Both Hydroxytoluene and Butylated

hydroxyanisole are food-fat preservatives. Other food additives are citronellal, cam-

phor, triacetin, cis-3-hexenol, phenyl ethyl alcohol, 1,8-cineole (eucalyptol), terpin-

eol, citral, and heliotropin.

6.6 Water Treatment By-products

The haloacetic acids and trihalomethanes are used for the water disinfection process

(Boorman 1999). N-nitrosodimethylamine (NDMA) is referred to as a drinking

water pollutantresulting reactions occurred in the chlorination process or industrial

contamination, due to high concentrations of carcinogen agents in wastewater dur-

ing the chlorination process is used intentional or unintentional in municipal waste-

water (Mitch etal. 2003). The disinfection by ozone instead of chloramines can

increase the potential risk of toxic products (Richardson and Bowron 1985). Other

products of water purication are epichlorohydrin and polyacrylamide (Mezcua

etal. 2004).

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

112

Table 6.3

US Geological Survey’s (USGS) National Water-Quality Assessment (NAWQA),

Compounds with Detections Meeting Applicable Criteria (Bexeld etal. 2019)

Analyte

Conc

used for

detections

(ng/L)a

Number

detections

meeting

criteria

Detection

frequency

(%)

Detection

frequency

for PAS

sites

alone (%)

Detection

frequency

for MAS

sites

alone (%)

Median of

detected

concentrations

(ng/L)

7-Dimethylxanthine’ 21 9 0.8 0.7 1.2 160

Bupropion 3.6 3 0.3 00 1.2 9.3

Cimetidine 21 1 0.1 0.1 0.0 23.6

Pseudoephedrine 5.5 4 0.4 0.0 1.6 8.1

Acyclovir 4.4 1 0.1 0.1 00 5.7

Atenolol 4.8 1 0.1 0.1 00 8.7

Carisoprodol 25 1 0.1 0.1 0.0 58.2

Caffeine 65.6 3 0.3 00 1.2 212

Carbamazepine 2.2 18 1.6 1.2 3.2 8.5

Acetaminophen 3.6 4 0.4 0.1 1.2 8.8

Hydrocortisone 29 1 0.1 0.1 0.0 69.3

Fluconazole 35 1 0.1 0.1 0.0 50.8

Lamivudine 3.2 1 0.1 0.1 0.0 11.4

Dextromethorphan 1.6 2 0.2 0.2 0.0 3.5

Fenobrate 71 1 0.1 00 0.4 32.9

Metformin 6.6 2 0.2 0.2 0.0 35.6

Fluoxetine 5.4 1 0.1 0.1 0.0 17.1

Methotrexate 26 3 0.3 0.4 0.0 39.1

Citalopram 3.3 2 0.2 0.1 0.4 5.5

Pentoxifylline 4.7 1 0.1 0.1 0.0 8.1

Meprobamate 17 8 0.7 0.7 0.8 21.1

Metaxalone 7.8 1 0.1 0.1 0.0 22.2

Lidocaine 19 2 0.2 0.1 0.4 33.6

Methadone 3.8 1 0.1 0.1 0.0 43.0

Nordiazepam 10 1 0.1 0.1 0.0 17.1

Hormone

Testosterone 1.6 1 0.1 0.1 00 3.0

Bisphenol A! 160 7 0.6 0.4 1.6 193

4,4′-Bisphenol F 10 1 0.2 0.3 00 70.8

Cholesterol 400 3 0.3 0.2 0.4 480

B. Ahmad and M. Imran

113

Groundwater Samples, and Summary of detections and detected Concentrations for Hormone and Pharmaceutical

Maxi- mum of

detected

concentrations

(ng/L)

Human-

health

benchmark

(ng/L)b

Human-

health

benchmark

type/

sources

Lowest

therapeutic

dose (mg/

day)’

Maximum

concentration

as % of HHB

Number

detections

> HHB

Number

detections

> 10% of

HHB

Maximum

lifetime

cumulative

mass as %

of LTD

416 – – NA NA NA NA

22.7 NA – 300 _ 0.48

23.6 30,000 MDH.WSV 0 0.079 0 0

15.2 NA 0.40

5.7 NA – 600 NA NA NA 0.06

8.7 2,000 MDH.WSV 0.44 0 0

58.2 30,000 MDH.WSV 0 0.19 0 0

667 – – NA NA NA NA

162 40,000 MDH.HRL 0 0.41 0 0

17.0 200,000 MDH.HRL 0.009 0 0

69.3 20 MDH.WSV 347 1 1

50.8 400 MDH.WSV 12.7 0 1

11.4 NA – 100 NA NA NA 0.73

5.2 NA – 60 NA NA NA 0.55

32.9 600 MDH.WSV 5.48 0 0

38.7 4,000 MDH.WSV 0 0.97 0 0

17.1 200 MDH.WSV 8.54 0 0

86.0 NA 0.7 780

7.4 NA – 20 NA NA NA 2.35

8.1 90,000 MDH.WSV 240

164 10,000 MDH.WSV 1.64 0 0

22.2 NA – 2400 0.06

39.6 NA NA NA NA NA NA NA

43.0 NA 5 55

17.1 NA NA

3.0 7,000 AUS 0.43

430 20,000 MDH.HRL 2.15

70.8 NA

570

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

114

6.7 Flame or Fire Retardants

The polybrominated diphenyl ether ame retardants utilized in industries and

household entered the environment through waste disposal by landlls or incinera-

tion processes. Phosphate-based retardants (tris-(2-chloroethyl) phosphate) formed

nonammable barriers, utilized in consumer products and industries (Rahman etal.

2001; Weil etal. 1996).

6.8 Surfactants

The cationic, amphoteric, anti-foaming anionic, and nonionic surfactants agents are

found in wastewater (Gonzalez etal. 2007). The priority pollutants, octyl and nonyl-

phenol (OP and NP), are used for the manufacturing of alkylphenol ethoxylates

(APEs) that produced by nonionic surfactants (Table6.2). The parent ethoxylates

and their metabolites, alkylphenols and carboxylic degradation products are persis-

tent in the aquatic atmosphere (Soares et al. 2008; Montgomery and Reinhard

2003). Nonionic polyethylene glycol-based composites and Siloxanes (anti- foaming

agents) were used in several PPCPs, having concern about the possibility of intoxi-

cation and transportation in the aquatic atmosphere (Richardson 2007).

The cationic surfactants contain quaternary ammonium salts, like emulsiers,

cetrimonium chloride (antiseptics), and homologs, recognized as ECs in marine

sediments (Ahrens etal. 2009). Amphoteric surfactants are coconut-based products

(Cocamidopropyl betaine). The anionic surfactants are peruorinated compounds

(PFOS and PFOA), being utilized in the surfactants, reghting foams cosmetics,

paints, food packaging, and cookware coatings. They are observed in wastewater

and surface water, persistent in the environment (Lara-Martin etal. 2010; Poynton

and Vulpe 2009). PFOS was found in the surface water and waste efuents of Japan

(Harada etal. 2003; Saito etal. 2003).

6.9 Hormones andSterols

Sex hormones, including androstenedione, testosterone, progesterone, estrone,

estriol, 17α-, and 17β-estradiol, as well as their synthetic hormones, such as nandro-

lone, and synthetic estrogens (xenoestrogens) such as diethylstilbestrol and

17α-ethinylestradiol, are commonly used as contraceptives agents (Table 6.2).

Several compounds were present in wastewater and treated as efuent (Vulliet and

Cren-Olive 2011; Johnson etal. 2000; Standley etal. 2008); the cholesterol and its

metabolite (5β-coprostanol), plant sterols (stigmasterol, β-sitosterol, and stigmasta-

nol), and related molecules. The sterol (phytoestrogens) is used in the plants which

B. Ahmad and M. Imran

115

Table 6.2 Different intensities of PPCPs were found in groundwater in 2012–2014

PPCPs Research area

Samples

Detection

frequency

(%)

Conc

(ng/L) References

Antibiotic

Sulfamethoxazole Switzerland 16 12–19 BDL-

Morasch

(2013)

Baix Llobregat,

Barcelona, Spain

121 29 9–46 Cabeza etal.

(2012)

Barcelona, Spain 32 80–100 BDL-

López etal.

(2013)

Jianghan Plain, China 27 4–42 BDL-

0.8

Tong etal.

(2014)

Vicinity of municipal

landlls in Guangzhou,

China

28 24 28.7–

124.5

Peng etal.

(2014)

Barnstable County,

Massachusetts, USA

20 60 0.1–

113

Schaider

etal. (2014)

Sulfamethazine Baix Llobregat,

Barcelona, Spain

121 46 BDL-

83.9

Cabeza etal.

(2012)

Barcelona, Spain 32 23–100 BDL-

29.2

Cabeza etal.

(2012)

Jianghan Plain, China 27 8–63 BDL-

1.2

López etal.

(2013)

Ooxacin Barcelona, Spain 32 100 10.2–

367

Tong etal.

(2014)

Jianghan Plain, China 27 10–68 BDL-

7.6

López etal.

(2013)

Vicinity of municipal

landlls in Guangzhou,

China

28 9 BDL-

44.2

Tong etal.

(2014)

Noroxacin A karst system near

Yverdon-les-Bains,

Switzerland

16 6–19 BDL-2 Peng etal.

(2014)

Barcelona, Spain 32 69–100 BDL-

462

Morasch

(2013)

Jianghan Plain, China 27 64–79 BDL-

47.1

López etal.

(2013)

Azithromycin Danube River, Serbia 44 5 BDL-

Tong etal.

(2014)

A karst system near

Yverdon-les-Bains,

Switzerland

16 12 BDL-

Radovic

etal. (2014)

Barcelona, Spain 32 80–100 BDL-

1620

Morasch

(2013)

Jianghan Plain, China 27 100 0.2–0.7 Morasch

(2013)

(continued)

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

116

Table 6.2 (continued)

PPCPs Research area

Samples

Detection

frequency

(%)

Conc

(ng/L) References

Trimethoprim A karst system near

Yverdon-les-Bains,

Switzerland

16 6 BDL-

0.4

López etal.

(2013)

Baix Llobregat,

Barcelona, Spain

121 19 BDL-3 Tong etal.

(2014)

Barcelona, Spain 32 20–100 BDL-

9.41

Morasch

(2013)

Jianghan Plain, China 27 4–68 BDL-

5.2

Cabeza etal.

(2012)

Vicinity of municipal

landlls in Guangzhou,

China

28 4 BDL-

10.5

López etal.

(2013)

Barnstable County,

Massachusetts, USA

20 5 BDL-

0.7

Tong etal.

(2014)

Anti-inammatories

Ibuprofen Serbia 6 17 92 Schaider

etal. (2014)

Barcelona, Spain 32 46–92 BDL-

988

Petrovic

etal. (2014)

Rastatt, Germany 51 2 BDL-

104

Petrovic

etal. (2014)

Vicinity of municipal

landlls in Guangzhou,

China

28 11 BDL-

57.9

López etal.

(2013)

An experimental

agricultural eld in

Ottawa, Canada

NA NA 10 Wolf etal.

(2012)

An urban-inuenced

karst aquifer in the

Wadi Shueib, Jordan

32 14 BDL-

Peng etal.

(2014)

Naproxen Serbia 6 17 27.6 Wolf etal.

(2012)

A karst system near

Yverdon-les-Bains,

Switzerland

16 6–12 BDL-

Gottschall

etal. (2012)

Baix Llobregat,

Barcelona, Spain

121 NA 145 Petrovic

etal. (2014)

Barcelona, Spain 32 8–40 BDL-

5.59

Morasch

(2013)

Vicinity of municipal

landlls in Guangzhou,

China

28 3 BDL-

86.9

Cabeza etal.

(2012)

(continued)

B. Ahmad and M. Imran

117

Table 6.2 (continued)

PPCPs Research area

Samples

Detection

frequency

(%)

Conc

(ng/L) References

Diclofenac A karst system near

Yverdon-les-Bains,

Switzerland

16 6–12 BDL-3 López etal.

(2013)

Baix Llobregat,

Barcelona, Spain

121 NA 15–55 Tong etal.

(2014)

Barcelona, Spain 32 40–100 BDL-

380

Morasch

(2013)

Rastatt, Germany 51 2 BDL-

129

Cabeza etal.

(2012)

Urban catchment area

in Singapore

138 4 BDL-

López etal.

(2013)

Salicylic acid Serbia 6 83 BDL-

2.5

Wolf etal.

(2012)

Baix Llobregat,

Barcelona, Spain

121 41 BDL-

9.3

Zemann

etal. (2015)

Barcelona, Spain 32 100 26.6–

620

Petrovic

etal. (2014)

Vicinity of municipal

landlls in Guangzhou,

China

28 98 BDL-

2015

Cabeza etal.

(2012)

Urban catchment area

in Singapore

138 58 BDL-

1994

López etal.

(2013)

Lipid regulators

Bezabrate Baix Llobregat,

Barcelona, Spain

121 45 BDL-

4.22

Zemann

etal. (2015)

Barcelona, Spain 32 54–100aBDL-

25.8

Peng etal.

(2014)

Rastatt, Germany 51 8 BDL-

Cabeza etal.

(2012)

Gembrozil Baix Llobregat,

Barcelona, Spain

121 NA 15.5 López etal.

(2013)

Barcelona, Spain 32 62–100 BDL-

751

Wolf etal.

(2012)

Rastatt, Germany 51 2 BDL-

Cabeza etal.

(2012)

Barnstable County,

Massachusetts, USA

20 5 BDL-

1.2

López etal.

(2013)

Urban catchment area

in Singapore

138 4 BDL-

Wolf etal.

(2012)

(continued)

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

118

Table 6.2 (continued)

PPCPs Research area

Samples

Detection

frequency

(%)

Conc

(ng/L) References

Clobric acid Barcelona, Spain 32 31 BDL-

7.57

Schaider

etal. (2014)

Rastatt, Germany 51 4 BDL-

1350

Zemann

etal. (2015)

Vicinity of municipal

landlls in Guangzhou,

China

28 3 BDL-

73.9

López etal.

(2013)

Urban catchment area

in Singapore

138 9 BDL-

Wolf etal.

(2012

Psychiatric drugs

Carbamazepine Serbia 6 17 3.4 Zemann

etal. (2015)

Danube River, Serbia 44 23 BDL-

Peng etal.

(2014)

Baix Llobregat,

Barcelona, Spain

121 48 BDL-

62.4

Petrovic

etal. (2014)

Barcelona, Spain 32 92–100a136bRadovic

etal. (2014)

Rastatt, Germany 51 33 BDL-

Cabeza etal.

(2012)

Barnstable County,

Massachusetts, USA

20 25 BDL-

López etal.

(2013)

Urban catchment area

in Singapore

138 67 BDL-

9.3

Wolf etal.

(2012)

An urban-inuenced

karst aquifer in the

Wadi Shueib, Jordan

32 13 BDL-

100

Schaider

etal. (2014)

Diazepam Baix Llobregat,

Barcelona, Spain

121 36 BDL-

8.28

Zemann

etal. (2015)

Barcelona, Spain 32 23–100a35.1bGottschall

etal. (2012)

Primidone A karst system near

Yverdon-les-Bains,

Switzerland

16 6–19aBDL-

Cabeza etal.

(2012)

Baix Llobregat,

Barcelona, Spain

121 41 BDL-

27.62

López etal.

(2013)

Berlin, Germany 36 NA BDL-

140

Morasch

(2013)

Stimulants

Caffeine Baix Llobregat,

Barcelona, Spain

121 40 BDL-

55.5

Tran etal.

(2014)

Urban catchment area

in Singapore

148 80–83aBDL-

16249

Cabeza etal.

(2012)

(continued)

B. Ahmad and M. Imran

119

Table 6.2 (continued)

PPCPs Research area

Samples

Detection

frequency

(%)

Conc

(ng/L) References

Insect Repellants

DEET Barnstable County,

Massachusetts, USA

20 5 BDL-6 Zemann

etal. (2015)

Urban catchment area

in Singapore

148 100 1.9–

3481

Cabeza etal.

(2012)

X-ray contrast media

Iopamidol Switzerland 8 100 36–94 Zemann

etal. (2015)

Rastatt, Germany 115 4 BDL-

Schaider

etal. (2014)

An urban-inuenced

karst aquifer in the

Wadi Shueib, Jordan

39 51 BDL-

1900

Hass etal.

(2012)

Diatrizoic acid Switzerland 8 100 24–32 Wolf etal.

(2012)

Rastatt, Germany 165 27 BDL-

4240

Gottschall

etal. (2012)

An urban-inuenced

karst aquifer in the

Wadi Shueib, Jordan

39 79 BDL-

220

Hass etal.

2012)

Beta-blockers

Propranolol Serbia 6 67 BDL-

4.5

Gottschall

etal. (2012)

Barcelona, Spain 32 23 BDL-

9.38

Wolf etal.

(2012)

Metoprolol A karst system near

Yverdon-les-Bains,

Switzerland

16 6–12 BDL-9 Petrovic

etal. (2014)

Barcelona, Spain 32 100 95.3–

355

López etal.

(2013)

Musks

Galaxolide Baix Llobregat,

Barcelona, Spain

121 100 42.9 López etal.

(2013)

Tonalide Baix Llobregat,

Barcelona, Spain

121 100 7.5 Morasch

(2013)

Sunscreen agents Cabeza etal.

(2012)

Octocrylene Baix Llobregat,

Barcelona, Spain

121 96 8.42 Cabeza etal.

(2012)

Ethylhexyl

methoxycinnamate

Baix Llobregat,

Barcelona, Spain

121 100 35.31 Morasch

(2013)

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

120

excreted in the wastewater that is considered the main source of these compounds

for the ecosystem (Liu etal. 2010).

6.10 Ionic Liquids

Ionic liquids exist in salts having low melting point, regarded as ‘green’ replace-

ments in industrial volatile composites (Table6.2). These mixtures have heterocy-

clic rings of pyrrolidinium or morpholinium moieties and pyridinium or quaternary

ammonium salts. Ionic liquids are not generally utilized, but their formulations are

important for water solubility, toxicity, and poor degradation (Petrovic and Barcelo

2006; Pham etal. 2010).

6.10.1 Antibiotics

Antibiotics’ existence are broadly utilized for human and animals diseases treat-

ment; metabolized and unmetabolized antibiotics excreted via feces and urine,

which are originated in wastewater purication plants and surface water which par-

tially decomposed in the environment which accumulated in the water. The pres-

ence of antibiotics at low concentrations might increase the risk of antibiotic-resistant

bacterial species in river base ow (streamow that is discharged from groundwater

and seeps streams) and some extent should increase drug resistance microorganisms

(Martínez 2008; Watkinson etal. 2009; McArthur and Tuckeld 2000).

The existence of antibiotics in the groundwater is more considered worldwide in

recent times. A national exploration was conducted in the USA; pharmaceuticals

and more organic pollutants in water sources indicated antibiotics in 47 groundwa-

ter samples with >30% detection frequency (Barnes etal. 2008). The drinking, sur-

face, and groundwater reportshow the contamination with pharmaceuticals products

such as antibiotics (including enoxacin, trimethoprim ciprooxacin, and ooxacin)

in pharmaceutical industrial area-collected water samples (Fick etal. 2009).

The groundwater was also reported contaminated with veterinary antibiotics

near farmland or breeding facilities. For example, the occurrence of veterinary

drugs such as sulfonamides (sulfamethazine, sulfamerazine, sulfathiazole, and sul-

famethoxazole), lincomycin, tiamulin, monensin, and erythromycin was detected

(29 ng/L–2000 ng/L) in groundwater samples collected from pools and adjacent

groundwater operational for beef and swine livestock facilities. The existence of

various veterinary antibiotics was detected in organic vegetable farms groundwater

of northern China.

The sulfamethazine, sulfamonomethoxine, and sulfadiazine drugs with 1.5, 130,

and 19 ng/L,1.5 concentrations, respectively, were found in Guangxi Province

groundwater samples collected from a pig farm. The antibiotics that were detected

in groundwater collected from many countries having variable concentrations and

B. Ahmad and M. Imran

121

species suggested distinct consumption habits (Bartelt etal. 2011; Hu etal. 2010;

Zhou etal. 2012).

6.10.2 Anti-inammatories andAnalgesics

The most frequently detectable analgesics and anti-inammatories in groundwater

are diclofenac ibuprofen and paracetamol since they are used in daily life. Several

pharmaceuticals and their metabolites such as diclofenac, ibuprofen, and ketoprofen

were found at different concentrations in the drinking groundwater of Berlin and

Germany (Heberer 2002b).

The exltration process for wastewater to groundwater found a high concentra-

tion of analgesics and anti-inammatories. The concentration of diclofenac

(120ng/L) and ibuprofen (250ng/L) was detected at depthof 0.5m below the main

drain sewer pipe in North East London; high concentrations indicate pollution in

wastewater exltration in the groundwater (Ellis etal. 2003).

Repercussions of recycling in the ground and surface water of a medium-sized

Mediterranean catchment showed diclofenac and paracetamol (211 ng/L) in the

drinking supply which probably contaminated the water (Rabiet et al. 2006). A

monitoring survey was done to investigate the ECs in Barcelona (Spain); ibuprofen

was found in higher concentration in aquifers rather than wastewater treatment plant

inuent or efuent, which indicates natural groundwater recharge consisting of

river water, crude wastewater, or other discharge sources of ibuprofen (Teijon

etal. 2010).

6.11 Lipid Regulators

The lipid regulators’ detection frequencies and their metabolites such as clobric

acid, bezabrate, and gembrozil in groundwater were low as comparedsome anti-

inammatories, anti-inammatories, carbamazepine, and caffeine. The groundwa-

ter of two municipalwater resources (Guangzhou and China) landlls gembrozil

and bezabrate were not detected; clobric acid was detected at 3%; salicylic and

sulfamethoxazole were found 98% and 24%, respectively (Peng etal. 2014).

The clobric acid and gembrozil were found <10 % in the groundwater samples

collected from Singapore sewerage drainage, while caffeine and carbamazepine

were detected up to 90% and 72%, respectively (Tran et al. 2014); bezabrate

(54–100%) and gembrozil (62–100%) were detected from Barcelona (Spain)

groundwater. Average levels of pharmaceuticals were higher which indicated severe

groundwater contamination and it might be possible for more frequent lipid regula-

tors detection (López etal. 2013).

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

122

6.11.1 Caffeine

Caffeine contaminates the wastewater through a household plumbing system or

human urine; the average amount of caffeine is 360 mg/L which is present in soft

drinks, tea, and coffee; early data presented the caffeine existence in landll leach-

ates, septic tanks, sewage efuent, and surface water pollution through wastewater

(Seiler etal. 1999; Gilbert etal. 1976). The groundwater may be contaminated with

caffeine by natural recycling. The caffeine concentration up to>16,000 ng/L with

detection frequency of 83% was recorded in the groundwater samples taken from

Singapore.

The North Shore of Kauai and Hawaii ground and surface water founded 100%

detection frequency of caffeine in August, which was 33% in February; maximum

concentration (88 ng/L) was noted in groundwater in the summer season. A larger-

scale survey was done; total 1231 samples werecollected from California, the caf-

feine was 290 ng/L in untreated groundwater that used for public water supply (Tran

etal. 2014; Knee etal. 2010; Fram and Belitz 2011).

Incidence of caffeine in ground and surface water was higheras compared with

PPCPs, could be removed through wastewater treatment or rapid degradation pro-

cess, and less constant to the subsurface environment (Bradley etal. 2007; Jim

etal. 2006).

In surface waters, caffeine was consider the most frequently utilized indicator for

human-derived waste of surface water; for groundwater, it could be an indicator of

discharge in certain conditions wherever the biodegradation process is limited,

which rapidly degrades groundwater rich in bacteria (Buerge etal. 2003; Glassmeyer

etal. 2005; Knee etal. 2010).

6.11.2 Carbamazepine

The carbamazepine is included in the list of specied ingredients for the monitoring

account by the EU Water Framework Directive (Stuart etal. 2012). The detectable

concentration in groundwater was high. The carbamazepine was detected 42% in 64

samples collected from 23 European countries; the highest concentration was 390

ng/L.In two German cities (Leipzig and Halle), carbamazepine concentrations was

2–75 and 2–51 ng/L in the groundwater, respectively. In Montana (USA), 12 out of

38 well water samples were tested, and carbamazepine was detected upto 400 ng/L

(Musolff etal. 2009; Loos etal. 2010; Miller and Meek 2006; Osenbrück etal. 2007).

The groundwater studies showed that the carbamazepine would survive intact

after 8–10 years in the subsurface, neither degraded nor adsorbed, which might be

ubiquity in the groundwater (Drewes etal. 2000; Clara etal. 2004).

B. Ahmad and M. Imran

123

6.11.3 DEET

The DEET is an active substance used in commercial as insect repellents globally

and enters the marine environment through septic system and sewage treatment.

The PPCPs were detected in groundwater underneath and adjacent wastewater treat-

ment systems of the coastal plain (North Carolina). Average concentrations of

DEET was 540–1010 ng/L in groundwater-dependent on location. However, its

presence on the ground and surface water showed that pathways and sources of

DEET in groundwater required further research. The DEET was universally

detectedin sewage-impacted groundwater samples and also detected in groundwa-

ter samples collected from catchment areas without identied wastewater sources

with comparatively higher concentration levels up to 298 ng/L (Del etal. 2014; Tran

etal. 2014).

6.11.4 Others PPCPs

Other PPCPs investigation consist of beta-blockers, X-ray contrast media, musks,

and sunscreen agents. A 5-year study was performed in urban areas of Wadi Shueib

(Jordan); diatrizoic acid was a standard compound in X-ray diagnostics broadly

used in 2008 with the continuous occurrence of up to 79% but moderately lower

concentrations (BDL-220 ng/L) in the groundwater. The iopamidol was gradually

detected with maximum concentration up to 1900 ng/L (Zemann etal. 2015).

The sunscreen agents (Ethylhexyl methoxycinnamate and octocrylene), the

musk (galaxolide and tonalide), were found in the groundwater samples taken from

Barcelona and Spain. The galaxolide and Ethylhexyl methoxycinnamate had been

detected at higher levels than 100 ng/L at least in the sample. The intensities of beta-

blockers in the urban groundwater were underlying; beta-blockers, propranolol and

metoprolol, were detected in Barcelona, Spain. Previously, it exhibited a quite low

detecting frequency (23%) and concentrations (BDL-9.38 ng/L); maximum concen-

tration was up to 355 ng/L in all groundwater samples (Cabeza etal. 2012; López

etal. 2013).

6.11.5 Sources ofPPCPs inGroundwater

The PPCPs in groundwater were directly associated with human activities, mostly

compounds used in products’ synthetic processes. Only several PPCPs such as caf-

feine can yield over 60 plant varieties (Knee etal. 2010). Common sources and

pathways used for PPCPs-contaminated groundwater are presented in Fig.6.2.

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

124

6.11.6 Wastewater andContamination ofSurface Water

Wastewater is known as the most signicant source of PPCPs in the aquatic atmo-

sphere. The household PPCPs excreted from a human after washing off through tap

water, sinks, and toilets and entered in the sewerage system; limited removal was

found during the primary treatment of sewage treatment plants (STPs) because

sludge absorbtionwas limited (Behera etal. 2011).

The biological purication variable elimination efciencies could be achieved;

the PPCPs in nal efuent were noted at various levels. The diclofenac showed low

degradation (< 25%); ibuprofen and ketoprofen were degraded (>75%), and both

were categorized in the same therapeutic group (Salgado etal. 2012).

The PPCPs containing efuents discharged contaminated surface water and

remained at the surface water body which undergoes low natural attenuation (Gurr

and Reinhard 2006). The PPCPs transferred from groundwater via the hyporheic

zone. The carbamazepine is used as an indicator for the surface trace wastewater

and underground water exchange procedures (Lewandowski et al. 2011; Gasser

etal. 2010).

The Managed aquifer recharge (MAR) term used for surface water;recycled

water to articially recharge groundwater structure and represented a signicant

probable source of PPCPs in groundwater, particularly when residence time is short

and wastewater treatment regulated inadequately. The Riverbank ltration and well

injection are widely adopted at MAR processes. The potential transportation pro-

cesses of various efuent-derived pharmaceutical contaminants from the surface to

shallow groundwater during riverbank ltration detected that inltration of efuent

contaminated surface water could lead to the existence of PPCPs. The carbamaze-

pine and sulfamethoxazole were found to be >20 ng/L in groundwater of stream

bank (Missimer etal. 2011; Bradley etal. 2014).

The selected PPCPs in groundwater recharge showed that diclofenac, naproxen,

caffeine, ketoprofen, gembrozil, and ibuprofen were prociently removed after <

Emerging contaminats

Household

PPCP

Soild

waste

Land fill

Soil

Toilet/Sink

Septic

System

Leakage or

Sewer

Industerial

waste

Contiminated

suface and groud

water

Hospital

Waste

Contiminated

suface and groud

water

Veterny

drugs

Live stock

waste or

animal

extceta

soils

Pesticide

Insecticides

Domestic

Waste

Fig. 6.2 Common sources and pathways used for PPCPs-contaminated groundwater

B. Ahmad and M. Imran

125

6 months where secondary or tertiary wastewater was treated. The primidone and

carbamazepine were endured in recharged groundwater with retention of 8 years

(Drewes etal. 2003).

The warnings must be taken in recharging of the aquifer with sewage efuents,

used to undergo advanced treatment methods that can efciently take out the resi-

due PPCPs or enhanced biodegradation of refractory PPCPs. Biodegradable metab-

olites of PPCPs were removed during residence times of riverbank ltration (Jurado

etal. 2014; Heberer etal. 2004).

6.11.7 Landlls

The most frequent way used for municipal solid disposal waste is landlled. The

advantage of this method is operational simplicity with low cost, but contamination

in the surrounding atmosphere cannot be unnoticed. Landlls are a decisive deposi-

tories technique for different solid and semisolid wastes containing PPCPs;

resources of PPCPs are soft drinks and unwanted medications. After being dis-

carded in landlls, the PPCPs can be either metabolized by the microorganism or

absorbed into the waste solids, but mostly dissolved in the land leachate. Numerous

PPCPs with signicantly high concentrations were found in landll leachates, For

example, naproxen (520 μg/L), ibuprofen (167 μg/L), and carbamazepine and phen-

azone (1000 μg/L) were found (Eggen etal. 2010; Musson and Townsend 2009;

Daughton and Ternes 1999; Kosjek etal. 2009; Slack etal. 2005). The anaerobic

state in landlls and groundwater can slow the biodegradation process of organic

compounds and resulted PPCPs’ abundance and persistence in groundwater (Erses

etal. 2008). The naproxen (67–87 ng/L), sulfamethoxazole (29–125 ng/L), and sali-

cylic acid (2000 ng/L) were detected in the groundwater of municipal landlls in

China (Peng et al. 2014). The landll leachate-affected ground water ibuprofen

(3100 ng/L)whichwas detected in Elkhart, Indiana (Buszka etal. 2009).

6.11.8 Septic Systems

Septic systems or on-site wastewater treatment systems are the sources of PPCPs

that contaminated the ground and surface water. The septic system is a small-scale

sewage dealing system, typically used in towns or rural areas where’s no main sew-

age pipes supplied wereavailable by local governments or private corporations. The

water utilized domestically or recycled to complement the local groundwater sup-

plies could provide opportunities to PPCPs enduring incomplete treatment into sep-

tic systems that entered into underground water. In certain regions of the northeastern

United States, around 85% of wastewater disposal is carried out by septic systems

(Godfrey etal. 2007).

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

126

With its widespread uses, it is tough to monitor effectively and regulate contami-

nation from septic systems. Concentrations of caffeine, paraxanthine, and other

micropollutants, in the residential septic system and downgradient ground

water were found. Ambient concentrations of caffeine (17,000–23,000 ng/) and

paraxanthine (55,000–65,000 ng/L) were high in the septic tank which was very

high concentrations of compounds in the nearest well (>1700 ng/L) which fail to

distance and depth.

Recent research has shown that pharmaceuticals and more micropollutants in

groundwater networks that inuenced by septic systems, for the levels of various

PPCPs such as carisoprodol and lidocaine, were >0.1 μg/L in groundwater beneath

and downgradient of the leaching bed (Swartz etal. 2006; Phillips etal. 2015).

6.11.9 Livestock Breeding

Veterinary medicine is used to treat disease and supported in livestock breeding

growing concerned, but it contaminatedthe environment. The veterinary used anti-

biotics not entirely absorbed or metabolized invivo. Almost 50–100% of antibiotics

secreted via urine and feces (Kim etal. 2011),stored on waste ponds and released

into the environment having a threat for groundwater contamination. The tetracy-

cline and sulfonamides with a maximum level of up to 250 μg/L in water and 170

μg/kg in the soil were detected near swine manure (Awad etal. 2014). The applica-

tion of veterinarian drugs contaminated manure for fertilizer and polluted the

groundwater (Hu etal. 2010).

The probable resource of veterinary drugs in soil and groundwater is farm burial

of livestock. The maximum concentration of monensin was found up to 12 μg/L in

leachate dead cattle burials (Bartelt-Hunt, 2013;Yuan etal. 2013).

6.11.10 Sewer Leakage

Leaky sewers arethe potential sources of pollutants in urban aquifers. Damaged

sewage systems pipelines linked in long time overuse unrepaired due to use of poor

material or negligence during construction. The PPCPs entered in soil zone by exl-

trating sewage through great probability to impact groundwater; concentration was

usually 1 to 2 orders of magnitude lower than sewage inuents of 50 urban ground-

water underlying Tokyo, where unintended ground contamination takes place due to

the sewer networks breakage; the concentration of the sample was quite compara-

ble. It was proposed that some PPCPs could act as preventive indicators of ground-

water contamination through sewage leakage. Specic tracers including X-ray

contrast agents, primidone, diclofenac, carbamazepine, ibuprofen, caffeine, and

articial sweeteners were tested (Wolf etal. 2012; Kuroda etal. 2012; Ellis etal.

2003; Buerge etal. 2003).

B. Ahmad and M. Imran

127

However, no markers are generally applicable for groundwater systems because

both the input and background concentrations vary spatially and temporally (Cronin

etal. 2006).

6.11.11 The Fate ofPPCPs intheUnderground Environment

PPCPs are measurable in groundwater, soils, and sediments. The major processes

are adsorption, degradation, and migration. Chemicals in the soil surface can trans-

fer down to the lower layer and saturated and unsaturated zones. The natural attenu-

ation was reduced in soil; pharmaceuticals could reach in groundwater (Laws etal.

2011). The fate of PPCPs changed in the ground environment affected by environ-

mental factors and physical and chemical properties.

6.11.12 Adsorption andMigration

Adsorption can affect the fate of PPCPs in underground environments having an

impact on their bioavailability, movement, and plant uptake (Lin and Gan 2011).

Chemicals that have strong absorption are typically less mobile in the soil with

limited leaching potential; however, ones with weak sorption probably move down-

gradient and permeate in groundwater.

The adsorption of residue PPCPs in the soil is related to physicochemical param-

eters like molecular structure, hydrophobicity, and water solubility. The carbamaze-

pine and gembrozil were inadequately adsorbed in soils, while triclosan showed

good adsorption and was instantly retained in the soils (Yu etal. 2013).

Such differences are probably due to its different chemical characteristics. The

strong propensity for triclosan will be sorbed on both silt loam soils and sandy loam.

The caffeine is proven strongly sorbed in sandy loam soil and hence had more

potential reasons for groundwater pollution (Karnjanapiboonwong etal. 2010).

Characteristics of soils, in particular the content of dissolved organic matter in

soils, effect on PPCPs adsorbing. A study of sulfadimethoxine, sulfamethazine, and

sulfaquinoxaline in four Brazilian soils showed sorption capacities; sulfonamides

were higher in clay soils than sandy soil. This concluded that sulfonamides lipophi-

licity and organic matter content of the soil are related to sorption (Doretto

etal. 2014).

The naproxen has a low sorption afnity with sandy aquifer material from low

organic matter which indicates a highly mobile compound in the aquifer media and

is ubiquitously detected in the groundwater (Teijón etal. 2013).

The environmental conditions also had an impact on PPCPs’ adsorption behavior

in the underground environment. The impacts of solution chemistry such as ionic

strength and pH on the conservation and transport of sulfamethoxazole and cipro-

oxacin in saturated porous media were noted. Solution for the ionic strength and

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

128

pH played a major role to control ciprooxacin transportation, but showed little

impact on sulfamethoxazole transport under the experimental conditions (Chen

etal. 2011).

The positive effect on the sorption of sulfonamides was noted at low pH because

cations existed at low pH.The attraction is toward negatively charged minerals sur-

faces by electrostatic interactions; even though the electrostatic repulsion among

negatively charged minerals and anionic sulfonamides at high pH would negatively

affect sorption afnity (Zhang etal. 2014).

These conclusions could have signicant consequences for the destiny of ionic

PPCPs during underground environment altering. The PPCPs undertake almost no

adsorption in soils; their migration in subsurface environments is principally

impacted by geological locations, aquifers hydraulic environments, and soil charac-

teristics. The high hydraulic conductivities and groundwater velocities in the satu-

rated and unsaturated zone of the karstic area probably did groundwater region

pollutants (Katz etal. 2009).

The groundwater below deposits may be exposed with PPCPs’ residues pollut-

ants emitted from wastewater efuents via articial aquifer recharge, primarily due

to the high transmissivity of shallow alluvium. The dynamic soil column leaching

test demonstrated the mobility of sulfadiazine that acted stronger in sandy soils as

compared to loamy soils and clays. The soil texture is considered the most impor-

tant factor affecting sulfadiazine’s downward movement (Heberer 2002; Bruchet

etal. 2005; Chefetz etal. 2008).

6.11.13 Degradation

It is broadly acknowledged that the multiple composites degraded quicker and eas-

ier in aerobic environments as compared to aerobic related with different microbial

activities (Johnson etal. 1998). In groundwater, microbes are rarer and more dis-

tinct in comparison to soils, and redox condition is poor (Lapworth etal. 2012).

The PPCPs in groundwater can endure imperfect degradation, possibly changed

into lethal metabolites, or will remain intact in groundwater for long. Redox con-

trols were commonly noted for groundwater PPCPs. The redox-dependent elimina-

tion of 27 wastewater-derived trace compounds with tank aeration tests, compounds

including propyphenazone, doxycycline, and phenazone, was prociently taken

away beneath oxic circumstances and exit in anoxic situations. Three antibiotics,

clarithromycin, clindamycin, and roxithromycin, have been removed under anoxic

circumstances (Burke etal. 2014a).

The fate of various PPCPs at the hyporheic zone was affected in the winter and

summer environment. The ndings proved that temperature changed the result;

iopromide, diclofenac, and metoprolol were more effective in summer (Burke

etal. 2014b).

Various physicochemical properties of various PPCPs biodegrade are different.

Caffeine and paracetamol were commonly used, endured more degradation in

B. Ahmad and M. Imran

129

wastewater treatment, and were transported in the subsurface; generally detected

less commonly as compared with other resistant degradant PPCPs such as sulfa-

methoxazole and carbamazepine (Benotti and Brownawell 2009; Grossberger

etal. 2014).

The degradation analysis of sulfonamides in sandy soils leads to the differences

in degradation (Zhang and Wang 2007). The environments difference inuences on

PPCPs degradation with various properties. The degradation rates of tetracycline,

chlortetracycline, and tetracycline were much different at changed pH and tempera-

tures. The sulfathiazole, sulfachlorpyridazine, and sulfadimethoxine were less sus-

ceptible to pH and temperature change; pH-associated reactions such as hydrolysis

were probably not the removal mechanisms in groundwater (Loftin etal. 2008)

(Table6.3).

6.11.14 Sources totheEnvironment

The contaminate transported in the aqueous environment is described via the source-

pathway- receptor model, shown in Fig. 6.3. Some of the contaminant pathway

receptor sources are unclear since there are limited data about such pollutants. The

direct pathways for pharmaceuticals and industrial contaminants are discharged by

landll leachate, efuent leaking sewers, leaking storage tanks and in-ground

bypassing the soil zone, like septic tanks. The humans and groundwater pathway,

human, animal, and pharmaceuticals were proposed (Daughton and Ternes 1999;

Stuart etal. 2012; Jones etal. 2002). Compounds which have threaten for world are

impossible to analyze at low levels and those that have physical and chemical prop-

erties enable them to persist in the water treatment procedure.

The soil surface contaminants could migrate across the soil to groundwater. This

practice is applied for biosolids to soil and is crucial part of world waste manage-

ment methods. The fertilizer application and biosolids from sewage sludge treat-

ment have an advantage for enriching soil nutrition, but residual concentrations in

the solids werefound in incomplete ECs’ removal during wastewater treatment. The

high concentrations in sludge and high solubility, the Halogenated hydrocarbons of

polychlorinated, and peruorochemicals alkanes are essential for groundwater con-

taminants with relatively higher concentrations and solubility. Veterinary antibiotics

and saccharin were reported in soil excrement (Sarmah etal. 2006; Hu etal. 2010;

Buerge etal. 2011; Focazio etal. 2008).

However, fertilizer and biosolid-derived ECs reached groundwater in elevated

levels through indirect routes, like excess and surface water-groundwater (SW-GW)

exchanging, rather than downward migration due to attenuation in soil and unsatu-

rated zone (Lapworth etal. 2012).

SW-GW interaction has a signicant pathway. The surface waters comprise

higher levels with large range ECs than groundwaters, indicating direct entry from

wastewater sources, short residence times, and limited dilution capability of surface

water compared with groundwater (Lapworth etal. 2009; Barnes etal. 2004).

6 Emerging Organic Contaminants, Pharmaceuticals and Personal Care Products…

130

Key:

Sourcesand pathways

Minor source

Majorpathway/flux

Majorsource

Minor pathway/flux

Majorremoval proc.

or pathway

Rapid route bypassing *

Natural/eng. attenuation

MAR: Merged artificial

recharge

Accidental leaks, emergencies, urbanrunoff

Untr

eated

disch

arge

Septic tanks

Sewerage system

Wastewater

treatment

proc.

Groundwater

Surfacewater

Receptors

Domestic

waste/eff.

Hospital

waste/eff.

Industrial

waste/eff.

Landfill

Leachate

Pesticide

and

herbicide

Animal

waste

Unsaturated

zone

Soil

WWTeffluent

&Biosolids

Fig. 6.3 The pathway receptor source approach for emerging contaminants ECs. (Adapted from Lapworth etal. 2012)

B. Ahmad and M. Imran

131

SW-GW exchange is signicant in aquifers below and adjacent to watercourses,

e.g., in shallow alluvial aquifers, essential sources of drinking water on the globe.

MAR refers to surface water use and treated wastewater to recharge aquifer arti-

cially. This is suitable in semiarid areas where water resources are scarce or replen-

ish aquifers or used as natural treatment and temporary storage systems (Buerge

etal. 2009; Drewes 2009; Mueller etal. 2011; Gasser etal. 2010)

However, articial recharge has short circuit natural attenuation mechanisms in

soil and subsurface and leads to potential long-term groundwater sources’ contami-

nation; diffuse leakage from poor maintenance and reticulated sewerage systems

can pose the risk of EC pollution in groundwater. Nonvolatile compounds can be

mobilized in atmospheric transmission route and aerial sources including industry,

agriculture, and transport dust; diffuse with low loading in land surface and not

known signicant for groundwater pollution (Hamscher and Hartung 2008;

Ellis 2006).

6.12 Conclusion andFuture Prospects

Over the past few years, emerging organic contaminants, personal care products,

and pharmaceuticals have been detected in the groundwater. More compounds may

be spotted with the help of advanced analytical methods and techniques. It is almost

impossible to remove these contaminants from the groundwater; hence, this is the

only robust approach to detect the source and control them at the source of release

to the water cycle. Momentarily, this is an immediate measure to regulate these

contaminants by awareness campaigns about toxicity, risks, distribution, and occur-

rence of these contaminants present in the underground drinking water.

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Chapter 7

Environmental andHealth Effects

ofHeavy Metals andTheir Treatment

Methods

HajiraHaroon, MuhammadRizwan, andNaveedAhmed

Abstract Heavy metals (HMs) are natural constituent that exist in ecosystem and

are used for various industrial and economics purposes. Mercury is the naturally

occurring heavy metal, mostly use in industries. It is commonly present in the form

of elemental mercury, methyl-mercury, and inorganic mercury. The main sources of

mercury and cadmium are earth crust, volcanoes, and vaporization from natural

water bodies. Mostly mercury is used in producing dental amalgams, thermometer,

and some batteries. It can be found in some chemicals, electrical equipment, metal

processing, and building industries. Mercury is released into the ecosystem by dif-

ferent ways such as agriculture sources in the form of seed preservation, pharma-

ceuticals, speeding organic reactions, and in chlorine and caustic soda production.

It has also many negative impacts on environment as well as human health.

Mercury and cadmium are the deleterious substances which have indirect role in

human chemical and physiochemical processes and do not naturally occur in living

bodies. Mercury and cadmium contamination occur in human beings through

anthropogenic activities such as municipal and industrial wastewater discharge and

through agricultural runoff. Mercury and cadmium produced during metal process-

ing and building industries can cause many health hazards such as blindness, deaf-

ness, and digestive problems. Fetal exposure to mercury will causes miscarriages,

inborn diseases, and mental retardation.

Mercury is present in an unreactive form in the air. Workers and residents living

near the mercury extraction sites have greater chances of exposure. According to the

U.S. Environmental Protection Agency, HMs are possible carcinogens. Methyl-

H. Haroon (*)

Department of Environmental Sciences, The University of Haripur, Haripur, KPK, Pakistan

e-mail: hajira@uoh.edu.pk

M. Rizwan · N. Ahmed

U.S.-Pakistan Center for Advanced Studies in Water, Mehran University of Engineering &

Technology, Jamshoro, Pakistan

e-mail: drmrizwan.uspcasw@faculty.muet.edu.pk; naveed.uspcasw@faculty.muet.edu.pk

144

mercury is made primarily by minute organisms present in water and soil. The cur-

rent standard of mercury by EPA and WHO for drinking water is 0.002 mg/L, and

for industrial efuent, it is 0.001 mg/L.

Removal of HMs from wastewater can be carried out by precipitation, coagula-

tion, ionic exchange, electrochemical operation, and biological treatment, while

removal of mercury from drinking water can be done by using coagulation, granu-

lated activated carbon, lime softening, and reserve osmosis. HMs pose serious

health issues andalso haveeconomic impacts such as decrease in working produc-

tivity, increase in health expenditure per person, and increase in mortality and mor-

bidity. Health is the basic right of every human, so strict protective measure should

be taken by workers which are mostly exposed to mercury. Hence, major research

is needed to further explicate the public health impact associated with human expo-

sure to such toxic metal.

7.1 Introduction

Increasing industrialization results in the generation of heavy metals, which causes

environmental pollution as a global issue (Usman etal. 2019). Heavy metals are

actually elements having atomic number and density greater than 20 and 5g/cm3,

respectively (Ali and Khan 2018). Arsenic (As), lead (Pb), copper (Cu), cadmium

(Cd), nickel (Ni), chromium (Cr), and mercury (Hg) are a few examples of heavy

metals and are toxic, bioaccumulative, and persistent in nature. They are released

into various components of the environment, i.e., water, air, and soil, from various

natural and anthropogenic sources like volcanic eruptions, weathering of rocks,

mining, industries, domestic, and various agricultural activities (Ali etal. 2019;

Usman etal. 2019).

Some heavy metals are known as essential metals as they play a vital role in vari-

ous biological functions of living organisms and are harmful beyond a certain dose

and exposure time. However, nonessential heavy metals are toxic even at a very low

concentration. Heavy metals are mutagenic, teratogenic, and carcinogenic, which

have serious effects on public health as well as on the environment (Mohamed etal.

2017). They result in the generation of ROS (reactive oxygenic species) and cause

oxidative stress. Oxidative stress in living organisms results in the development of

various abnormalities and diseases like renal, brain, and neurological disorders

(Alietal. 2019).

Chronic or long-term exposure to heavy metals is a real hazard for the environ-

ment and living organisms (Wieczorek-Dąbrowska etal. 2013). The most common

routes of chronic exposure of heavy metals to human beings and animals are through

inhalation of pollutants, utilization of contaminated food and water, or exposure to

contaminated soil and industries (Mohammadi et al. 2019a; Shen et al. 2019).

Contamination of various sources of food like vegetables, fruits, shes, and grains

can also occur by the accumulation of heavy metals in them from polluted water and

soil sources (Sall etal. 2020). Heavy metals’ exposure can result in various diseases

H. Haroon etal.

145

in humans like cancers, respiratory, neurological, and kidney problems. For instance,

carcinogenic chromium can aggravate skin abrasions, cancer, and respiratory prob-

lems (Mohammadi etal. 2019a).

Heavy metals’ concentration above the threshold limit not only reduces fertility

of soil, but also affects its microbiological balance (Barbieri 2016). Bioaccumulation

of heavy metals in biota of various ecosystems has different adverse effects on liv-

ing organisms (Malik and Maurya 2014).

Many elements are classied into the category of heavy metals, for instance Cr,

Ni, Zn, Cu, Pb, As, and Hg, but some are relevant in the environmental context

(Barakat 2011). Chromium and copper are among various environmentally toxic

heavy metals (Ali etal. 2019), and in the current chapter, our focus is on these two

heavy metals.

7.1.1 Chromium andIts Oxidation States

French chemist Louis Vauquelin, in 1797, discovered chromium in the mineral

crocoite (lead chromate) and named it chromium as its compounds have different

colors. Chromium is derived from the Greek word (χρωα) chroma, meaning color.

Chromium has the atomic and mass number of 24 and 51.99, respectively. It is pres-

ent in the IV period and group VI B of the periodic table. The gemstones emerald

and ruby contain chromium (chromic oxide) in their structure, so they have green

and red colors, respectively. Chromium is the abundant element, i.e., on number 21

on the earth’s crust, and is also the sixth most plentiful transition metal (Mohan and

Pittman Jr 2006).

Chromium occurs in nature in different oxidation states from −2 to +6 (Tumolo

etal. 2020). However, chromium usually exists in water in two main stable oxida-

tion states, i.e., trivalent Cr (III) chromium and hexavalent Cr(VI) chromium,

whereas other oxidation states of chromium are unstable in aqueous solution

(Honnannavar and Hosamani 2014). Cr (III) has less solubility and mobility and is

adsorbed by the soil particles which prevents it to enter into underground water and

ultimately stops its uptake by the plants (Haroon etal. 2020).

Cr as Cr (III) is a signicant element which helps in the metabolism of lipid and

protein (Briki etal. 2017). However, Cr (VI) has high solubility, mobility, and oxi-

dizing power; that’s why it is 100 folds more toxic compared to the trivalent chro-

mium and it remains available within the human body for 39h. Cr (VI) is 1000

times more toxic, cytotoxic, mutagenic, teratogen, and cancer-causing chromium

than Cr (III) in living systems (Bansal etal. 2019; Haroon etal. 2016). The United

States Environment Protection Agency and International Agency for Research on

Cancer classied Cr (VI) as a Group A and Group I carcinogen, respectively, for

humans because of its highest toxicity level (Xia etal. 2019). Cr (VI) is included in

the list of eigh most toxic chemicals for human beings and has been found com-

monly as a third hazardous pollutant on the waste dumping sites (Jin etal. 2016).

The main focus of Erin Brockovitch, the Hollywood blockbuster movie, is on the

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

146

toxicity of hexavalent chromium (Saha and Orvig 2010). Cr (VI) toxicity was linked

with its oxidizing power; it strongly oxidizes various biomolecules, for instance,

protein and DNA (Parlayıcı and Pehlivan 2019). High mutagenic properties of Cr

(VI) can trigger the reproductive system and the DNA and can cause several birth

defects (Parlayıcı and Pehlivan 2019).

According to EPA guidelines, many countries have the standard limits of Cr

(VI), i.e., 0.05mg L1, 0.1mg L−1, and 0.25mg L−1 for drinking water, inland surface

water, and industrial efuent, respectively. Cr (VI) is usually present in the form of

hydrogen chromate (HCrO4) and dichromate (Cr2O72−) anions in acidic conditions

and as chromate (CrO42−) anions in basic media (Jobby etal. 2018). These all Cr

(VI) ions are highly soluble and have strong oxidizing property which make them

very active in various environmental portions like water and soil (Antoniadis

etal. 2018).

Because of the elevated level of Cr (VI) solubility as well as mobility in aqueous

solution, it can easily move into various living biota and causes numerous physio-

logical disorders, for example, anemia, diarrhea, nausea, epigastric discomfort, cir-

culatory shutdown, internal hemorrhaging, stomach damage, skin irritation, ulcers,

vomiting, lung cancer, and kidney cancer (Jobby etal. 2018).

7.1.2 Copper andIts Oxidation States

Copper (Cu) is the transition element which is placed in the fourth period and group

IB of the periodic table (Wuana and Okieimen 2011). It has the atomic and mass

number of 29 and 63.546, respectively. Globally, it is the third most used element

and is twenty-fth most abundant constituent of the earth (Karlin and Tyeklár 2012).

There are three main oxidation states of copper, metallic or solid copper having

zero oxidation state, i.e., Cu (0), whereas cuprous Cu(I) and cupric Cu (II) ions are

other two forms. The most important oxidation state of copper is Cu (II), which is

coordinated with six water molecules and is usually encountered in water.

Compounds of cupric are of green or blue color and commonly water-soluble. After

entering into the environment, Cu (II) binds itself with the various organic and inor-

ganic materials which are present in the water, soil, and sediments depending on the

presence of various competing ions, pH, and oxidation-reduction potential of the

environment.

7.2 Sources ofChromium andCopper

Chromium and copper enter into the environment from both natural and anthropo-

genic processes (Fig.7.1). However, its concentration is low, when occurs naturally,

and becomes high when released into the environment from industries.

H. Haroon etal.

147

7.2.1 Natural Sources

Chromium occurs naturally in different types of rocks, minerals, and ores and is

released into the environment by its natural degradation, interaction, and reactions.

It is thetwenty-rst largely available element in the rocks, having an average con-

centration of 100mg/kg rock. Some examples of natural rocks having chromium are

igneous rocks, sedimentary rocks, ultramac rocks, and felsic rocks (granites).

Chromite and a range of spinel-type minerals are a natural source of chromium

(Kabata-Pendias and Mukherjee 2007).

Likewise, copper is a reddish-brown element which exists naturally in rocks,

sediments, soil, air, and water. Out of total copper, which is present on earth, almost

two-third is present in igneous (volcanic) while one-fourth in sedimentary rocks. It

is also released through volcanic eruptions, windblown dust, forest res, decaying

of organic material, and sea spray.

7.2.2 Anthropogenic Sources

Man-made activities are the major source of environmental contamination with

chromium. Some major sources of chromium are brass, paper and pulp, automobile,

fertilizer, steel, textile, metal nishing, chromite ore processing industry, magnetic

tapes, wood protection, leather tanning, petroleum distillation, electrical equipment,

etc. (Kabata-Pendias and Mukherjee 2007; Mohan and Pittman Jr 2006). These all

sources produce a huge quantity of chromium-containing efuents which pollute

Fig. 7.1 Different sources of chromium and copper

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

148

both surface and groundwater resources. Although chromium can be derived from

natural sources, a high amount of it is entering into the environment as a result of

industrial activities, like electroplating and leather tanning (Blowes 2002). During

chrome tanning process of hides, almost 40% of unused salts of chromium are

released in the efuents (Chowdhury etal. 2016). Other important anthropogenic

chromium sources are municipal wastes and resultant sludge of municipal waste.

Industrial and residential sewage treatment plants also discharge a signicant

amount of chromium into water bodies. More or less, all chemical laboratories such

as research, academic, and industrial releases signicant chromium (both trivalent

and hexavalent) amount into the environment (Testa etal. 2004).

Vehicles are another contributor of Cr emission into the environment (Ferretti

etal. 1995). Incineration, coal, and wood combustion also release 50,000 tons per

year of Cr worldwide (Merian 1984). A signicant amount of Cr is present in fertil-

izers (Krüger etal. 2017). According to the International Agency for Research on

Cancer (IARC), normally the cigarettes made in the US have 0.24–6.3mg of Cr per

kg. Higher levels of Cr have been found in areas near landlls and hazardous waste

disposal sites. House dust and soil also contain Cr (VI) (Shankar and

Venkateswarlu 2011).

Copper is also released through various anthropogenic sources, for instance,

mining, fossil fuel combustion, solid waste, trafc emissions, and wastewater of

various industries like chemicals, paints, fertilizer, fungicides, etc. (Ameh and Sayes

2019). Bulk of copper is mined each year because of its application in different

processes, so copper mining itself is a cause of pollution as it involves different

steps from mining to milling of copper and is therefore deteriorating the environment.

Another main source of copper release into the environment is through various

agricultural practices. Copper in the form of copper sulfate has been known to be

used as the rst chemical against various plant diseases, whereas other hydroxides

and oxychlorides of copper are also used as pesticides, herbicides, fungicide, nema-

ticides, etc. (El-Hak and Mobarak 2019; Iwinski etal. 2017). Phosphate-based fer-

tilizers also contain a large quantity of copper and are a key source of copper in soil.

Copper is also used for wood preservation. In North America, greater than 79,000

tons of copper are used annually, which showed a 50% share of the wood preserva-

tion in the global market (Anjum etal. 2015). Because of the antimicrobial proper-

ties of copper, it also has wide applications in the eld of medicines (Anjum

etal. 2015).

7.3 Environmental Effects ofChromium andCopper

Environmental pollution due to Cr (VI) is attaining more attention as it is present

globally with elevated levels in water and soil due to both natural and anthropogenic

sources (Ashraf etal. 2017; Brasili etal. 2020). These comprise mining, dyeing,

incineration, fertilizers, wood, and paper processing which results in elevation of Cr

(VI) in water and soil (Jones etal. 2019; Yang etal. 2020).

H. Haroon etal.

149

Chromium has been reported globally above the permissible limit in water and

soil of different countries like Pakistan, China, and India (Bhattacharya etal. 2019;

Raza et al. 2017). A number of tanneries (both registered and unregistered) in

Pakistan are releasing chromium in their efuent, which ultimately contaminates

the environment. Drinking water pollution with a high chromium concentration of

5.50mg L−1 has also been noticed in Sahiwal, Pakistan (Zahir etal. 2015). Increase

in chromium concentration in the soil results in the appearance of genetic modica-

tion in the plants. Acidication of soil can also affect the utilization of chromium by

plants (Hayat etal. 2012). Plant physiology is also affected by Cr (VI), along with

reduction in plant growth, chorosis, and necrosis (Haroon etal. 2020). Literature

showed that numerous medicinal plants which are grown near industries have accu-

mulated various heavy metals like chromium and copper (Bolan etal. 2017; Kohzadi

etal. 2019). Even though Cr (III) is a vital nutrient for humans’ metabolism, if its

concentration increases from 150mg L−1, it is harmful for the plant physiology

(Haroon etal. 2016).

In Mexico (Sonora), almost 43% of drinking water from different sources (stor-

age tanks and wells) showed higher amount of Cd, Cu, As, and Pb (Organization

2018). Elevated levels of Cu, Cd, and Pb have been reported in the drinking water

of 10 different cities of Saudi Arabia which is ascribed with Kuwaiti and the Gulf

War oil res (Chowdhury etal. 2016). Another report of ten years in rural regions of

India indicated the high values (above WHO values) for As, Cr, Mn, Pb, Zn, and Ni

in groundwater, which was associated with the pharmaceutical, pesticide, paint, and

fertilizer industries (Bajwa etal. 2017; Chowdhury etal. 2016). Wastewater from

industries pollutes the nearby water bodies. Coal combustion in industries is the key

source of air pollution, as coal contains trace amounts of chromium, while dumping

of resultant chromium-containing solid waste will result in elevated concentration

of chromium in air and soil, respectively. In contrast, globally, the release of chro-

mium in soil, water, and air is 896, 142, and 30 thousand metric tons per year,

respectively (Mohan and Pittman Jr 2006).

Copper is a vital micronutrient for different biotic components of the environ-

ment (Zitoun 2019), but a high level of copper can also result in environmental

pollution. It is known as a priority pollutant as reported by US-EPA and is normally

present in various water bodies (Sruthi etal. 2018). Copper speciation in the water

bodies is actually responsible for the toxicity of copper (Tait etal. 2018). Cu has

attained great consideration because of its dual effect towards plants, i.e., at opti-

mum amount, it is essential, whereas it becomes toxic at higher concentrations

(Ameh and Sayes 2019). Copper is among the eight important micronutrients which

are needed for the growth of plants (Nazir etal. 2019) and is also linked with several

physiological as well as biochemical processes (Garcia etal. 2014). Copper is a part

of the structures of various regulatory proteins (enzymes) and helps in protein syn-

thesis, respiration of mitochondria, metabolism of cell wall, photosynthetic electron

transport, oxidative stress response, and hormone signaling (Nazir et al. 2019;

Zhang etal. 2019). Plastocyanin (an electron carrier proteins) also contains a large

amount (50%) of the copper inside the plastids (Zhang etal. 2019). Copper has the

ability to easily gain and lose electrons; therefore, it acts as a cofactor in various

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

150

enzymes like laccase, polyphenol oxidase, and amino oxidase and plays an impor-

tant role of antioxidants under conditions of stress (Nazir et al. 2019; Zhang

etal. 2019).

On the other hand, exposure to excess copper by the plants will affect various

bio-physiochemical processes (Ameh and Sayes 2019; Jaime-Pérez etal. 2019) and

will result in oxidative stress along with alterations in RNA and DNA (Ameh and

Sayes 2019; Jaime-Pérez etal. 2019). 20–30mg kg−1 is the toxic range of copper for

plants (Marschner 2011). Excess uptake of Cu can affect photosynthesis, enzymatic

activity, respiration, and growth of plant (Lillo etal. 2019; Zhang et al. 2019).

Various visual symptoms of excess copper content in plants are chlorosis, nutrient

deciency, necrosis, reduced growth of shoots and roots, and even death in severe

toxic conditions (Zhang etal. 2019).

In the soil of the USA, the threshold limit of copper for crops plantation is

100mg kg−1 (Kabata-Pendias 2010). As copper has high density, so its mobility in

soil is less and it mostly accumulates in topsoil (Araújo etal. 2019; Ju etal. 2019).

About 80% of copper is present in soil as suldes and oxides, which are not soluble

and have low phytoavailability (Mihaljevič etal. 2019). However, some Cu (20%)

is present as carbonates and hydroxyl compounds in soil and is mostly available to

the plants in this form. Copper in Cu2+ form is generally absorbed by plants because

of its strong binding ability with organic materials than other species of copper

(Ogunkunle etal. 2019). The presence of a higher amount of copper in soil reduces

crop production and ultimately threatens the health of humans (Rizwan etal. 2016).

Another source of environmental pollution is the release of inorganic Cu into the

atmosphere in the form of particulate matter, mist, and dust particles (Fang etal.

2011). High concentration of copper has been found in the river (Nyam-wamba)

near the copper mine of Kilembe, Western Uganda. Another study showed a high

copper level of 15.01 mg/L in both ground and surface water at 33 places, which are

located near mines of copper at Malanjhkhand in India. Cu’s highest concentration,

i.e., 2.8 mg/L, was reported in well water of Pothi Bala (AJ&K) (Javaid etal. 2008).

The permissible Cu concentration in the case of soil on which application of sewage

sludge is carried out is 50–140mg/kg as per European Standards (Radojevic and

Bashkin 2006). Different regions of Pakistan revealed the copper range of

<6–412mg/kg in both dust and soil, whereas the highest content of copper was

reported in contaminated soil of the Kohistan region (Muhammad etal. 2011). The

industrial area of Islamabad (Pakistan) also showed elevated copper concentration

level, from 8.88 to 357.40 mg/kg (Malik etal. 2010). A high concentration of cop-

per was found in the sediments of Malir River (Karachi, Pakistan), i.e., 272 mg/kg,

and River Ravi (Punjab, Pakistan), i.e., 159.79mg/kg (Abdul etal. 2009; Siddique

etal. 2009). Elevated range of copper (09–75mg/kg) was reported in different veg-

etables grown in Gillgit (Northern Pakistan) (Khan etal. 2010). The mentioned

values here are alarming as the allowable intake value for copper is 10mg per day.

The maximum amount of Cu reported in Chile, Hong Kong, India, Nigeria, and the

USA was 1.2mg/L, 4.6mg/L, 1.9mg/L (Xu etal. 2006), 0.01mg/L (Olalekan etal.

2018), and 4.8 mg/L, respectively (Zahoorullah and Zai 2003).

H. Haroon etal.

151

7.4 Health Effects ofChromium andCopper

On the basis of time of exposure, toxicity can be dened as acute and chronic. Acute

toxicity is displayed within a short time due to the short-term single exposure of a

few minutes or several days with the toxic substance like heavy metals and is used

to indicate a hazardous event or toxic properties of a substance. However, chronic or

toxic effects (toxicity) are dened as sub-lethal effects due to the prolonged expo-

sure generally to a small quantity of toxic substances.

Public health concerns in the case of chromium are mainly related to the Cr (VI),

due to its toxic properties on animals, microorganisms, plants, and humans

(Alemayehu etal. 2011). The human health risks depend on dosage, exposure level,

and time duration of Cr (VI). Chromium enters into the body of living organisms

through either food or water, whereas acute and chronic effects include neurologi-

cal, cardiovascular, renal, hematological, gastrointestinal, hepatic, and even death.

A long-term and continuative exposure, i.e., occupational exposure, to even low

amount of chromium, can affect the blood, skin, immune, and respiratory system

(Zhang etal. 2014). Nonoccupational exposure includes cigarette smoke, contami-

nated water, air, and food (Shankar and Venkateswarlu 2011). Workers in a German

chrome ore industry developed lung cancer. Numerous studies also conrmed ele-

vated level of cancers (lung and nose) in people exposed to different Cr processing

industries (Shankar and Venkateswarlu 2011).

The genotoxicity effect of chromium at cell level results in the damage of DNA,

oxidative stress, and development of the tumor (Wise etal. 2019). According to

USEPA (United States Environmental Protection Agency), Cr(VI) is listed among

seventeen hazardous metalloids and metals that are risky to the health of humans.

Moreover, exposure to Cr (VI) by other living things like animals and plants also

results in severe health issues in them (Jobby etal. 2018).

In order to protect environmental health, the recommended maximum permissi-

ble limit of Cr is 64mg per kg (Shahid etal. 2017). Literature revealed the elevated

levels of various heavy metals including Cr in the blood of welders who are occupa-

tionally exposed to the fumes of welding and also displayed more oxidative stress

than control group (Mahmood etal. 2015). Similarly, welders working in the stain-

less steel industry are exposed to the Cr (VI) and have high risk of pharynx and

larynx cancer (Gustavsson etal. 1998). Another study in Lahore, Pakistan, reported

higher amount of Cr, Pb, and Cd in cancer and diabetic patients (Shaque etal. 2011).

Cr analysis in groundwater catchment of Luan River (China) indicated 2.074

hazard value for people living in the surroundings of the study area, which is greater

than the permissible value (1) and 3.99× 10−5 was the average carcinogenic risk

value for studied metal of Cr (Liu and Ma 2020). Literature revealed the highest

cancer risks (6.54 × 10−3) probability in public of Khorramabad, Iran, through

drinking water contaminated with chromium (Mohammadi etal. 2019b). Cr (VI)

was also reported in the ground (1.35mg L−1) and surface water (0.027–2.48mg

L−1) of India in Odisha state of the Sukinda area. The cancer risk due to Cr

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

152

contaminated water in children and adults was 1.05×10−3 and 1.21×10−3, respec-

tively, while the oral hazard index was 1.64 and 1.90 times higher in children and

adults, respectively (Naz etal. 2016). Generally, chromium does not accumulate in

the body of sh, but when a large amount of chromium enters into surface water it

can affect sh gills. In the case of animals, chromium can weaken the immune sys-

tem and cause respiratory difculties, genetic disorders, infertility, and development

of tumors. Chronic exposure of chromium in humans can result in skin lesions and

causes various respiratory diseases even cancer of broncho pulmonary (Ahmad

etal. 2012).

Copper is an important element for living organisms, but in excess amount it has

many negative effects on plants, animals, and humans (Zhou etal. 2018). Daily

intake of copper occurs through diet, i.e., 75% and 25% through food and drinking

water, respectively (Brewer 2015). Copper is mainly present as organic cuprous

(Cu+) form in solid food (Ceko etal. 2014) and as inorganic cupric (Cu2+) form in

drinking water. The Cu2+ is toxic and carcinogenic when used in excess amount

through ingestion. The excessive consumption of Cu2+ will result in its liver deposi-

tion following vomiting, abdominal pain, headache, liver failure, etc. (Akar

etal. 2009).

The average intake of Cu from drinking water is in the range of 0.1–1mg per day.

The permissible limit of Cu2+ for industrial efuent is 1.3 mg/L by US, EPA

(Shawabkeh etal. 2004), whereas for drinking water the allowable limit of Cu2+ is

1.5mg/L as recommended by WHO (Organization 2018). The acute effects of cop-

per intake in humans include various gastrointestinal symptoms, for example,

abdominal pain and nausea (Taylor etal. 2020). The RfD (oral) value of 0.04mg

Cu/kg/day is protective for children and adults of any acute or chronic toxicity

(Taylor etal. 2020). It is reported that excess amount of copper in drinking water

has caused pink disease (toxic syndrome) in infants (Thornton 1983). However,

another disease (chronic) due to the excess use of copper is hepatolenticular degen-

eration, also known as Wilson’s disease, which damages various body organs of a

person and will result in death (santé etal. 2004).

Another occupational hazard of copper intake through aerosol is the vineyard

sprayer’s lung disease (Todd etal. 1934). Exposure to a large amount of copper for

a long time will result in a high percentage of copper in tissues and serum, which

affects the immune system and leads to oxidative stress (Turnlund etal. 2004). If

excess of copper is present in freshwater bodies, then it will impair the osmoregula-

tory mechanism of aquatic organisms (Lee etal. 2010).

Copper piping network is mostly used in homes and public supply of drinking

water which is the main source of copper exposure to people (Uauy etal. 2008).

Cases of liver cirrhosis were reported in various regions of India in some young

children, when they used milk which was stored in the copper containers (Nayak

and Chitale 2013; Uauy etal. 2008).

H. Haroon etal.

153

7.5 Treatment Methods forHexavalent Chromium

andCopper Removal

7.5.1 Physicochemical Methods

7.5.1.1 Adsorption ofChromium andCopper

Adsorption is considered an effective method for the removal of heavy metals. It is

an economical method capable of removing heavy metals at very low concentration

(Ali 2012). During adsorption, soluble gases and liquids attach onto the surface of

adsorbents. The adsorbents used for the removal of heavy metals include activated

carbon (Sounthararajah etal. 2015), y ash (Weng and Huang 2004), modied chi-

tosan (Justi etal. 2005), landll clay (Ghorbel-Abid and Trabelsi-Ayadi 2015), peat

(Ho and McKay 1999), and manganese oxides (Kim etal. 2013).

Adsorption can be divided into two main types, i.e., physisorption and chemi-

sorption. In physisorption, van der Waals force is responsible for the attachment of

pollutant and adsorbent. On the other hand, chemisorption occurs as a result of

chemical bonding between adsorbent and adsorbate. Adsorption capacity of the

adsorbents depends upon the characteristic of adsorbent surface. For example, sur-

face charge, surface area, and functional groups on the adsorbent can have different

removal efciencies for different pollutants.

Several studies have been focusing on the removal of hexavalent chromium using

natural (Enniya etal. 2018), synthetic (Huang etal. 2015), waste (Valentín-Reyes

etal. 2019), and composite materials (Geng etal. 2019; Vakili etal. 2018). A wide

variety of adsorbents can be used for the treatment, such as activated carbon

(Valentín-Reyes etal. 2019), carbon nanotubes (Huang etal. 2015), chitosan (Vakili

et al. 2018), graphene oxide (Geng et al. 2019), apple peels, etc. (Enniya et al.

2018). Recent studies on chromium removal are shown in Table7.1.

The Fourier Transform Infrared (FTIR) results before and after Cr (VI) adsorp-

tion suggest that band stretching of C = O, C-O-C, C = C, and C≡C groups was

involved for the binding of Cr (VI) (Enniya etal. 2018). The nitrate, amine, and

amide groups can also be involved in the binding process (Geng etal. 2019). Other

mechanisms involved chelation, electrostatic interaction, and reduction (Geng etal.

2019; Vakili etal. 2018). Several studies focused on the reduction of Cr (VI) to Cr

(III) besides adsorption, as 50% reduction was observed on modied activated car-

bon (Valentín-Reyes etal. 2019).

Several factors might affect the removal efciency of the Cr (VI). Mostly, the

highest adsorption occurs at acidic pH 2.0 (Enniya etal. 2018; Geng etal. 2019;

Haroon etal. 2017; Vakili etal. 2018), with adsorption capacity ranging from 39 to

436.2 mg/g. It ts best with Freundlish isotherm, follows pseudo-second-order

kinetics, and is spontaneous and endothermic reaction (Enniya etal. 2018; Huang

etal. 2015). The Langmuir isotherm is also reported (Huang etal. 2015), while

Geng etal. reported that Cr (VI) adsorption initially followed pseudo-second-order

and at the end it became multistep inuence (Geng etal. 2019). This suggests that

Cr (VI) adsorption is highly dependent on the type of adsorbent used.

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

154

Table 7.1 Technologies used for chromium removal

no. Method Types Mechanism

Removal

effciency

(%)

Adsorption

capacity (mg

g −1) Medium References

01 Adsorption Activated carbon,

graphene oxide,

apple peel,

Chelation, reduction,

binding with acid

components, etc.

99 39–436 Aqueous Enniya etal. (2018), Geng etal.

(2019), Huang etal. (2015), Vakili

etal. (2018), and Valentín-Reyes

etal. (2019)

02 Electrocoagulation Use of iron,

aluminum, copper

as electrodes.

Charge neutralization,

aggregate formation, and

reduction to Cr (III)

88–100 – Aqueous Arroyo etal. (2009), Khan etal.

(2019), Mahmad etal. (2016), Pan

etal. (2017), and Pikna etal. (2020)

03 Membrane

ltration

Microltration Cr (VI) aggregation by

micelle, coagulation, etc.

and size-based separation.

99.6 – Aqueous Doke and Yadav (2014), Liu etal.

(2020), Vasanth etal. (2012), and

Visvanathan etal. (1989)

Ultraltration Cr (VI) size enhancement

and size-based separation.

90–100 – Aqueous Aliane etal. (2001), Aroua etal.

(2007), Ghosh and Bhattacharya

(2006), and Muthumareeswaran

etal. (2017)

Nanoltration Selective removal of

divalent and larger ions and

particles.

80–99.8 – Aqueous Mnif etal. (2017), Wei etal. (2019),

and Zolfaghari and Kargar (2019)

Reverse Osmosis Selective rejection of

monovalent and larger ions.

99 – Aqueous Gaikwad and Balomajumder (2017)

and Piedra etal. (2015)

04 Ion exchange Anion exchange Adsorption or binding with

functional groups on ion

exchange resins.

97–100 236–277 Aqueous El-Mehalmey etal. (2018),

Meshram etal. (2018), Rapti etal.

(2016), and Xie etal. (2019)

05 Bioremediation Fungi Reduction of Cr (VI) to Cr

(III) and bioaccumulation.

89–99.4 2.12–4.9 Aqueous bibi etal. (2018) and Kumar and

Dwivedi (2019a, b)

Bacteria Reduction using chromate

reductase enzyme.

92–100 – Aqueous Baldiris etal. (2018), Hossan etal.

(2020), Tariq etal. (2019), and

Tharannum (2020)

H. Haroon etal.

155

Different studies on copper removal are shown in Table7.2. In a study, chitosan

was modied with ethylenediaminetetra-acetic acid (CS-EDTA) and was used for

copper removal from aqueous solution. The adsorption capacity of CS-EDTA was

also compared with chitin and chitosan. The adsorption capacity of CS-EDTA for

copper was maximum, i.e., 58. 67 and 110mg g−1. The adsorption kinetics was best

t to pseudo-second-order (Labidi etal. 2016). In another study, sulfur microparti-

cles were synthesized by using facile method. These microparticles were used for

the removal of copper from aqueous solution of ethanol. Sigmoidal kinetic mode

best explained the adsorption process. Sulfur microparticles caused physical adsorp-

tion (Xie etal. 2017). Batool etal. (2017) removed copper from water using low-

cost farmyard and poultry manure-derived biochars. Both types of biochars

efciently removed copper from water. The adsorption capacity of farmyard-based

biochar was maximum (44.50 mg/g). Chemisorption was observed during that study

(Batool etal. 2017). Anbinder etal. 2019, studied the structural mechanism involved

in the adsorption of copper. The interaction between copper and chitosan matices

was through NH2 groups in a pendant fashion. In the case of chromium, the adsorp-

tion was due to azanide and OH functional groups (Anbinder etal. 2019). Dong

etal. (2019) recently removed copper ions from aqueous solution by using modied

wheat straw. The wheat straw was modied with polyethylenimine (PEI) by using

epichlorohydrin (ECH) as grafting agent. The mechanism behind this adsorption

was coordination. The adsorption capacity of modied wheat straw was 48.6 mg/g.

The copper adsorbed wheat straw was also regenerated by using 0.1 molar HCl

solution (Dong etal. 2019).

7.5.1.2 Electrocoagulation-Based Chromium andCopper Removal

Electrocoagulation (EC) is the electrochemical process which generates metal ions.

These metal ions destabilize the pollutants by neutralizing the electric charge on

them. The charged metal ions with the oppositely charged pollutants form ocs. EC

process is very effective for the removal of pollutants. This process produces little

amount of sludge, there is no chemical requirements, and its operation is simple

(Rajeshwar and Ibanez 1997).

Electrochemical process mechanism in an aqueous solution is very complex (Lin

etal. 1998). There are three most commonly involved mechanisms during the elec-

trochemical process, i.e., electrocoagulation (EC), electrooxidation (EO), and elec-

trootation (EF). EC process results in the destabilization of pollutants by the

production of electric current. During the EC process, metals and metal hydroxide

cations are used. EO process breaks down organic pollutants into carbon dioxide,

water, and other oxides by oxidation. EF, on the other hand, produces hydrogen and

oxygen gas bubbles which carry the pollutants to the surface. Other possible mecha-

nisms during electrocoagulation are sorption and coagulation (Malkin 2003).

The electrocoagulation is a simple electrochemical process relying on the ow of

current through electrodes (usually Iron or Aluminum) which dissociates in the

solution to neutralize the Cr(VI). Compared to aluminum anodes, the iron anodes

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

156

Table 7.2 Technologies used for copper removal

Method Types Mechanism

Removal

efciency

(%)

Adsorption

capacity (mg

g−1) Medium References

Adsorption Chitosan- ethylenediaminetetra-

acetic acid (CS-EDTA)

Pseudo-second-order – 58. 67 and

110

Aqueous Labidi etal.

(2016)

Sulfur microparticles Mass transfer, coordination and

physical adsorption

– – Ethanol-

aqueous

solution

Xie etal.

(2017)

Farmyard and poultry

manure-based biochars

Multilayer sorption, chemical

interaction

– 44.50 Water Batool etal.

(2017)

Chitosan matrix Amino groups in a pendant fashion – – Aqueous Anbinder

etal. (2019)

Wheat straw (WS) was

modied by polyethylenimine

(PEI)

Coordination – 48.6 Aqueous Dong etal.

(2019)

Electrocoagulation

Mucilage of Opuntia cus

indica (OFI)

Electrochemical production of metal

ions and buoyant gas bubbles

100 – Water Adjeroud

etal. (2018)

New cell design Electrochemical production of metal

ions

98 – Copper plating

plant Efuents

Kilany etal.

(2020)

Electro-Fenton and

electrocoagulation

Oxidation, electrochemical production

of metal ions

– – Wastewater Guan etal.

(2018)

Photovoltaic Electrocoagulation Electrochemical production of metal

ions

99.01 – Aqueous

solution

Thanh etal.

(2019)

H. Haroon etal.

157

Method Types Mechanism

Removal

efciency

(%)

Adsorption

capacity (mg

g−1) Medium References

Ion exchange Polymeric submicron ion

exchange resins

Solid phase ions shared with equal ion

numbers from contaminated water

46 – River water Murray and

Örmeci

(2019)

Amberlite IRC-86 Solid phase ions shared with equal ion

numbers from contaminated water

78.9 – Bioleached

wastewater

Choi etal.

(2020)

Chelating resins Solid phase ions shared with equal ion

numbers from contaminated water

– 167 Synthetic

efuents

Edebali and

Pehlivan

(2016)

Phosphorylated fullerene/

sulfonated polyvinyl alcohol

(PFSP) cation exchange

membrane

Solid phase ions shared with equal ion

numbers from contaminated water

73.2 1.67 Wastewater Rikame etal.

(2017)

Hydrophilic nanoporous ion

exchange barrier membrane,

Stripping 100 – Aqueous

solution

Song etal.

(2018)

(continued)

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

158

Table 7.2 (continued)

Method Types Mechanism

Removal

efciency

(%)

Adsorption

capacity (mg

g−1) Medium References

Membrane

ltration

PEI-based nanoltration

membranes

The membrane structure acts as a

selective barrier that allows movement

of molecules to pass through with the

help of a driving force producing large

residual volumes

86 – Wastewater Bandehali

etal. (2019)

Reusable novel membranes Bacterial cellulose (BC) nanobril

network as a template and chitosan

(Ch) as the active phase

50 – Wastewaters Urbina etal.

(2018)

Modied cellulose acetate

ultraltration membranes

Increases the available sites in the

modied membranes

99.1 – Synthetic

wastewater

Kanagaraj

etal. (2020)

Novel membranes based on

polyethersulfone (PES)

Increases the available sites in the

nanocomposite membranes

90 – Water Raeian

etal. (2019)

Electrospun nanober

membrane

Pseudo-second-order, Langmuir-type

adsorption

– 120.77 Industrial

wastewater

Chen etal.

(2018)

H. Haroon etal.

159

Method Types Mechanism

Removal

efciency

(%)

Adsorption

capacity (mg

g−1) Medium References

Bioremediation Myriophyllum aquaticum Metabolism by the plants and

biodegradation by rhizosphere

microorganisms

– – Wastewater Guo etal.

(2020)

Aquatic plant species Metabolism by the plants – 63.1 mg/kg Synthetic

wastewater

Lu etal.

(2018)

Pistia stratiotes First-order elimination kinetics 96.38 – Surface and

distilled water

Tang etal.

(2020)

Limnocharis ava 1st order, Rate Law model 39.9 – Distilled,

mineral, and

surface water

Alikasturi

etal. (2019)

Pseudomonas stutzeri LA3 Breaking complex pollutants into

simpler form

50 – LB broth Palanivel

etal. (2020)

Escherichia coli Adsorption 91.5 – Aqueous

solutions

Wang etal.

(2019)

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

160

are preferred due to their higher removal efciency and afnity for Cr(VI) (Pikna

etal. 2020). This is an efcient method for recovering Cr(VI) in solid form. The

method has been applied on several types of wastewaters and aqueous media such

as leachate (Arroyo etal. 2009; Mahmad etal. 2016).

The mechanism of electrocoagulation depends on the generation of coagulant

from the anodes due to oxidation, destabilizing contaminants, breaking of emul-

sions, particulate suspension, and forming ocks by aggregating destabilized phases

(Arroyo etal. 2009). The iron (II) gets oxidized into iron (III) besides Cr (VI) into

Cr (III) and forms oxides of iron with chromium (Pan etal. 2017). Usually, Cr (VI)

can be recovered as precipitates in the EC process in the form of oxides of iron and

Cr (VI) with 20% Cr by weight. The solid precipitates are mainly chromite (FeCr2O4)

or their hydroxides or Cr2O3, Fe2O3, FeCr2O4 mixtures (Arroyo etal. 2009; Pikna

etal. 2020).

The parameters affecting the EC process are pH, current, and electrolyte concen-

tration. Pikna etal. (2020) optimized Cr (VI) recovery from four steel slag leachates

in 140–430min, pH 6.0, and 0.1–0.5 A to completely remove 1g/L of Cr (VI)

(Pikna etal. 2020). Khan etal. reported a 100% removal efciency at 1.48 A cur-

rent, pH 3.0, and process time of 21.47min (Khan etal. 2019). The iron-based

anodes have superior removal efciency at pH 7.0, while aluminum electrode is

active at acidic pH (3.0) with comparatively lower removal efciencies (Mahmad

etal. 2016).

The cost effectiveness of this process should be considered as it is an energy-

consuming process. The pH and electrolyte concentrations are very important in

energy efciency of EC process as pH 6.0 is efcient and higher pH (8.0) can con-

sume more current. In contrast, low electrolytes (1000 mg/L NaCl) consume more

current compared to higher electrolytes (50,000 mg/L NaCl) (Pikna etal. 2020).

The energy consumed per gram Cr (VI) removed is 12.97–Watt/hour during an EC

process (Khan etal. 2019).

Electrocoagulation-electrootation (EC-EF) process was used for the removal of

copper from water by using Opuntia cus indica (OFI) plant mucilage. The OFI

mucilage removed copper completely. Mucilage also increased the sludge settling

rate. OFI mucilage which is found to be an active natural coagulant can be used for

copper removal instead of chemical coagulants (Adjeroud etal. 2018). Kilany etal.

2020, developed a new electrocoagulation reactor. In a new design, a helical tube

anode was placed between two (vertical cylindrical screen) cathodes. The new reac-

tor was used for both oil and Cu removal from electroplating plant efuent. Under

optimum conditions, copper and oil removal was 98% and 85%, respectively

(Kilany et al. 2020). Guan et al. (2018) designed electrochemical reactor for

Cu-EDTA degradation. In electrochemical reactor electro-Fenton and electrocoagu-

lation process were used. During Electro-Fenton process, •OH radicals were gener-

ated which were responsible for Cu-EDTA destruction which releases copper ions.

These copper ions were removed by using the electrocoagulation process (Guan

etal. 2018). A solar photovoltaic cell (PV) was used as renewable energy source for

the electrocoagulation process. This process was highly efcient for copper removal

H. Haroon etal.

161

(99.01%) and energy saving (1.039 kWh/m3). The use of PV system with electroco-

agulation process can make it a sustainable process (Thanh etal. 2019).

7.5.1.3 Membrane Filtration-Based Chromium andCopper Removal

Membrane ltration technologies are broadly divided into ve major processes, i.e.,

microltration (MF), nanoltration (NF), ultraltration (UF), reverse osmosis (RO),

and electrodialysis (ED). The major difference in these technologies includes pore

size, permeability, and operating pressure (Murthy and Chaudhari 2009). The main

advantages of membrane technologies include high efciency, complete removal of

pollutants, and sometimes they consume less energy than thconventional methods

(Farno etal. 2014; Marjani etal. 2012; Rezakazemi etal. 2013a; Rezakazemi etal.

2015). Due to the above-mentioned advantages, this technology was used for the

removal of heavy metals from different industries wastewater (Baheri etal. 2015;

Rezakazemi etal. 2012, 2013b).

Due to the simple separation mechanism of membrane technologies, they are

widely used for treatment of water and wastewater (Murthy and Chaudhari 2009;

Padaki etal. 2015). This separation mechanism is same for almost all membrane

processes with minor exceptions. The rejection of pollutants is due to higher trans-

membrane pressure (Sutherland 2008). The separation of pollutants takes place with

the help of semipermeable membrane. This semipermeable membrane blocks the

passage of pollutants through the membrane (Sutherland 2008; Van der Bruggen

and Vandecasteele 2003).

Microltration and ultraltration cannot remove dissolved Cr (VI) due to larger

pore size. The removal can be enhanced by preltration aggregation of the Cr (VI)

by various means. A surfactant-based separation process utilized the use of cetyl-

pyridinium chloride (CPC) to create Cr (VI) micelle that further passed through

titanium-based microltration membrane with 99% removal (Doke and Yadav

2014). Precipitating Cr (VI) into hydroxides with electric eld across the microl-

tration membrane reduced the membrane fouling besides removing Cr (VI)

(Visvanathan etal. 1989). Similarly, biomass-assisted ceramic membrane microl-

tration using baker’s yeast removed 94% of 100 mg-Cr (VI)/L (Vasanth etal. 2012).

A composite polyacrylonitrile electrospun membrane was effectively removing Cr

(VI) and Cd (II) with nanoparticles having 90% regeneration ability (Liu etal. 2020).

A similar method can be applied for Cr (VI) removal by ultraltration. The

polymer- enhanced ultraltration using chitosan, polyethyleneimine, and pectin was

used to remove 100% Cr (VI) (Aroua etal. 2007). A micelle-enhanced ultraltration

using cetyl pyridinium chloride (CPC) as surfactant was good for low concentration

feed, but pressure started increasing when the concentration was increased upto 50

mM (Ghosh and Bhattacharya 2006). An indigenously prepared hydrolyzed polyac-

rylonitrile membrane effectively rejected 90% of ≤25mg Cr (VI)/L at neutral pH in

drinking water (Muthumareeswaran etal. 2017). Water-soluble macroligand formed

complexation with Cr (VI) before ultraltration to achieve 95% removal efciency

(Aliane etal. 2001).

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

162

Nanoltration is highly suited for the divalent ion removal from water. Zolfaghari

and Kargar (2019), optimized the membrane ltration containing microltration

and nanoltration as: pH 10.0, pressure: 0.1MPa pressure, 0.1 mg-Cr (VI)/L, and

500 mg-sulfate/L to achieve 99.8% removal (Zolfaghari and Kargar 2019).

Nanoltration membrane with enhanced negative charges showed comparatively

better Cr (VI) and sulfate rejection (80%) at pH 7 than the positively charged mem-

brane at similar permeance of 11.5Lm−2h−1 bar−1 (Wei etal. 2019). Similarly,

99.7% Cr (VI) rejection was obtained using commercial nanoltration membrane

on shock absorber manufacturing wastewater (Mnif etal. 2017).

Reverse osmosis (RO) membrane selectively removes monovalent ions and uti-

lizes the semipermeable membrane that only allows water molecules to pass under

high pressure. A near 100% removal efciency of 228 mgCr(VI)/L was reported

with a polyamide reverse osmosis membrane with 30 bar pressure, 29% ux, and

95% water recovery (Piedra etal. 2015). The at sheet polyamide RO membrane

simultaneously rejected 99.7% of 5 mg/L uoride and Cr (VI) with at 16 bar pres-

sure and pH 8.0 (Gaikwad and Balomajumder 2017).

Bandehali etal. (2019) removed lead and copper from wastewater using modi-

ed PEI-based nanoltration membrane. The water ux of modied membrane was

higher than the PEI membrane. The lead and copper rejection of modied mem-

brane was 85 and 86%, respectively. The lead and copper removal of this membrane

was better than other membranes reported in the literature (Bandehali etal. 2019).

A novel membrane using in situ and ex situ route was developed by Urbina etal.

(2018) for the removal of copper from wastewater. Bacterial cellulose and chitosan

were the main components of these novel membranes. The highest removal of cop-

per was achieved with the membranes synthesiszed by using in situ biosynthesis.

These novel membranes are easy to clean and can also be reused (Urbina etal.

2018). Recently Kanagaraj etal. 2020, used phase inversion technique for the devel-

opment of a modied cellulose acetate (CA) membrane for the removal of humic

acid and copper. The maximum humic acid and copper rejection was 98.5 and

99.1%, respectively. The newly developed membrane also had higher ux rate and

hydrophilicity. The modied CA membrane also had better anti-fouling property

(Kanagaraj etal. 2020). In a novel membrane, polyethersulfone (PES) and amine-

functionalized cellulose nanocrystals (CNC) were used for Cu and dye removal

from water. The surface of CNC was further modied with the help of triethoxysi-

lane. The modied membrane was able to enhance the removal of copper and dye to

90 and 99%, respectively. The modied membrane had been found as simple and

highly efcient technique for pollutants’ removal (Raeian etal. 2019). Chen etal.

(2018) removed copper from wastewater by using electrospun nanober membrane.

The maximum adsorption capacity of this membrane for copper was 120.77mg/g.

The membrane was able to prevent adsorbents’ loss and aggregation. The mecha-

nism behind copper removal followed Langmuir-type adsorption (Chen etal. 2018).

H. Haroon etal.

163

7.5.1.4 Ion Exchange-Based Chromium andCopper Removal

Ion exchange results in the interchange of ions between liquid and solid phases

(Kurniawan etal. 2006). During the ion exchange process, resins remove ions from

electrolytic solution and replace other ions of the same concentration. There is no

structural change of resins (Rengaraj etal. 2001; Vigneswaran etal. 2005). There is

also recovery of heavy metals from inorganic compounds existing in the wastewater

(Daṃbrowski etal. 2004). Ion exchange is an economical and efcient process for

the removal of heavy metals. There is less generation of sludge during this process

(Chiarle etal. 2000; Lacour etal. 2001; Lin etal. 2000; Rengaraj etal. 2001).

Ion exchange takes place in three stages. At rst, there is physical adsorption

followed by formation of complex between heavy metal ions and oppositely charged

ions; at the end, there is hydration on the surface of adsorbents (Ferreira etal. 1999).

There is reversible exchange of ions between solid and liquid phases. During the ion

exchange process, strong acidic cations can effectively remove heavy metals (Kang

etal. 2004).

Strong base anion exchange is an effective way to remove aqueous Cr (VI). This

technology utilizes a lter bed lled with polymeric resins with functionalized sur-

faces (quaternary amines) (Gorman et al. 2016). These resins when completely

exhausted with the pollutants can be regenerated using 4 Molar acid (Rapti etal.

2016), 15% base (Meshram et al. 2018), or 15% sodium chloride solution

(Subramonian and Clifford 1988) and efciently removes monovalent and more

selectively divalent anions (Subramonian and Clifford 1988).

A novel composite metal organic framework silica gel has been reported to

uptake 277 mgCr(VI)/g even in the presence of competitive ions (El-Mehalmey

etal. 2018). A protonated amine-functionalized metal organic framework in a col-

umn has been reported to remove over 1000 mgCr(VI)/L at pH 3.0 and very low

concentrations of 6ppm to 47ppb which is difcult to remove by precipitation

method (Rapti etal. 2016). Hypercrosslinked imidazolium-based polyionic liquids

were reported to effectively adsorb 236 mgCr(VI)/L with 84% adsorption sites as

anionic exchange resin at a broad pH range (Xie etal. 2019). Similarly, a strong

base anion exchange membrane (Amberlite IRA400 and IRA900) was able to

achieve over 97% Cr (VI) removal of 50ppm from aqueous solutions and real

wastewater (Meshram etal. 2018).

The limitation of this technology is the generation of spent brine containing Cr

(VI). Chen etal., adapted a photochemical technique with carbon-centered radicals

to reduce Cr (VI) into Cr(III) precipitates in the spent brine containing Cr(VI).

Acidic pH enhanced the reduction and presence of chlorides decreased the removal

efciency (Chen and Liu 2020).

Polymeric submicron ion exchange resins (SMR) were used for the removal of

copper, nickel, and zinc from water. The copper removal from river water was 46%,

while in wastewater copper removal was 38% (Murray and Örmeci 2019). Choi

etal. 2020, removed copper from bioleached wastewater by using Amberlite IRC-86

ion exchange resin. The copper removal was pH-dependent. The maximum Cu

removal was 78.9% at pH value of 5. Two-step sequential process was more

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

164

effective in copper removal (Choi etal. 2020). Bispicolylamine and iminodiacetate

were used as chelating resins for copper removal from water. These chelating resins

required a short contact time for copper removal. These resins were reusable with-

out a major reduction in their removal capacity (Edebali and Pehlivan 2016). Rikame

et al. (2017) developed phosphorylated fullerene/sulfonated polyvinyl alcohol

(PFSP) cation exchange membrane capable of not only removing copper from

wastewater but also produced electricity. The cationic membrane was used in micro-

bial fuel cell (MFC). The ion exchange capacity of the membrane was 1.67 meq/g.

PFSP cation exchange membrane removed 73.2% copper from wastewater. Copper

removal efciency and electricity generation of PFSP cation exchange membrane

were better than Ultrex membrane (Rikame etal. 2017). In another study, Song

etal. (2018) removed copper and nickel from aqueous solution using hydrophilic

nanoporous ion exchange barrier membrane. The membrane was highly selective

for copper and nickel removal. Higher copper ux was observed during the separa-

tion. Stripping was the major mechanism behind copper removal. The membrane

showed high stability in organic extract (Song etal. 2018).

7.5.2 Bioremediation-Based Chromium andCopper Removal

Bioremediation is the removal of pollutants with the help of microorganisms. These

pollutants act as food and energy source for the microorganisms (Azubuike etal.

2016). The microorganisms break down complex and toxic pollutants into a simple

and less toxic form (Ayangbenro and Babalola 2017). Microorganisms are grown in

a polluted environment so that they can produce enzymes and metabolites. These

metabolites are capable of breaking complex pollutants into a simpler form. During

the breakdown of pollutants, energy is also released which is used by the microor-

ganisms for their own growth (Azubuike etal. 2016). Microorganisms capable of

heavy metal transformation can be isolated from both aerobic and anaerobic condi-

tions. Mostly, aerobic microorganisms are used for bioremediation (Azubuike etal.

2016). Phytoremediation, on the other hand, is removal of pollutants with the help

of plants. This technique is widely used in constructed wetlands and oil spills. It is

also called green technology due to its environment friendliness, cost-effectiveness,

and efciency (Ali etal. 2013). Several mechanisms can be involved during the

phytoremediation process. The major six mechanisms involved during phytoreme-

diation are phytoltration, phytovolatilation, phytostabilization, phytoextraction,

rhizodegradation, and phytodegradation (Ali etal. 2013).

The removal or conversion of pollutants by living forms is one of the cost-

effective and easy methods. Several fungal species have been reported to tolerate

and reduce Cr (VI). A 1000 mgCr(VI)/L and many other heavy metal tolerating

Trichoderma lixii was able to reduce Cr(VI) into Cr(III) under various environmen-

tal stresses (pH, temperature, tannary wastewater, etc.) by 99.4% (Kumar and

Dwivedi 2019b). Aspergillus avus tolerating 800 mgCr(VI)/L was also reported to

reduce 89% Cr(VI) into Cr(III) (Kumar and Dwivedi 2019a). Fungi isolated from

H. Haroon etal.

165

contaminated soil showed promising results of intracellular (Rhizopus sp.) and

extracellular (Aspergillus fumigatum and Penicilium radicum) reduction of Cr (VI)

with 95% removal efciency in addition to the safe production of Lactuca sativa L

crop by acting as in situ biofertilizer (bibi etal. 2018).

A bacterial strain Staphylococcus aureus could tolerate 22 mM Cr (VI) and

removed 99% of 100 mgCr(VI)/L in 24h (Tariq et al. 2019). A range of Cr (VI)

stress (10–500 mg/L) on Stenotrophomonas maltophilia with 92–100% removal

efciency at 37oC and pH 7.0. The higher ability of this strain might be associated

with the chromate reductase gene ChrR and soluble fraction of the cell (Baldiris

etal. 2018). An attempt to improve strain of Bacillus amyloliquifaciens by physical

(UV irradiation) and chemical mutagens (acrylamide, ethidium bromide, and ethyl

methane sulphonate) improved the removal efciency of wild type (74%) to a higher

level of 83% and 96% by UV irradiation and acrylamide, respectively (Tharannum

2020). Another strain of Klebsiella sp. also reduced 95% Cr (VI) in Luria-Bertani

broth and only 63% in real tannery wastewater. This suggests that any bioremedia-

tion method utilized should be checked in real or natural conditions as well (Hossan

etal. 2020).

Guo etal. (2020) recently used Myriophyllum aquaticum for the removal of tet-

racycline and copper from wastewater. M. aquaticum effectively removed both pol-

lutants. In the presence of low copper concentration, tetracycline removal was

higher. The role of M. aquaticum in the removal of tetracyclines was major as com-

pared to the microbial biolms (Guo etal. 2020). Eight aquatic plants were used for

the removal of copper from wastewater. The copper removal was maximum in the

presence of Eichhornia crassipes and Pistia stratiotes. Copper was mostly accumu-

lated in the roots and shoots of these aquatic plants. Copper removal was affected by

the presence of lignin contents in the aquatic plants. The higher the concentration of

lignin in plants, the greater was the copper removal (Lu etal. 2018). Tang etal.

(2020) used Pistia stratiotes for copper removal from distilled and surface water.

Pistia stratiotes effectively removed copper from both distilled and surface water.

The maximum removal efciency for copper was achieved in surface water

(96.38%). First-order elimination kinetics was dominant during copper removal

from both types of water. The species got the ability to remove copper from both

nutrient-rich and nutrient-decient wastewater (Tang etal. 2020). Alikasturi etal.

(2019) removed copper from surface, mineral, and distilled water by using

Limnocharis ava. Maximum copper removal efcency was achieved in distilled

water, i.e., 39.9%. First-order rate law model best t the absorption process

(Alikasturi etal. 2019). Palanivel etal. (2020) used Pseudomonas stutzeri LA3 for

copper removal. The maximum copper removal efciency was 50%. Copper

removal was by adsorption and absorption process. Bacterial cell structure was also

altered due to copper absorption. (Palanivel etal. 2020). Genetically engineered

Escherichia coli cell were used by Wang et al. (2019) for copper removal from

aqueous solution. The plasmid of E. coli was modied by adding a copper sensor

and copper adsorbent in the plasmid. The modication enhanced the copper removal

efcency of E. coli. The maximum copper adsorption was 91.5% (Wang etal. 2019).

7 Environmental andHealth Effects ofHeavy Metals andTheir Treatment Methods

166

7.6 Conclusion

Among the various oxidation states of chromium and copper, Cr (VI) and Cu (II) are

the most toxic forms, and when they enters into the environment, they have negative

effects on the environment (air, water, soil) as well as on the health of all living

organisms. There are different methods which can be used for the treatment of both

chromium and copper, like adsorption, ion exchange, membrane ltration, electro-

coagulation, and bioremediation. Based on the current study, it is concluded that

both adsorption and bioremediation are economical and efcient solutions for the

treatment of chromium- and copper-contaminated water.

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Chapter 8

Organophosphates’ Pollution Status

andTheir Remediation Through Microbial

Interaction intheTwenty-First Century

SalihaAhmad, Shazmin, MazharRaque, FawadAli,

MuhammadFarooqHussainMunis, SyedWaqasHassan, TariqSultan,

TariqJaved, andHassanJavedChaudhary

Abstract Organophosphorus pesticides (OPPs), being an attractive alternative to

persistent organochlorine pesticides, are widely used in agriculture. The OPPs are

the main components of herbicides, insecticides, and pesticides. They are deriva-

tives of phosphoric acid having amide, ester, or thiol group possessing aliphatic,

cyclic, or heterocyclic structure. The OPPs are soluble in water as well as organic

solvents owing to their degradable organic nature. Currently more than 140 OPPs

are being used all over the world and their careless handling, and inappropriate

application contaminating environment by negatively affecting non-target species

of humans, birds, animals, and plants through both systematic and non-systematic

actions. The OPPs are utilized as fertilizers, agrochemicals, fungicides, pesticides,

insecticides, acaricides, herbicides, plasticizers, ame retardants, plant growth

S. Ahmad · Shazmin · F. Ali · M. F. H. Munis · H. J. Chaudhary (*)

Department of Plant Sciences, Quaid-i-Azam University, Islamabad, Pakistan

e-mail: munis@qau.edu.pk; hassaan@qau.edu.pk

M. Raque

Department of Soil & Climate Sciences, The University of Haripur, Haripur, Pakistan

e-mail: mazhar.raque@uoh.edu.pk

S. W. Hassan

Department of Biosciences, University of Wah, Wah, Pakistan

e-mail: waqas.hassan@uow.edu.pk

T. Sultan

Land Resources Research Institute, National Agricultural Research Centre,

Islamabad, Pakistan

T. Javed

Department of Botany, Faculty of Life Sciences, Government College University,

Faisalabad, Pakistan

e-mail: mtariqjaved@gcuf.edu.pk

178

factors, chemical warfare agents in agriculture, industrial sectors, as well as for

household purposes. The injudicious utilization of OPPs is casting serious threats to

global environment and health of living organisms. Nervous system of aquatic and

terrestrial fauna is affected due to anti-acetylcholinestrase activity of OPPs such as

chlorpyriphos, dimethoate, phorate, trichlorfon, glyphosate, etc. Their soluble

nature makes them part of water bodies, thus because of various biotic and abiotic

factors, OPPs become part of food chain. Regarding huge devastation caused by

OPPs, it is needs of time to eliminate them from ecosystem. Therefore, their detoxi-

cation from the environment is necessary. There are various chemical, physical,

and biological methods which have been used to reduce OPPs. The photocatalytic

degradation of various OPP compounds has been investigated using UV light and

TiO2 as photocatalyst. Chlorination of water has been reported to degrade OPPs.

Bioremediation is considered as eco-friendly and economical process for the

removal of these toxins as compared to other chemical and physical methods.

Various microorganisms have been investigated which can degrade OPPs into less

toxic compounds. Microbes use OPPs as carbon, phosphorous, and sulfur source,

and electron donor by disrupting OPPs native structure, ultimately converting them

to fewer toxic compoundsin favourable conditions. This chapter highlights toxico-

kinetic study of organophosphates and their mechanism of action in living organ-

isms. This chapter also highlights various microorganisms, i.e., bacteria, fungi, and

algae, potentially involved in biodegradation of OPPs and their mechanism of

bioremediation.

8.1 Introduction

The United Nations Organization for Food and Agriculture (FAO) stated that pesti-

cides either as a single compound or in a combination of different compounds are

anticipated for controlling the growth of unwanted plant species, disease-causing

vectors, or pests that are causing hindrance in agricultural and food-based processes

(Sancho-Martínez et al. 2012). Pesticides target the enzymatic activities of pests

involved in different metabolic pathways. However, pesticides are advantageous

regarding pest elimination and increasing food production. Pesticides are usually

classied on the basis of (i) target pests, (ii) level of toxicity and their potential risk

for human beings, and (iii) chemical structure and properties (Upadhyay and Dutt

2017) (Fig.8.1).

Organophosphates (OPs) are extensively utilized pesticides globally. All OP

compounds have a phosphate group and other organic groups depending on the

nature of the compound. Such compounds are repeatedly practiced in agriculture,

pharma application, cosmetics industry, etc. (Upadhyay and Dutt 2017). Considering

their application in agriculture, OP compounds are largely applied as insecticides,

with an estimated sale of 34% as an insecticide worldwide (Singh et al. 2006).

Tetraethyl pyrophosphate, being the rst OP insecticide, was developed in 1937,

S. Ahmad etal.

179

leading to the worldwide production and commercialization of other pesticides for

pests’ control in houses and agriculture (Singh etal. 2006).

8.1.1 Characteristics ofOrganophosphates

Organophosphate pesticides are organic in nature with high water solubility, low

persistence, and relatively easy degradation as compared to carbamates and organo-

chlorine pesticides (Kumar etal. 2018). Structurally, these compounds are deriva-

tives (amide, ester, and thiol) of phosphoric acid, where R1 is alkyl and R2 is aryl

group bonded to phosphorus atom. They can attach to carbon through oxygen

(phosphates), sulfur (phosphorothiolates or phosphorothioates), or nitrogen atom

(phosphoramidates). Here, X is a variable (aromatic, aliphatic, or heterocyclic) and

is called leaving group because after hydrolysis of ester it is cleaved from phospho-

rus (Fig.8.2) (Sogorb and Vilanova 2002; Vale and Lotti 2015; Dar etal. 2020). The

residual half-life of aryl-substituted OPs is observed more as compared to alkyl-

substituted Ops, leading to their stability and more persistence in the environment.

Low water solubility is found for compounds that are more complex and less polar

Fig. 8.1 Classication of pesticides. (Adapted from Singh etal. 2006)

Fig. 8.2 General structure

of organophosphate

compound. (Kaur and

Goyal 2019)

8 Organophosphates’ Pollution Status and Their Remediation Through Microbial…

180

like ethyl derivatives in relation to methyl derivatives (Chiou etal. 1979). In addi-

tion, OP pesticides have anti-enzymatic function owing to high biological actions as

they can cause irreversible inhibition of acetyl cholinesterase enzyme, required for

normal activity of the brain (Galloway and Handy 2003; Van der Oost etal. 2003).

8.1.2 Sources andDistribution ofOrganophosphates

intheBiosphere

The OP pesticides are available under various trade or brand names and are widely

applied that encounter different non-target living organisms. Regarding their pres-

ence in the biosphere, they are found throughout the world, such as in water bodies,

sediments, in bodies of living organisms, and the atmosphere. Long-term consump-

tion of pesticides put natural resources and biodiversity on stake due to persistent

nature (Kole etal. 2001). Over and non-judicious applications of pesticides pollute

groundwater reservoirs, air, and soil (Aktar et al. 2009; Schafer et al. 2012).

Contamination of water bodies around agricultural land involves simple drifting,

surface run-off, seepage through soil, or spillage causing considerable disturbances

(Moss 2008). Owing to the cumulative and heterogeneous nature of pesticides, they

nd their way into food chains depending on the species, susceptibility to toxins,

and their metabolic peculiarities (Wilkinson etal. 2000; Hodgson 2010). Pesticides,

if used according to the standard agricultural practices, can still enter into the food

chain, destroy the ecosystem balance, and cause signicant ecological changes.

Residues of pesticides enter into the atmosphere by means of evaporation, drift, or

wind erosion and re-enter into the ecosystem through precipitation (Dubus etal.

2000; Lushchak etal. 2018). Rate of pesticide application, their half-life, disposal,

and solubility are key factors that determine the impact of pesticides on soil, plants,

and water resources as they are non-biodegradable and toxic (Anju etal. 2010).

8.1.3 Applications ofOrganophosphates

The OP pesticides are used for the prevention of crops against pests, crop manage-

ment, fruits (storage, packaging, and transportation), pulses, vegetables, as well as

other food supplies (Upadhyay and Dutt 2017). As many of the OP compounds are

soluble in fat and readily enter the body via the skin, they are applied to control

pests present on the bodies of animals. These applications are suggested due to their

fast degradation rate depending on temperature, sunlight availability, and pH along

with other environmental conditions (Ragnarsdottir 2000; Kumar etal. 2018). In

addition, they are also practiced as chemical warfare agents, plasticizers, and air-

fuel ingredients (Singh etal. 2006). Among other OPs, insecticides have replaced

many compounds used earlier due to high impact on insects, adaptation of some

S. Ahmad etal.

181

insects to organochlorine compounds, and rapid degradation in contrast to other

persistent compounds with long residual life such as organochlorines (Chiou

etal. 1979).

Insecticides such as parathion applied to rice elds, fruits, cotton, and soilare

biodegradable. It has been banned in some countries due to its toxic nature (López-

García etal. 2003). Malathion is an active ingredient of many products including

sprays and hair oils for use against head lice and eas as well as small ying insects

and mosquitoes (Aktar etal. 2009). Chlorpyrifos has been used since 1965 against

termites, beetles, grasshoppers, scales, moths attacking on row crops, fruit trees,

and vegetables and became the fourteenth highly used pesticide (Gomez 2009).

Dimethoate is also an insecticide used against many aphids, thrips, and mites caus-

ing damage to cash crops, ornamentals, vegetables, as well as fruits (Van Scoy etal.

2016). Despite these, monocrotophos, profenofos, phorate, diazinon, and disulfoton

are also used as OPPs with diverse actions (Pehkonen and Zhang 2002).

8.2 Toxicokinetics ofOrganophosphates

Pesticides are one of the most harmful pollutants in the environment because of

their mobility and effects on living organisms (de María etal. 2006). Among the

diverse groups of pesticides, the widely used OPPs affect non-target plant species

and animal species found in various terrestrial and aquatic ecosystems (Blann etal.

2009). The toxicokinetics and toxicodynamics of OPPs differ with the level of expo-

sure and the pesticide’s structure (Mkandawire etal. 2014).

8.2.1 Effects onPlant Community

The OPPs adversely affect the plant community and thus the process of photosyn-

thesis (Zobiole etal. 2012). The increasing concentration ofOP insecticide dimeth-

oate i.e., 20, 40, and 80 ppm, showed inhibition in the growth and photosynthetic

activity of pigeon pea plants (Pandey etal. 2015). Foliar spray of glyphosate in

velvet leaf (Abutilon theophrasti) decreases gaseous exchange due to decrease in

stomatal conductance, which results in gradual inhibition of photosynthesis (Fuchs

etal. 2002). The OPPs also affect plant mineral nutrition, carbon metabolism, nitro-

gen metabolism, fatty acid synthesis, and amino acid synthesis (Zobiole etal. 2010,

2011). It has been reported that chlorpyrifos applied at different concentrations on

Vigna radiata cause reduction in nitrogen metabolism and plant growth (Parween

et al. 2011). It has also been reported that OPPs affect photochemical reactions

(Vivancos etal. 2011). Chlorophyll and nitrogen contents decrease with the increas-

ing concentration of OP insecticide (Shams-El-Din etal. 1995). The OPPs reduce

the germination process (Stevens etal. 2008) (Fig.8.3). Barley (Hordeum vulgare

L.) seeds were treated with various concentrations (0.05, 0.1, and 0.5%) of two OP

8 Organophosphates’ Pollution Status and Their Remediation Through Microbial…

182

insecticides, monocrotophos and alphamethrin. These insecticides were investi-

gated to produce chromosomal aberrations and mitotic aberrations in barley

(Srivastava etal. 2008). The OPPs affect the chlorophyll biosynthetic pathway by

preventing the synthesis of catalase, peroxidase, and d-aminolevulinic acids (ALA)

(Barcelos etal. 2012). They change the accessibility of metal ions associated with

photosystems I and II (Cakmak etal. 2009). The OPPs cause oxidative stress in

plants (Vagi et al. 2017). Application of chlorpyrifos, dimethoate, and dieldrin in

Spinacea oleracea L. disturbs the balance of reactive oxygen species (ROS), which

ultimately cause oxidative damage (Singh and Prasad 2018). Glyphosate is reported

to lower the level of ascorbate peroxidases and glutathione peroxidases, which play

a role in scavenging ROS (Gomes et al. 2017). Glyphosate lowers the level of

ribulose- bi-phosphate (RuBP) and phosphoglyceric acid (PGA); hence, it affects

the activity of Rubisco (de María etal. 2006). It has been reported that dimethoate

(0.06%) was sprayed on cotton and soybean. It was observed that dimethoate causes

inhibition of photosynthetic pigments in cotton and soybean (Mishra etal. 2009).

8.2.2 Effects onAnimals

The OPPs adversely affect both aquatic and terrestrial fauna by inhibiting acetyl-

cholinesterase activity, thus affecting their nervous system (Muhammad etal. 2017).

The OP fosthiazate causes acute toxicity in honeybees with small LC50 (Li etal.

Fig. 8.3 Toxicity of organophosphates in plants

S. Ahmad etal.

183

2020). The OPs affect the social role of honeybee and cause colony collapse disor-

der (CCD) (Kiljanek etal. 2016). It has been investigated that dimethoate is toxic

for common carp Cyprinus carpio. After a period of 24, 48, and 96h, the values of

LC50 were recorded as 84, 1.78, and 1.6mg L−1. Low rate of opercular movement,

erratic swimming, and effect on maintaining normal posture were investigated

(Singh etal. 2009). Dichlorvos affects the acetylcholinesterase activity in gill tis-

sues of Pacic oyster (Crassostrea gigas) (Anguiano etal. 2010). The OPPs cause

toxicity in Clarias garipenus and observed inhibition in acetylcholinesterase activi-

ties in plasma and eye homogenate by 84% and 50% (Mdegela et al. 2010).

Malathion exposure to freshwater agellate (Euglena gracilis) is reported to affect

motility, cell shape, and cell density (Azizullah etal. 2011). Exposure of chlorpyri-

fos at different concentrations causes toxicity in larvae of common toad (Dutta

phrynus melanostictu), which slows down swimming activity, decreases growth,

and delays metamorphosis (Wijesinghe etal. 2011). Diazinon is reported to decrease

the concentration of cholinesterase (CheS), lactate dehydrogenase (LDH), testoster-

one, leucocyte count (WBC), hemoglobin (Hb), and erythrocyte count (RBC) in

kutum (Rutilus frissi) (Shamoushaki et al. 2012). Studies on rats indicated the

effects of monocrotophos at various concentrations (0.625, 1.25, 2.5, 5.0, and

10.0 ml kg−1 body weight/day) for a period of 14 days. Liver cells of rats have

shown decreasing levels of aspartate aminotransferase and ALT (alanine amino-

transferase) (Sunmonu and Oloyede 2012). The OPs have been suggested toxic for

algae (Ma etal. 2005). Microalgae of Chlorella were studied to evaluate the toxicity

of chlorpyrifos. The EC50 was found ranging from 7.63 to 19.64mg L−1 (Chen etal.

2016), which may dysfunction homeostatic mechanisms and may inuence sur-

vival. Adult tilapia sh (Oreochromis niloticus) was exposed to diazinon for 30 days

at various concentrations of 1.0, 2.5, 5.0, 7.5, and 10.0mg L−1. The LC50 for diazi-

non was reported to be 7.65mg L−1 after 96h. The concentrations of proteins were

considerably decreased in different body parts, i.e., liver, gills, muscle, plasma, and

kidney (Soyingbe etal. 2012). Diuron and diazinon cause toxicity in the embryo of

zebrash. The LC50 at 96 h was found to be 6.5mg L−1 and EC50 was 4mg L−1,

which changed the behavior of sh (Velki etal. 2017). The effect of diazinon at dif-

ferent concentrations such as 0.25, 0.5, 1, 2, 4, and 8mg L−1 on the embryo of com-

mon carp has been studied. The mortality rate of embryos increases on exposure to

diazinon (Aydın and Koprucu 2005). Monocrotophos cause reproductive toxicity in

female Goldsh (Tian etal. 2010). The OP monocrotophos on exposure to Cirrhinus

mrigala cause histopathological effects on gill, kidney, and intestinal tissues

(Velmurugan etal. 2007; Zahran etal. 2018). The OPPs disrupt steroid metabolism

as well as hepatic phosphagen system (Southam etal. 2011). The OP diazinon has

histopathological effects in the spleen, intestine (lamellar fusion, curling of second-

ary lamellae), gills, and kidneys (glomerulus shrinking, glomerulus lesions, enlarge-

ment of space in Bowman’s capsule) of Rainbow trout (Onchorhyncus mykiss)

(Banaee etal. 2013). The OP malathion causes respiratory stress and instant death

of sh (Subburaj etal. 2018).

8 Organophosphates’ Pollution Status and Their Remediation Through Microbial…

184

8.2.3 Effects onHuman Health

The OPs produce various types of toxicity, and their poisoning results in more than

100,000 deaths each year (Gunnell etal. 2007). The OPP common route for entry in

humans is skin (Kamanyire and Karalliedde 2004). They inhibit acetylcholinester-

ase activity (AChE) causing changes in the peripheral, autonomic, and central ner-

vous systems (cholinergic effects) (Ray and Richards 2001; Ross etal. 2013). The

esterase inhibition occurs because OPP reacts with the active serine center by phos-

phorylation (Das etal. 2006). The OPs cause endocrine, metabolic, neurological,

and hepatorenal disorders (De Silva etal. 2006). Monocrotophos cause neurotoxic-

ity in human brain cells (Tripathi etal. 2017). The OPPs’ acute exposure in humans

results in acute cholinergic crisis, causing intermediate syndrome consisting of

paralysis of proximal limbs, neck, and respiratory muscles 24–96h after the cholin-

ergic crisis. After 2–3weeks of poisoning, it results in distal polyneuropathy (De

Silva etal. 2006). The OPP monocrotophos cause death of children due to choliner-

gic syndrome (Krause etal. 2013). The OPP can cause severe poisoning and cata-

lyze teratogenic or carcinogenic processes (Tankiewicz etal. 2010). Glyphosates

are carcinogenic agents (Carvalho 2017). The International Agency for Cancer

Research investigated that malathion and diazinon have probability to cause human

cancer and reported parathion and tetrachlorvinphos as possible carcinogens. The

OPP causes hyperactivity of Cdk5 kinase and tau hyperphosphorylation which leads

to disruption of microtubules in Alzhiemer’s disease patients. Humans exposed to

acute poisoning of OP display memory and learning issue (Zaganas etal. 2013;

Costa 2018). The OPP causes neurodegenerative diseases, such as Parkinson’s dis-

ease. Workers on exposure to OP leads to respiratory tract infections, decrease in

serum, RBC, and inuenza-like symptoms. Cardiac problems (hypotension, hyper-

tension, cardiac arrest, cardiomyopathy) and hyperamylasemiais were also reported

in case of long-term exposure to OPPs. Gastrointestinal problems such as diarrhea

can occur through OPP ingestion. Humans on exposure to OPP may experience

high fever that may last for several days. The OPPs are responsible for many psy-

chiatric disorders because of the inhibition of acetylcholinesterase activity in farm-

workers (Serrano-Medina etal. 2019). The OPPs cause myopathic disorders, i.e.,

muscular weakness in animals. Paralysis occurs within 24h of OP exposure in hens.

The OP insecticides inhibit the activity of several enzymes such as lipases, chymo-

trypsin, and trypsin by phosphorylation of these enzymes (Karalliedde and

Senanayake 1989). The OPPs can cause genotoxic and mutagenic effects. It is evi-

dent from various studies that OPPs cause chromosomal aberrations and genetic

mutations (Gökalp Muranli etal. 2015). The OPs damage various organs such as the

liver, brain, and kidneys (Fig.8.4). The OPP causes urinary and histopathological

disorders including several diseases such as diabetes, abdominal pain, polyuria,

miosis, dyspnea, bradycardia and rhinorrhoea, eczema, nausea, headache, dyspnea,

and hepatitis (Azmi etal. 2006; Malekirad etal. 2013).

S. Ahmad etal.

185

8.2.4 Effects onSoil Biota

Soil is a reservoir of pesticide residues and microorganisms (Jain etal. 2015). The

knowledge about relationship of pesticides with soil is important to understand

where soil-pesticide minerals, soil-pesticide interaction with organic matter, and

related soil fertility mechanisms are of key importance (Polubesova and Chefetz

2014). In soil, the interaction of pesticides depends on four factors such as nature of

solute and solvent, soil constituents, and its pH (Iovino etal. 2008). The OPPs affect

biochemical processes driven by soil microorganisms such as mineralization, nitri-

cation, denitrication, ammonication, and redox reactions (Mahía etal. 2008).

The OP fungicides affect enzymatic activity phosphatase, dehydrogenase, and ure-

ase (Shukla 2000). Monocrotophos and other OPPs affect survival, growth, repro-

duction, and membrane permeability of algae Scenedesmus bijuga and

Ankistrodesmus falcatus (Nayak etal. 1996). Cypermethrin and monocrotophos are

toxic for soil bacteria and related microbes (Madhuri and Rangaswamy 2002;

Survery etal. 2004). Different types of OP insecticides, i.e., dimethoate, diazinon,

chlorpyrifos, quinalphos, and malathion inhibit growth and population of soil fungi,

soil bacteria, and enzymes (Pandey and Singh 2004; Singh etal. 2005a). The effect

of OP herbicides such as glyphosate, OP insecticide imidacloprid, and fungicide

metalaxyl on PGP activities of Mesorhizobium sp. was studied. It was found that

selected OPPs cause progressive decline in plant growth-promoting (PGP) traits of

Mesorhizobium sp. strain MRC4 (Ahemad and Khan 2012). The OPP chlorpyrifos’

effect on soil microbes was evaluated, and a decrease in the colony-forming units

(CFU) of bacteria and fungi was reported (Supreeth etal. 2016). Glyphosates affect

Fig. 8.4 Toxicity of OPs on aquatic fauna, humans, and soil microbes. (Ahemad and Khan

2011;Tripathi etal. 2017; Subburaj etal. 2018)

8 Organophosphates’ Pollution Status and Their Remediation Through Microbial…

186

the symbiotic relationship of fungus with peanut plant (Pasaribu et al. 2013).

Earthworm species were treated with different concentrations (450, 500, and 600

ppm) of OPP monocrotophos for 45 days. It resulted in reproductive toxicity and

histopathological abnormalities in earthworm species (Gowri and Thangaraj 2020).

Several studies revealed the effect of pesticides on soil microbial biomass and soil

respiration. The decrease in soil respiration reects decrease in microbial biomass.

It was observed that dimethoate at 10mg L−1 completely inhibited biological activ-

ity and growth of Xanthobacter autotrophicus (Hussain etal. 2009b).

8.3 Strategies toMitigate Impact ofOrganophosphates

There are various strategies used for mitigation of OPs, i.e., chemical-based strate-

gies and microbial interaction-based strategies. Different processes are involved in

the remediation of OPs. Chemical methods lead to the production of less toxic com-

pounds, while in microbial degradation methods complete mineralization of OPs

can occur.

8.3.1 Chemical-Based Strategy

There are various chemical methods used for the degradation of OPs. Photocatalytic

degradation and chlorination are the different methods for the degradation of OPs

(Kamel etal. 2009; Sud and Kaur 2012). Chemical agents such as DS2, sodium

hydroxide, and hypochlorite can be used for decontamination of OPs (Kitamura

etal. 2014). The mechanism used by chemical reagents for breakdown of pesticides

includes hydrolysis, oxidation, and reduction (Jacquet etal. 2016). Advanced oxida-

tion processes constitute homogeneous photocatalysis and heterogeneous photoca-

talysis. Homogeneous photocatalysis includes use of various photocatalyst (H2O2,

O3, NaOCl) in the presence of light. Heterogeneous photocatalysis includes use of

semiconductor catalysts such as TiO2, ZnO, and ZrO2 in combination with UV/solar

radiation. The most evolving degrading technology is heterogeneous photocatalysis

using TiO2 as photocatalyst (Sud and Kaur 2012; Mirmasoomi etal. 2017). However,

the mechanism of photocatalytic degradation depends on experimental conditions

such as concentration of oxygen, dose of catalyst, temperature, and pH (Sud and

Kaur 2012). Chlorination of water is another chemical-based method reported to

oxidize OPs. It has been studied that organic thiophosphate compounds (having

sulfur atom bonded to phosphorous atom) undergo oxidation process and form

oxons on reaction with chlorine atom during the disinfection process. However,

some pesticides become unstable in presence of chlorine atoms (Magara etal. 1994;

Kamel etal. 2009). Chlorpyrifos undergo oxidation process in the presence of free

chlorine and oxidize to chlorpyrifos oxon (Duirk and Collette 2006; Acero et al.

S. Ahmad etal.

187

2008). Dimethoate degrades in the presence of chlorine dioxide under water treat-

ment (Pergal etal. 2020).

8.3.2 Microbial Interaction-Based Strategy

In microbial interaction-based strategy, physical interaction between microorgan-

isms and toxic compounds takes place that results in the production of nontoxic

products. Many bacterial and fungal species have been exploited for this purpose.

Several bacteria have been found in contaminated sites and that showed potential to

either consume or decontaminate toxins (Silar etal. 2011; Dubinsky etal. 2013;

Prakash et al. 2013; Gustavsson etal. 2016; Thakur et al. 2019). The microbial

adaptability and versatility have made bioremediation a “biologically friendly”

strategy to remove many toxins that are produced as a result of various anthropo-

genic activities. Microbial degradation usually occurs via co-metabolism or miner-

alization. Co-metabolism involves the conversion of parent compound into less

toxic or water-soluble form. Mineralization accompanies complete conversion into

nontoxic products (CO2, NH3, water, or inorganic compounds) (Upadhyay and Dutt

2017; Yigit and Velioglu 2019).

8.4 Importance ofBioremediation

Due to OPs’ high toxicity, it is important to develop cost-effective and efcient

methods for the removal and detoxication of OP residues in a polluted environ-

ment (Cycon etal. 2013). Bioremediation is promising, cost-effective, highly ef-

cient, nontoxic, relatively simple, and eco-friendly method for the elimination and

detoxication of OPs. Bioremediation involves the use of biological agents that

include plants, microorganisms, or enzymes for the elimination and degradation of

toxic compounds from the polluted environment (Yair et al. 2008; Hussain etal.

2009a). Diazinon treatment in soil results in signicant increase in bacteria by 14%

(p<0.05) and Azotobacter by 27% (p<0.05) (Singh etal. 2005b). Fungi and bac-

teria are well known for their phosphate solubilizing activity. The OPPs increase

phosphate solubilization activity and soil dehydrogenase activity (Majumder and

Das 2016). Pesticides can be harmful for a certain group of organisms and have

benecial effect on other organisms. It was investigated that pesticides’ application

inhibited the activity of certain fungi and increased bacterial activity (Gowri and

Thangaraj 2020). The bacterial strain Serratia marcescens had bioremediation

potential against OPPs polluted soils (Cycon etal. 2013). Bacterial species which

are commonly reported for bioremediation of OP are Bacillus sp., Pseudomonas

sp., Klebsiella sp., and Enterobacter sp. (Raeder etal. 2008; Singh etal. 2020). A

very efcient bacteria Paracoccus sp. was found to degrade 92.47% of OP mono-

crotophos (100mg L−1) in 24 h (Jia etal. 2007). Pseudomonas peli can degrade

8 Organophosphates’ Pollution Status and Their Remediation Through Microbial…

188

100% of OP chlorpyrifos (20mg L−1) (Hossain etal. 2015). Pseudomonas putida

can remediate 100% of OP dimethoate (2mg L−1) within 96h (Nazarian and Amini

2008). Different types of enzymes present in bacteria and fungi can be used for

detoxication and degradation of OPs (Yair et al. 2008). The OP hydrolyzing

enzymes, i.e., cell-free enzyme system, are proven to be effective for bioremedia-

tion of OP (Thakur etal. 2019). Genetically engineered enzyme was used to study

OPP degradation of malathion, monocrotophos, and parathion (Qiao etal. 2003).

Phytoremediation is effective for phytoaccumulation of harmful toxins and meta-

bolic breakdown of pollutants within plant tissues. Plantago major L. effectively

removes chlorpyrifos by 43.76% (Romeh 2020). Lemna forma L. has the ability to

remediate OP glyphosate (Dosnon-Olette etal. 2011). Endophytic bacteria present

in plants enhance phytoremediation of OP (Chen etal. 2012). Aquatic plant Scirpus

validus removes 59.8% of 5mg L−1 dimethoate in 10 days (Fu etal. 2006). OP

chlorpyrifos is accumulated by Populus sp. and Salix sp. (Lee etal. 2012).

8.5 Soil Organisms Play Their Role inBiodegradation

ofOrganophosphates

8.5.1 List ofSoil Microbes Involved inBioremediation

ofOrganophosphate

Several organisms including bacteria, fungi, algae, etc. have bioremediation poten-

tial. However, the extensive role of bacteria has been observed among other micro-

organisms (Sylvia etal. 2005). Active bacterial biodegraders belong to the following

classes: (i) alpha-proteobacteria such as Sphingomonas; (ii) Gamma-proteobacteria

such as Pseudomonas, Aerobacter, Acinetobacter, Moraxella, and Plesiomonas;

(iii) beta-proteobacteria such as Burkholderia and Neisseria; and (iv) actinobacteria

such as Micrococcus and avobacteria such as Flavobacterium (Geetha and Fulekar

2008; Matsumoto etal. 2008; Rao and Wani 2015). Nineteen bacterial and two fun-

gal genera having the potential for degradation of chlorpyrifos are also enlisted

(Table8.1). Four bacterial and four fungal genera playing their role in degradation

of monocrotophos are shown (Table 8.2). Six bacterial and two fungal genera

involved in degradation of glyphosate are enlisted in Table8.3, while seven bacte-

rial and two fungal genera reported as efcient degraders of profenofos are also

enlisted in Table8.4.

S. Ahmad etal.

189

Table 8.1 Microorganisms involved in the degradation of OP chlorpyrifos

Microorganisms Source Reference

Sphingobacterium sp.Soil from paddy eld Abraham and Silambarasan

(2013)

Enterobacter sp. Soil Singh etal. (2004)

B. aryabhattai Soil Pailan etal. (2015)

Providencia stuartii Soil Rani etal. (2008)

Stenotrophomonas sp.Soil and sludge Li etal. (2008) and Deng etal.

(2015)

P. aeruginosa Paddy elds and industrial

soil, moist soil, eld soil,

soil from paddy eld

Lakshmi etal. (2008, 2009),

Lati etal. (2012), and Sasikala

etal. (2012)

Serratia marcescens Agricultural soil, paddy

elds, and industrial soil

Lakshmi etal. (2009) and Cycon

etal. (2013)

Sphingomonas sp.Soil and wastewater Li etal. (2007, 2008)

Bacillus cereus Paddy elds and industrial

soil, eld soil

Lakshmi etal. (2008, 2009)

Trichosporon sp., Serratia sp.Sludge Xu etal. (2007)

Enterobacter aerogenes, P.

pseudoalcaligenes, P.

maltophilia, P. vesicularis

Agricultural soil Awad etal. (2011)

P. peli, Burkholderia

caryophylli

Botanical garden soil Hossain etal. (2015)

Pseudomonas nitroreducens Efuent, storage ponds,

moist soil

Lati etal. (2012)

P. putida Efuent, storage ponds,

moist soil, soil from paddy

eld

Lati etal. (2012) and Sasikala

etal. (2012)

Bacillus sp. Soil from groundnut elds,

soil and industrial water,

agricultural farm soil

Li etal. (2008), Madhuri and

Rangaswamy (2009), and Maya

etal. (2011)

Leuconostoc mesenteroides,

Lactobacillus sakei

Kimchi (during

fermentation)

Cho etal. (2009)

Brevundimonas sp., B.

diminuta

Soil and water Li etal. (2008) and Hossain etal.

(2015)

Cupriavidus sp. Sludge Lu etal. (2013)

Pseudomonas uorescence Field soil Lakshmi etal. (2008)

Streptomyces chattanoogensis,

S. olivochromogenes

Soil from blueberry eld Briceno etal. (2012)

Cladosporium

cladosporioides

Industrial soil Gao etal. (2012)

Lactobacillus brevis, L.

plantarum

Not available Zhang etal. (2014)

(continued)

8 Organophosphates’ Pollution Status and Their Remediation Through Microbial…

190

8.5.2 Mechanisms Involved inBioremediation

The pesticides’ removal via biodegradation has positive impact on soil fertility. The

rate of degradation of pesticides depends upon their structure as some pesticides are

persistent due to anionic property in their structure (Javaid etal. 2016). Major reac-

tions considered in microbial degradation include hydrolysis, oxidation, alkylation,

and dealkylation. The OP compounds may have P=O or P=S bond. They get easily

Table 8.1 (continued)

Microorganisms Source Reference

Pseudomonas sp. Soil and water Li etal. (2008), Madhuri and

Rangaswamy (2009), Farhan

etal. (2012), and Maya etal.

(2011)

Brucella melitensis Field soil Lakshmi etal. (2008)

Bacillus subtilis Field soil Lakshmi etal. (2008)

Alcaligenes faecalis Soil around factory Yang etal. (2005)

Klebsiella sp. Sludge treatment plant, soil

from paddy eld, paddy

elds and industrial soil,

eld soil

Ghanem etal. (2007), Lakshmi

etal. (2008, 2009), and Sasikala

etal. (2012)

Pseudomonas stutzeri Soil from paddy eld,

agricultural soil

Awad etal. (2011) and Sasikala

etal. (2012)

Stenotrophomonas

maltophilia

Riverbank soil Dubey and Fulekar (2012)

Mesorhizobium sp.Agricultural soil Jabeen etal. (2015a)

Agrobacterium spp.Soil Maya etal. (2011)

Bacillus pumilus Soil Anwar etal. (2009)

Table 8.2 Microorganisms involved in the degradation of OP monocrotophos

Microorganisms Source Reference

Aspergillus avus, Macrophomina

sp., Fusarium pallidoroseum

Agricultural soil Jain etal. (2014) and

Jain etal. (2015)

Rhodococcus phenolicus,

Rhodococcus ruber

Groundnut (Arachishypogaea L.)

soil

Srinivasulu etal.

(2017)

Bacillus subtilis Vegetable and cotton elds Acharya etal. (2015)

Starkeya novella Soil samples of a paddy eld Sun etal. (2016)

Aspergillus sojae Contaminated paddy eld soil Abraham etal. (2016)

Aspergillus niger, Penicillium

aculeatum

Agricultural soil containing

chickpea, pearl millet, and mung

beans

Jain etal. (2015)

Bacillus sonorensis, Pseudomonas

stutzeri, Bacillus licheniformis

Agricultural soil Buvaneswari etal.

(2018)

Aspergillus sp. Gourd crop Trichosanthes

cucumerina L. eld

Anitha and Das

(2011)

S. Ahmad etal.

191

hydrolyzed due to ester bonding, thus providing several sites for hydrolysis (Briceno

et al. 2007). Microorganisms generally degrade OPs through hydrolysis of P-O-

alkyl or P-O-aryl bonds. It is the rst step in the degradation mechanism and involves

OP hydrolase enzymes (Upadhyay and Dutt 2017) (Fig. 8.5). Two hydrolases,

namely OP hydrolase (OPH) and OP acid anhydrase (OPA), have been isolated

from different microbes. The OPH was isolated from several Pseudomonas strains

and found to be encoded by opd gene. The OPA enzyme has been isolated from

Altermonas (bacterium) and Pleurotus ostreatus (fungus). Esterases such as ami-

dases, carboxylesterases, and phosphatases catalyze hydrolytic reaction of OPs

Table 8.3 Microorganisms involved in the degradation of OP glyphosate

Microorganisms Source Reference

Achromobacter sp.Glyphosate-contaminated soil,

methylphosphonic acid contaminated soil

Ermakova etal. (2017) and

Sviridov (2012)

Bacillus cereus Glyphosate-polluted soil in the herbicide

plant

Fan etal. (2012)

C. odontotermitis Glyphosate-contaminated soil Firdous etal. (2017a)

E. cloacae Rhizoplane of various plants Kryuchkova etal. (2014)

Enterobacter sp.Sandy soil Benslama and Boulahrouf

(2016)

caldoxylosilyticus

Central heating system water Obojska etal. (2002)

O. anthropi Glyphosate-contaminated soil Sviridov (2012)

O. intermedium Glyphosate-contaminated indigenous soil Firdous etal. (2017b)

Ochrobactrum sp.Soil Hadi etal. (2013)

Aspergillus oryzae Aeration tank in a pesticide factory Fu etal. (2017)

P. chrysogenum Soil Klimek etal. (2001)

Table 8.4 Microorganisms involved in the degradation of OP profenofos

Microorganisms Source Reference

P. putida

Burkholderia gladioli

Profenofos exposed soil Malghani etal. (2009a)

P. aeruginosa Profenofos exposed soil, cotton

eld soil, chili farm soil

Malghani etal. (2009b),

Jabeen etal. (2015b), and

Siripattanakul-Ratpukdi etal.

(2015)

Bacillus subtilis Grapevines or grape rhizosphere

soil (culture collection of centers)

Salunkhe etal. (2013)

A. sydowii, P. raistrickii Sponge Chelonaplysillerecta Da Silva etal. (2013)

P. plecoglossicida Chili farm soil Siripattanakul-Ratpukdi etal.

(2015)

P. suwonensis Soil Talwar and Ninnekar (2015)

Achromobacter

xylosoxidans, Bacillus sp.,

C. koseri

Cotton eld soil Jabeen etal. (2015b)

Stenotrophomonas sp. Sludge Deng etal. (2015)

8 Organophosphates’ Pollution Status and Their Remediation Through Microbial…

192

(Kumar etal. 2019). Several other enzymes such as paraoxonase, phosphodiester-

ase, and their respective genes are efciently playing their role in the degradation of

OP pesticides. However, complete degradation of OP involves oxidation, alkylation,

and dealkylation of the parent compound, resulting in the production of CO2 and

water, which is the energy source of microbes. Efcient degradation of OPs is

highly based on microbial diversity along with other optimum environmental condi-

tions (temperature, moisture content, pH, and nutrients available in soil) (Sidhu

etal. 2019). Modication of different bacterial specimens through genetic engineer-

ing also enhances the potential of applied microbes (Doolotkeldieva etal. 2018).

8.6 Case Study

Considering the most widely used pesticides such as chlorpyrifos and extensively

exploited microorganisms for biodegradation, this case study is divided into three

parts: (i) harmful effects of OP on fauna and ora, (ii) role of microbes, and (iii)

level of achievement through microbial mitigation.

(i) The World Health Organization (WHO) has classied chlorpyrifos in class II

owing to its moderate toxicity (Kumar etal. 2010). It is deleterious to different

organisms including soil biota, sh, birds, humans, animals, and plants.

Considerable residues of chlorpyrifos have been detected in the food chain

(Aysal etal. 2004). The residues of chlorpyrifos have toxic nature and property

of bioaccumulation (Fang etal. 2008).

(ii) Chlorpyrifos is generally degraded into 3,5,6-trichloro-2-pyridinol (TCP) and

diethyl thiophosphate (DETP) by microorganisms present in the soil. They

Fig. 8.5 General formula of organophosphate pesticides and their biodegraded products. (Singh

etal. 2006)

S. Ahmad etal.

193

utilize chlorpyrifos as a source of C, P, and N and nally mineralize into CO2

and water (Singh etal. 2004; Yang etal. 2005; Yang etal. 2006; Ghanem etal.

2007). Important bacterial and fungal strains involved in the degradation of

chlorpyrifos have been enlisted (Table8.1). These strains can tolerate chlorpy-

rifos up to 500 ppm in soil and liquid media.

(iii) The degradation percentage of chlorpyrifos varies depending on abiotic condi-

tions and microorganism exploitation. A Cupriavidus sp. was found to com-

pletely degrade chlorpyrifos within 6 h; Cupriavidus nantongensis has the

potential to degrade 200mg L−1 of chlorpyrifos within 48h (Lu etal. 2013;

Taozhong Shi etal. 2019). Several other species such as Stenotrophomonas sp.,

Sphingomonas sp., Bacillus sp., and Brevundimonas sp. completely degraded

chlorpyriphos within 20–24 h (Li et al. 2008). Two strains of bacteria,

Achromobacter xylosoxidans and Ochrobactrum sp., were reported to degrade

84.4% and 78.6% of chlorpyriphos (100mg L−1) within 10 days while com-

plete degradation was noticed after 35 days (Akbarand Sultan 2016).

8.7 Concluding Remarks

Organophosphates (OPs) are widely used around the world, having extensive appli-

cation in agricultural practices. They are highly toxic and have detrimental effects

on all organisms, i.e., plants, animals, humans, and soil biota. There are various

strategies which can be used to mitigate the impact of OPs, i.e., chemical-based

strategies and microbial interaction-based strategies. Chemical-based strategies

have drawbacks, as chemicals used for remediation have corrosive nature and they

are not safe to use chemicals. Bioremediation is an eco-friendly, relatively simple,

cost-effective, and efcient method for detoxication of harmful OP pollutants.

Microorganisms such as bacteria and fungi have been found to be effective for deg-

radation of OPs into less toxic compounds, and in some cases, microbes mineralize

OPs into CO2 and H2O. There are a large group of bacterial and fungal species

which have been reported for their efcient OP degradation ability. The general

mechanism involved in microbial degradation of OPs includes hydrolysis, oxida-

tion, alkylation, and de-alkylation reactions. There are various enzymes involved in

these reactions such as organophosphorus hydrolase (OPH), paraoxonase, phospho-

diesterase, and organophosphorus acid anhydrase (OPA). Conclusively, bioremedi-

ation is a biologically friendly method for decontamination of harmful OP pollutants

from the environment. The use of recent technological approaches in the twenty-

rst century considering the humans, plants, animals, and soil health is important to

remediate polluted sites and mitigate their negative effects for food security and

quality environment.

8 Organophosphates’ Pollution Status and Their Remediation Through Microbial…

194

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Associated Treatment Technologies, https://doi.org/10.1007/978-3-030-96523-5_9

Chapter 9

Toxic Organic Micropollutants

andAssociated Health Impacts

MuhammadIjaz, ToqeerAhmed, andAlishbahIftikharAhmad

Abstract Toxic organic micropollutants (TOMPs) are produced during any incom-

bustion process e.g., industrial plants and road transport. These chemicals are highly

toxic and some of these are carcinogens. These include poly aromatic hydrocarbons

(PAHs), polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins (diox-

ins), polychlorinated dibenzofurans (furans), and polybrominated diphenyl ethers

(PBDEs). PAHs are emitted from municipal incinerators, coal gasication plants,

aluminum industries, and coal tar and asphalt production facilities. PCBs have been

used as a coolant in electric transformers and capacitors. Other uses include as a

plasticizer in plastics, paints, dyes, carbonless copy papers and during heat transfer.

The main sources of dioxins and furans are incinerators, industrial processes,

incomplete combustion, and volcanic eruption. PBDEs are ame retardants and

have been used in plastics, electronic enclosures, cell phones, personal computers,

textiles, foam-based packaging, adhesives, and paint products.

There is no threshold limit for these pollutants as these can cause health damages

even in small quantities. PCBs have been declared as Group I carcinogens by the

International Agency for Research on Cancer (IARC). PCBs are also linked with

adverse effects on kidney, liver, endocrine, and neurological systems. PAHs are

genotoxins with irreversible genetic damage to humans. Exposure to PAHs leads to

risk of lung, bladder, and skin cancers. Dioxins and furans cause cancer, endocrine

disruption, effects on reproductive systems, and impairment of immune system.

M. Ijaz

Department of Chemistry, University of Wah, Wah Cantt, Pakistan

T. Ahmed (*)

Centre for Climate Research and Development (CCRD), COMSATS University Islamabad

(CUI), Islamabad Campus, Islamabad, Pakistan

e-mail: toqeer.ahmed@comsats.edu.pk

A. IftikharAhmad

Department of Chemistry, COMSATS University Islamabad (CUI), Islamabad Campus,

Islamabad, Pakistan

206

PBDEs are associated with neurodevelopment, liver and thyroid dysfunction, and

endocrine disruption.

Once released into the environment, these micropollutants undergo physical,

chemical, and biological processes such as atmospheric transport, volatilization,

deposition, partitioning, and bioaccumulation. There is a need to implement regula-

tory measures for safe handling, transport, and use of organic micropollutants and

to reduce the health impacts through appropriate treatment.

9.1 Introduction

Advances in evolution occur day by day. Chemical constituents are used in modern

culture to furnish the requirements of humans. Some of these substances are danger-

ous and are detectable in various matrices such as food, soil, water, and air. Over

time, organic micropollutants (OMPs) have become signicant sources of pollution

and pose threats to ecosystems, human health, and safety. OMPs include various

classes such as microplastics, endocrine-disrupting compounds (EDCs), polycyclic

aromatic hydrocarbons (PAHs), pharmaceuticals, personal care products (PCPs),

agricultural products, ame retardants, and industrial chemicals (La Farre

etal. 2008).

Air contamination and its unfavorable consequences for humans have become

issues of great concern. There are signicant sources of air poisons—for example,

inorganic gases, natural impurities, and particulate matter. Even nonindustrialized

nations have recognized problems with air contamination caused by trafc, devel-

opment outows, inappropriate garbage disposal and reuse, and modern and horti-

cultural manufacturing practices (Anh etal. 2019; Bi etal. 2002).

There is an established relationship between everyday clinical manifestations of

severe respiratory illnesses and concentrations of common air toxins (for example,

SO2 and NO2), such as those seen in the metropolitan spaces of Hanoi and Ho Chi

Minh City (Bohlin etal. 2008; Birgul etal. 2017). Nonetheless, more hazardous

concentrates, including exceptionally harmful steady natural contaminations

(POPs), in air are moderately restricted in most part because of the absence of

appropriate inspecting strategies and savvy evaluation apparatuses (Bi etal. 2002;

Jaward etal. 2004).

Some legacy POPs (for example, dichlorodiphenyltrichloroethane (DDT) and

polychlorinated biphenyls (PCBs)) are highly concentrated in the atmosphere in

Vietnam and several other Asian nations (Akutsu etal. 2001). Raised concentrations

of PCBs and polybrominated diphenyl ethers (PBDEs) have been measured in the

air and around the people using part of the waste as recycling material in some parts

of the world especially in Southeast Asia (Alaee etal. 2001). Similarly, a study

reporting OMP pollution in groundwater in China screened about 1300 micropollut-

ants in 13 samples from rural areas, although the carcinogenic risk was low, as only

two samples had high micropollutant concentrations (Li etal. 2016).

M. Ijaz etal.

207

9.2 Types andSources ofAtmospheric Toxic

Organic Micropollutants

Harmful natural micropollutants are formed during incomplete combustion cycles,

operation of chemical plants, and operation of road transport vehicles. These syn-

thetic compounds are exceptionally harmful, and some (such as PCBs, polychlori-

nated dibenzodioxins (PCDDs, or dioxins), PAHs, polychlorinated dibenzofurans

(PCDFs, or furans), and PBDEs) are cancer-causing agents (Li etal. 2016).

PAHs are emitted from metropolitan incinerators, coal gasication plants, alumi-

num smelters, and coal tar and asphalt production facilities. In industry, PCBs have

been utilized as coolants in electric transformers and capacitors. Their different uti-

lizations include plasticizers in plastics, paints, dyes, carbonless copy paper, and

heat transfer (Huang etal. 2006).

The main sources of dioxins and furans are incinerators, industrial processes,

incomplete combustion, and volcanic eruptions. PBDEs are ame retardants and are

used in plastics, electronic equipment, cell phones, personal computers, textiles,

foam-based packaging, adhesives, and paint products (Gouin etal. 2005).

During thermal and combustion processes, dangerous OMPs (such as PAHs,

PCBs, furans, and dioxins) are formed (Gevao etal. 2006). Because they are semi-

volatile, they occur in gaseous form or are associated with particulate matter in the

atmosphere. When these compounds are released in atmosphere, they can be trans-

ferred or accumulated to the terrestrial as well as aquatic environment through

deposition (wet and dry) (Chen etal. 2017b).

The zone of inuence is a major issue associated with emission of the com-

pounds mentioned above, and this determines whether such emissions have mainly

local or regional impacts, or whether they inuence global background pollution

levels. The existence of these compounds (PCBs, PAHs, dioxins, and furans) was

recently investigated in the Eordaia basin in northwest Greece, where intensive coal

burning takes place for power generation (Chen etal. 2017b; Hien etal. 2007).

Toxic organic compounds were formed by the burning of materials such as quan-

tities of transformer oil, mineral oil and plastic wires etc. in a closed room. Similarly,

indoor concentrations of semivolatile organic compounds in gas phase, settled dust,

and airborne particles has been detected (Blanchard etal. 2014; Schröder etal. 1997).

Plastics play signicant roles in overall advancement of human well-being—for

example, by enabling creation of disposable clinical equipment and expansion of

food handling. However, plastic waste entering the environment may have the oppo-

site impact—for example, by creating conditions conducive to disease transmission,

encouraging breeding of mosquitoes, obstructing water drainage, and causing ood-

ing. Lack of appropriate waste management is believed to have resulted in accumu-

lation of over 250,000 tons of oating plastic pieces in the seas (Rappe etal. 1986).

It was estimated that coastal nations discarded 4.8–12.7million metric tons of

plastic into seas in 2010 (Eriksen etal. 2014). In the environment, plastic waste

(which frequently originates as consumer goods waste that has been disposed of

9 Toxic Organic Micropollutants andAssociated Health Impacts

208

inappropriately) undergoes slow degradation via photodegradation, thermo-

oxidation, and (to a lesser degree) biodegradation, degrading the integrity of the

materials and causing them to disintegrate into parts less than 5mm in size, which

are known as secondary micropollutants (Brown etal. 2001; Rappe et al. 1986).

When plastic particles of small sizes are purposely created to be utilized in con-

sumer goods (such as makeup, exfoliants, or toothpaste) or commercial applications

(such as air blasting), they are called essential microplastics.

Microplastics are now found in seawater in concentrations of up to 102,000 par-

ticles per cubic meter and are additionally responsible for contaminating freshwater

(Vickers 2017; Zagorski etal. 2003) and even staple commodities such as beer, sea

salt, and tap water (Sakurai etal. 2000).

The pervasive presence of microplastics in the environment and in consumer

goods prompts inevitable human exposure to these particles. The results of this

exposure are not yet fully known. The current evidence regarding the impacts of

environmental exposure to microplastics on human well-being has been explored to

some extent, giving rise to theories regarding the mechanisms of exposure and the

extent of microplastic toxicity, and providing a basis for additional research.

However, the available data on the effects of microplastics on humans are limited

because of ethical issues, the strict biosecurity measures required when performing

research involving human subjects, and restrictions on the locations where such

research can be conducted (Birnbaum and DeVito 1995).

Different types of toxic OMPs and their sources are shown in Fig.9.1.

9.3 Health Effects ofToxic Organic Micropollutants

There is no known safe concentration of these toxins, as they can damage human

health even in small quantities. PCBs are classied as group1 carcinogens by the

International Agency for Research on Cancer (IARC) and are associated with harm-

ful effects on the kidneys, liver, endocrine system, and neurological system. PAHs

Fig. 9.1 Types of toxic organic micropollutants and their sources

M. Ijaz etal.

209

are genotoxins and cause irreversible genetic damage in humans. Exposure to PAHs

poses risks of lung, bladder, and skin cancers (Kouimtzis etal. 2002).

Dioxins and furans cause malignancies, endocrine dysfunction, effects on repro-

ductive systems, and immune system impairment. PBDEs are associated with endo-

crine, neurodevelopmental, liver, and thyroid dysfunction (Lee etal. 1999).

After these micropollutants are delivered into the environment, they go through

physical, chemical, and organic processes such as volatilization, atmospheric trans-

port, distribution, and bioaccumulation. There is a need for appropriate measures to

manage transport and utilization of natural micropollutants safely and to decrease

their impacts on health through suitable treatment (Mandalakis etal. 2002). Different

types of toxic OMPs, their transport media, and their associated health inuences

are listed in Table9.1.

Table 9.1 Types of organic micropollutants, their transport media, and associated health impacts

Organic

micropollutants

Transport

media Adverse health impacts References

Microplastics Water,

soil,

air

Disruption of photosynthesis in primary

producers; reduced food intake and

energy levels; disturbances producing

inammation and oxidative stress in

higher vertebrates; cell damage and

inammatory and immune reactions

Revel etal. (2018)

and Vethaak and

Legler (2021)

Pharmaceuticals

(β-blockers,

anti-inammatory

drugs, antibiotics,

neuroactive

compounds)

Water,

soil

Toxic effects on biota, harming aquatic

and terrestrial environments

Larsson etal.

(2007) and

Manzetti and Ghisi

(2014)

PCPs

(e.g., antiseptics,

fragrances)

Water,

soil

Breast cancer; asthma; autism;

reproductive problems; other health

issues

Paulsen (2015)

EDCs Water,

soil,

air

Endocrine disorders (e.g., adrenal

disorders); neurodevelopmental

dysfunction in children; endocrine-

related cancers; bone and metabolic

disorders; male and female reproductive

disorders

Meek etal. (1994),

International

Agency for

Research on

Cancer %J Lyon

(2010), Grob,

(2015), and

Chávez-Mejía etal.

(2019)

PAHs Water,

soil,

air

Effects on reproduction, development,

and immunity in terrestrial invertebrates;

carcinogenic effects (e.g., benzo[a]

pyrene is a group1 carcinogen);

mutagenic effects, posing serious threats

to human health; increased risks of lung

cancer

humans (2010),

Latimer and Zheng

(2003), and Kim

etal. (2013)

(continued)

9 Toxic Organic Micropollutants andAssociated Health Impacts

210

9.4 Toxic Organic Micropollutant Exposure

Micropollutants are far-reaching foreign substances. Exposure of the human body

to micropollutants occurs through ingestion of food containing toxic substances,

inhalation of micropollutants in the surrounding air, and also skin contact with par-

ticles contained in items, materials, or dust (Nakao etal. 2002). Possible effects of

exposure to toxic OMPs on human health are shown in Fig.9.2.

Table 9.1 (continued)

Organic

micropollutants

Transport

media Adverse health impacts References

Agricultural waste

(pesticides)

Water,

soil,

air

Harmful effects through antagonism or

mimicking of natural hormones in the

body, as well as hormone disruption;

immune suppression; diminished

intelligence; cancers; reproductive

abnormalities in humans; adverse health

effects of pyrethroid pesticides (e.g.,

immunotoxicity, teratogenicity,

carcinogenesis, mutagenicity)

Aktar etal. (2009)

and Zhou etal.

(2019)

Flame retardants Air,

dermal

contact,

dust

ingestion

Ripple effects on wildlife and the

environment; minor respiratory irritation;

BFRs affect the endocrine, neural,

reproductive, immune, and cardiovascular

systems

Feiteiro etal.

(2021)

PCBs Water,

soil,

air

Skin and eye irritation; decreased

pulmonary function; decreased birth

weight in offspring of occupationally

exposed mothers; variable effects on

cancer formation; altered reproductive

and thyroid function in both males and

females

Safe (1994), Ross

(2004), and

Carpenter (2006)

PCDDs,

PCDFs

Air,

soil,

food

Adverse effects on the immune, nervous,

and endocrine systems with long-term

exposure; impaired reproductive

function; high TCDD levels cause dermal

problems with acne-like lesions

(chloracne) on the face or upper body;

reduced motility, abnormal morphology,

and reduced capacity of sperm to

penetrate oocytes, resulting from

ingestion of PCDDs or PCDFs in food

Guo etal. (2000)

and Zheng etal.

(2008)

BFR brominated ame retardant, EDC endocrine-disrupting compound, PAH polyaromatic hydro-

carbon, PCB polychlorinated biphenyl, PCDD polychlorinated dibenzodioxin, PCDF polychlori-

nated dibenzofuran, PCP personal care product, TCDD 2,3,7,8-tetrachlorodibenzodioxin

M. Ijaz etal.

211

9.4.1 Inhalation Exposure

Micropollutants are delivered into the air by various sources, including manufac-

tured materials, scraping of materials (for example, vehicle tires and structures), and

resuspension of micropollutants from surfaces. One study of atmospheric micropol-

lutants measured outdoor concentrations of 0.3–1.5 particles per cubic meter and

indoor concentrations of 0.4–56.5 particles per cubic meter (33% from polymers),

including particles of inhalable sizes. It has been estimated that, on average, an

individual person inhales 26–130 airborne micropollutant particles per day (Dayan

and Koch 2002).

According to an atmospheric examination utilizing a life-sized model, it is com-

mon for a male individual performing light movements to inhale 272 micropollut-

ants during each day. Various assessments have focused on the inuences of

variations in aspects such as space use factors, cleaning processes, furniture materi-

als, exercise, and seasons. The properties of molecules, such as their size and thick-

ness, inuence their effects on the respiratory system; smaller and thinner particles

are breathed into deeper parts of the lungs than larger or thicker particles

(Carroll 2001).

There is evidence that macrophage activation or movement of particles into the

circulation or the lymphatic system may lead to transport of microparticles within

the body. The huge surface areas of tiny particles in the respiratory system may

elicit major chemotactic responses, inhibiting macrophage movement and increas-

ing the ability of particles to penetrate different tissues and cause persistent irrita-

tion, known as residue overburden (Wobst etal. 1999).

In one study, the presence of polystyrene nanospheres (64nm in size) prompted

neutrophil convergence and aggravation in the lungs of rodents. Moreover, proin-

ammatory responses were observed in epithelial cells as a result of greater oxidant

activity brought about by the huge surface area of the nanospheres (Brown etal.

Fig. 9.2 Routes and effects of exposure to toxic organic micropollutants on human health. (Revel

etal. 2018)

9 Toxic Organic Micropollutants andAssociated Health Impacts

212

2001). In an invitro study, polyvinyl chloride (PVC) particles (2 μm in size) created

by emulsion polymerization caused hemolysis and critical cytotoxicity in rodent

and human airway cells (Su and Christensen 1997).

Respiratory symptoms that have previously been linked to increases in aviation

and interstitial lung disease have also been associated with exposure to airborne

micropollutants in factory workers, workers managing livestock, and workers in

PVC production facilities, with the same effects being replicated (Barboza etal.

2018; Agarwal etal. 1978).

Filaments 205nm in size have additionally been identied in human lung biop-

sies and associated with malignant growths, although causation has not yet been

demonstrated. All things considered, under conditions of high xation or individual

susceptibility, airborne micropollutants can injure the respiratory system (Donaldson

etal. 2000).

9.4.2 Dermal Exposure

Dermal contact with micropollutants is considered a less critical means of exposure,

although it has been postulated that nanoparticles (<100nm in size) could cross the

dermal barrier (Barboza etal. 2018).

This route is regularly associated with exposure to monomers and plastic sub-

stances such as bisphenolA, phthalates, and EDCs via daily utilization of com-

mon equipment. The likelihood that nanoparticles do cross the dermal barrier and

cause harm should not be discounted without conrmation. The presence of plas-

tics in medications can cause minor inammatory responses, as well as less com-

mon reactions such as brosis. However, in one study, sutures utilizing interlaced

polyester and monolament polypropylene were found to cause more minor reac-

tions and brosis than silk after 21days (Vickers 2017; Eriksen etal. 2013). In a

study using mice, different types of plastic plates 10mm in size were implanted

subcutaneously and then removed after 98days. Polyethylene plates were found

to cause the least aggravation, but PVC plates stabilized with organo-tin or plasti-

cizers caused toxic effects, with moderate degeneration and rot, perhaps due to

leachate toxicity (Canesi etal. 2015). Although microparticles and nanoparticles

may cause aggravation and unusual bodily reactions, differences in surface prop-

erties could elicit particular results. Human epithelial cells have been shown to

exhibit harmful effects with exposure to micromaterials and nanomaterials (Frias

etal. 2010).

Accordingly, the known adverse effects of nanoparticles and inevitable dermal

exposure to plastic particles (for example, from engineered strands, dust, and

microbeads in cosmetic products) support the requirement for further research in

this area.

M. Ijaz etal.

213

9.4.3 Oral Exposure

Ingestion is viewed as one of the most signicant routes of human exposure to

micropollutants. In view of the widespread utilization of these substances (for

example, in food packaging), it has been estimated that each person ingests

39,000–52,000 micropollutant particles per year (Cole etal. 2013).

Particles may enter the gastrointestinal system through mucociliary clearance

after inhalation, and they may cause major inammation, increased tissue penetra-

bility, and changes in gut microorganism populations and digestion (Karami etal.

2017). The presence of micropollutants has been documented in food items such as

mussels, sh, table salt, sugar, and ltered water. In Europeans, exposure to micro-

pollutants via bivalve consumption has been estimated to be 11,000 particles per

year (Saravia etal. 2014). Moreover, it has been estimated that each year, Europeans

ingest 37–100 micropollutant particles per capita through consumption of table salt.

However, some researchers have suggested that settling of micropollutant resi-

due on dinner plates may be a more signicant source of micropollutant consump-

tion than the presence of these pollutants in the food itself (Furukuma and Fujii

2016). Incidence of dementia are higher while living near highways as compared to

Parkinson’s disease and multiple sclerosis (Chen etal. 2017a).

Particles of insoluble substances may inltrate digestive uid through an increase

in their dissolvability via adsorption of a “crown” of intestinal substance or because

of their small sizes, so it was observed that particles present in rodent intestinal seg-

ments are of polystyrene latex with a size range of 14 nm to 415 nm (Sternschuss

etal. 2012).

Another possible means of inltration of these particles is persorption, with para-

cellular movement of particles through a single layer of intestinal epithelium.

Micropollutants would be exposed to these equivalent systems according to their

toxic nature especially in circulatory system. This has been demonstrated invivo

after oral administration. For example, in a study of rodents, 6% of polystyrene

particles (0.87mm in size) entered the circulation within 15min of oral administra-

tion. In another study, oral administration of 1.25mg kg of polystyrene particles

50nm in size resulted in 34% absorption, perhaps via transport through the mesen-

tery lymph system into the circulatory system prior to accumulation in the liver

(MohanKumar etal. 2008).

Polystyrene nanospheres were delivered by human colon broblasts across the

cell layer. After disguising by human gastric adenocarcinoma cells, these polysty-

rene particles inuence the quality of articulation, hinder cell viability and initiate

provocative reactions (Li etal. 2016).

Humans are exposed to micropollutants through inhalation and ingestion because

our environment is now signicantly contaminated with micropollutants. However,

the dangers associated with bodily contamination by micropollutants are not yet

adequately understood, because of a lack of research assessing general human expo-

sure and its consequences (Saravia etal. 2014).

9 Toxic Organic Micropollutants andAssociated Health Impacts

214

9.5 Conclusion

Polyaromatic hydrocarbons, polychlorinated dibenzodioxins, polychlorinated

biphenyls, polychlorinated dibenzofurans, and polybrominated diphenyl ethers are

highly toxic substances emitted from incinerators, coal gasication plants, the alu-

minum industry, and coal tar and asphalt production facilities. There is an urgent

need to reduce the presence of these toxic pollutants in the atmosphere and in the

environment. The following are important recommendations to help achieve

this goal:

1. Open burning of garbage should be limited (especially in periurban areas), and

emissions from chimneys and brick kilns should be permitted only under strictly

controlled conditions.

2. Use of older vehicles should be banned, especially those that have been running

for more than 20years and those with outdated engine, because road trafc emits

toxic lead and other pollutants, which can impact not only human health but also

the health of plants and trees growing along roadsides.

3. Industries should be required to limit their waste, and there should be appropriate

mechanisms for waste management, especially in the steel and plastic industries.

4. Policies regarding emissions should be enforced strictly, and action should be

taken against anyone violating these policies or polluting the environment.

5. Activities should be undertaken to increase awareness of environmental pollu-

tion and discourage it at all levels.

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Associated Treatment Technologies, https://doi.org/10.1007/978-3-030-96523-5_10

Chapter 10

Impact ofAerial Fungal Spores onHuman

Health

SadiaAlam, MaryamNisar, SyedaAsmaBano, andToqeerAhmad

Abstract Fungal spores are present in almost all types of environments and prevail

in certain environmental conditions. The composition of aeromycoora of a particu-

lar area plays an important role in the spreading of many respiratory allergies. The

indoor and outdoor aerial fungal spores may be different due to many factors. The

aerial fungal spores play an important role in public health as many fungal spores

are potent allergens for human population. These fungal spores may also cause

some important mycolic infections. Indoor environments are possible sources of

fungal spores which can be injurious to human health. These fungal spores can

endure for months in suitable conditions. Many environmental factors such as high

temperature, high humidity, dampness physical activity, and the wind speed play

effective role in the release and distribution of fungal spores in air and which can

impede wellness of local population. Aerial fungal spores are the major cause of

allergic diseases and infections in immunocompromised patients in many parts of

the world. The aerial fungal spores of Alternaria, Aspergillus, Cladosporium,

Candida, Curvularia, Epicoccum, Fusarium, Geotrichum, Helminthosporium,

Mucor, Penicillium, Rhizopus, Trichoderma, and Trichothecium were found as dom-

inant in the air of many cities of the world. Variations in composition of aerial fun-

gal spores occur due to environmental and meteorological factors. Some fungal

spores are seasonal, and therefore, these spores are linked with some seasonal

mycotic infections. They are also established to cause Type I hypersensitive dis-

eases with IgE- mediated response. Fungal spores are present in both outdoor and

indoor environments and behave as suspended bio pollutants of the air. Many aerial

S. Alam (*) · M. Nisar · S. A. Bano

Department of Microbiology, The University of Haripur,

Haripur, Khyberpukhtunkhwa, Pakistan

e-mail: sadia.alam1@uoh.edu.pk

T. Ahmad

Centre for Climate Research and Development (CCRD), COMSATS University Islamabad

(CUI), Islamabad, Pakistan

e-mail: Toqeer.ahmed@comsats.edu.pk

220

fungal spores are found as main cause of respiratory tract allergies. Many fungal

spores can penetrate in lower respiratory airways of human lungs and intercede

allergic reactions. These fungal spores can be a serious health hazard for immuno-

compromised persons. The sensitization to fungal spores may cause some fungal

allergies inlocal population. The seasonal data of aerial fungal spores and their pat-

tern of distribution can help to prevent fungal allergies and mycotic diseases.

10.1 Introduction

10.1.1 Composition ofAeromycoora

Fungi are omnipresent in the world’s environment and are an integral part of air-

borne microbiome. Particulate matter dispended in air includes bacteria, fungi, clay,

and sand particles of 10μm or smaller to below 0.1μm and gases including ozone

(O3), nitrogen dioxide (NO2), and sulfur dioxide (SO2) (Ministry of Environmental

Protection of the People’s Republic 2017). Alternaria is the most common fungus

present in outdoor and indoor environment. Indoor environment also contains

Aspergillus fumigatus and Alternaria spp. Both species have positive impact on

developing asthma (Shabankarefard etal. 2017). Humans are continuously affected

by aerosols because of domesticated animals, plants, plumbing systems, heating

and cooling systems, and saprophytic molds along with suspended dust particles

that contribute to a type of airborne fungus. Yamamoto etal. (2015) detected differ-

ent types of yeasts in classroom environment including Rhodotorula, Candida,

Cryptococcus, Malassezia, and Trichosporon. Certain researchers have indicated

that most of the fungi found in indoor environment comprise of the genera prevail-

ing in outdoor environment (Barberan etal. 2015). Goh etal. (2000) studied library

environment and found that indoor fungi concentration was 50 times less than that

of outdoor environment.

10.1.1.1 Allergenicity ofAirborne Fungal Spore

The huge diversity of fungal kingdom is well known. A variable lot of fungal spe-

cies exist; some of them disseminate airborne spores, conidia hyphae, or other frag-

ments that are inhaled by human beings. Three taxonomic groups of fungi and their

112 fungal genera including Basidiomycota, Ascomycota, and the Deuteromycota

release those allergens which spread allergic diseases. Associated components of

fungal conidia are unlike any other bio aerosol in that theseare heterogeneous;

those which have pathogenic and inammatory properties are actively secreted by

biological dynamic particles. In several multi-studies sensitization of fungi has been

identied which is considered to be a risk factor for severe asthmatic patients. The

hypersensitivity to fungal allergens ranges from as low as 2% to as high as 90%

(Arbes etal. 2005; Zureik etal. 2002), and it was reported that sensitization of fungi

S. Alam etal.

221

is dependent on different exposure as with most allergens just like source and com-

mercial skin test extracts, based on selection criteria of test subject and analysis

methods. There are several subject methods which are used to measure exposure

such as spore count, endure assessments of visible growth of fungi, and this proce-

dure is also used to understand the relationship of exposure to clinical outcome.

Fungi including Aspergillus, Cladosporium, Penicillium, and Alternaria species

have been investigated for human exposure. These genera have been found in abun-

dance and a cause of maximum human exposure to airborne fungal spores. These

have been detected in vast geographic area and can be detected through various

diagnostic means (Cruz etal. 1997).

10.1.1.2 Fragments ofFungi intheEnvironment

Indoor environment is polluted by airborne fungal spore which is characterized by

numerous diagnostic methods. The particulate matter in air have been studied rarely

for personal exposure. Many studies’ procedures have been promulgated to verify

presence of hyphal fragments in indoor environment that indicates the amount of

particles in air amounting to 6–56% of total fungal particles (Li and Kendrick 1995;

Foto etal. 2005). These fragments of aerosols actually originate from indoor pol-

luted surfaces, and these particles may even persist in indoor environment for quite

long in viable form thus aiding to fungal dispersion (Madelin and Madelin 2020). It

has been detected from different epidemiological studies that multitudinous frag-

ments of fungal hyphae are associated with acute high expiratory ow rates (Delno

etal. 1997).

Submicron Fungal Fragments

Those particles which are derived for intracellular and extracellular structure are

known as submicron fungal fragments that have been aerosolized from fungal col-

ony (Górny etal. 2002). Their usual size is around 1mm and they lack morphologi-

cal features. Reports related to submicron fungal fragments are few as it is a bit

difcult to collect and identify fungal fragments from polluted environment and its

isolation is totally based on experimental conditions (Gorny etal. 2002; Gorny

2004; Cho etal. 2005). Dr. Tinna Reponen and Rafal Gorny developed aerosoliza-

tion chamber, and its purpose was to assess gradual release and collection of bio

aerosols. Aerosolization of submicron fungal fragments studied by different authors

from culture medium vessels, building internal tiles were found polluted with

Aspergillus versicolor (Górny etal. 2002, 2003). An aerosolization chamber was

researchers found different fungal species involved in formation of submicron frag-

ments on internal tiles of buildings and culture vessels. The species involved were

Aspergillus versicolor, Penicillium melinii, Cladosporium cladosporioides, and

Stachybotrys chartarum. The small hyphal segments related to these species have

10 Impact ofAerial Fungal Spores onHuman Health

222

been indicated in aerosols with spores but to large concentration (320–514 times

higher). These ndings depict that colony structure, desiccation stress, air velocity,

degree of vibration, and moisture conditions may all affect aerosolization rate

(Górny etal. 2002; Górny 2004). Various study methods have investigated respira-

tory disposition of submicron fungal fragments and inammation. All are based on

computer-based models. Cho and colleagues currently explained that the presence

of S. chartarum fragments is in higher concentration than spores, but in case of

A. versicolor, a total count 230–250 was similar to the spore. The model was uti-

lized to predict infants’ environment, and it was known that sedimentation rate was

a 4–5 times multitude of the value associated with young ones (Cho etal. 2005).

Further investigation is needed to determine personal fungal exposure from a clini-

cal point of view.

Larger Fungal Fragments

Conidia in broken form and visible septate hyphae or mycelium are considered as

larger fungal fragments. Their size exceeds 1mm and comprised of fragmented

hyphae (Green etal. 2005). As compared to submicron particle, these fungal frag-

ments are larger in size, easier to be visualized by light microscopy and environ-

mental air samples. In some geographical locations, their concentration can range

up to 56% of the total aerospora (Li and Kendrick 1995). Larger fungal fragments

related research is scarce as compared to submicron fragments in aerosols. But it is

evident that their presence is based on a number of similar variables including sub-

strate disturbance, wind, speed, and wind direction (Green etal. 2005). Filamentous

fungi reproduce through hyphal fragmentation. Fragmentation is continued by vac-

uole formation following a reduction in nutrients that may be induced by environ-

mental stress (Papagianni etal. 1999; Paul etal. 1994). This stress and nutrient

depletion zone proceeds towards hyphal separation at septal junctions, and their

dissemination is made through wind blowing (Marfenina etal. 1994). The process

of conidial fragments formation has not yet been investigated thoroughly and

remains undiscovered. It is considered that multicellular conidia get rupture near

cross walls of hyphae due to different osmotic potential or when they differ in mois-

ture content (Taylor and Jonsson 2004; Schäppi etal. 1999).

10.1.2 Taxonomy ofAllergic Fungi

Kingdom fungi have huge diversity of eukaryotic organisms including mushrooms,

molds, bracket fungi, puffballs, smuts, plant rusts, and yeast. Fungi contain different

metabolic processes which differ from animals to plants. They secrete enzyme into

environment, and their function is also to absorb the breakdown product of enzyme

action. Some of these enzymes are also well-classied allergens. Phylogenetic rela-

tionships were unclear among different classes of fungi, but currently its classica-

tion is based upon morphological characterization and sexual state. Deuteromycetes

S. Alam etal.

223

or fungi imperfecti at fungal phyla are resolved by DNA sequencing. On the basis

of DNA sequencing, it has been found out that three fungal phyla are mostly associ-

ated with important aeroallergens; Basidiomycota, Ascomycota, and Zygomycota.

Many fungal allergens have been categorized. Specic immunoglobulin E (igE)

level in individuals sensitized to fungi has a close relationship between fungal phy-

logeny, and this is a great benet from this study. This strongcorrelationbetween

molecular fungal systematics and IgE sensitization gives a strong evidence about

cross reactivity of fungal allergens with human immunity response (Levetin

etal. 2016).

10.1.3 Common Fungal Aeroallergens

Aeroallergens are the substances that are dispersed in air as spore or pollens and are

able to cause an allergic reaction.

10.1.3.1 Pollens

Aeroallergens are found in certain seasonal plants, and when pollens acting as aero-

allergens cause sensitivity reactions in patients, the response is called “hay fever.”

Because it is the most common illness during haying season in summer months of

May and June in Northern areas, some individuals may suffer from this seasonal

allergy throughout the year. Hay fever caused by pollens differs from region to

region and person to person; small, hardly visible pollens of wind pollinated plants

are the main cause of hay fever. The insect pollinated plants have larger pollens that

are much larger to remain in air and cause no risk. The plants responsible for pollen

allergy or hay fever include trees: alder (Alnus), birch (Betula), hornbeam

(Carpinus), cedar (Cedrus), hazel (Corylus), willow (Salix), olive (Olea), poplar

(Populus), linden lime (Tilia), horse chestnut (Aesculus), and plane (Platanus).

Grasses [family Poaceae] especially ryegrass (Lolium sp.) and timothy (Phleum

pratense) are involved in causing allergies. An estimated proportion of 90% of hay

fever sufferers are allergic to grass pollens. Plantain (plantain), ragweed (ambrosia),

nettles/Parietaria (Urticaceae), fat hen (Chenopodium), sorrel/dock (Rumex), and

mugwort (Artemisia) also cause allergic immune sensitivity.

Ranging from the mid spring to early summer, the pollen count is the highest in

a year. The pollen-sensitive patients may anticipate at the onset of the season and

when the season ends.

10.1.3.2 Spores

Both sexual and asexual spores in many fungi actively spread by strong ejection

from their reproductive structure or sporangium, which spread through the air to

distant area. Many fungi have special physiological and mechanical processes as

10 Impact ofAerial Fungal Spores onHuman Health

224

well as spore structure and surface structure formation like hydrophobic character-

istics for spore ejection. This process consists of strong discharge of ascospores

enabled by structure of ascus and accumulation of solutes causing osmotic potential

in the uid that push the spores towards dispersal at high velocity into the air (Trail

2007). When single spores get discharged, this process is known as ballistospore

dispersal and involves small water droplet formation (Buller’s drop), which when

link with spore it moves toward projectile ejection with a starting acceleration rate

of more than 10,000g. Other fungi depend on alternative mechanisms for spore

ejection which include mechanical forces like puffballs.

Peanuts and other food material may become airborne thus causing aller-

gic reactions in disease-prone individuals like children, immunocompromised

people, pregnant women, and elderly adults. Currently concern has been raised

about peanuts protein related allergens in the air that may cause a full-blown

anaphylaxis and in the result respiratory exposure can occur. In schools setting

as a protein food for children, even in well-ventilated restaurants, when air-

borne peanut protein exposure occurs, different allergic responses were explored.

Children have been detected with peanut-associated allergic reaction. No peanut

allergen was found in air after subjects consumed peanut (Perry etal. 2004). Dr.

Michael Young (2006) reported that peanut allergy may result in life-threating

anaphylactic response, but its association with airborne allergy is unconrmed.

Eosinophilic gastroenteritis is an uncommon and heterogeneous condition involv-

ing eosinophilic inltration of gastrointestinal tissue rst described by Kaijser in

1937 (Whitaker etal. 2004).

The stomach is the type of organ which is mostly affected followed by the small

intestine and colon. Eosinophil is commonly found in gastrointestinal mucosa, like

a part of host immunity mechanism; its nding in deeper areas is mostly pathologic.

Pathogenic mechanism of disease occurs. Viable IgE and food allergy correlation

have been observed in some patients. Eosinophilic aggregation in tissue for inam-

mation is a complicated process which occurs by different processes of accumula-

tion of cytokines. Cytokines IL 3, IL 5, and granulocytes macrophages colony

stimulating factor [GM –CF] are involved in activation, and it has been observed in

histological examination of the intestinal wall. Stomach/intestinal allergies are

treated by corticosteroids, and its response rate is much positive.

10.1.4 Respiratory Disease Caused by Aeromycoora

Fungal ora is found everywhere in the environment. Mycopathogens are omnipres-

ent in the environment. Serological reports have revealed that major human popula-

tion proportion have been affected with fungus respiratory diseases during their life

span. Even symptomatic infections by these fungi are infrequent in healthy and

vigorous individuals. This indicates the possible hazard of developing a respiratory

system disease.

S. Alam etal.

225

10.1.4.1 Histoplasmosis

Histoplasmosis is a respiratory disease caused by fungal pathogens and commonly

occurs in the South America, Africa, Australia, Asia, and Mississippi Valley of the

United States. Histoplasma is a dimorphic fungus that grows in the environment as

a lamentous mold, but during human infections they occur as budding yeast. Soil

is the primary reservoir of this fungal pathogen, especially inlocation rich in bird

and bat feces. Histoplasma is not transmitted from human to human, and its acquisi-

tion is made through inhalation of microconidial spores in the air. In endemic areas,

histoplasmosis is high, and the 60–90% of population harbor anti-Histoplasma anti-

bodies depending on the locating habitat, but few individuals experience symptoms.

Young ones are most likely to be affected and immunodecient adults. The disease

pattern of histoplasmosis is similar to tuberculosis in many ways. Following inhala-

tion this disease gets symptoms similar to tuberculosis because spores go to the

respiratory organs and are engulfed by alveolar macrophages. Fungal cells increase

in number and sustain even after being engulfed by these phagocytes. Granulomatous

lesions caused by focal infections are similar to the Ghon complexes of tuberculosis

even in symptomless conditions. Histoplasmosis can become severe and reactivate

and spread to other areas of the body such as the spleen and liver. Symptoms and

signs of histoplasmosis contain headache, fever, chest discomfort, and weakness.

Initial diagnosis of this disease depends on cultures grown on fungal-selective

media (Sabouraud Dextrose Agar) and chest radiographs. Giemsa staining and

direct uorescence antibody staining technique can also be utilized for detection of

the disease. In some conditions this infection may be restricted and antifungal ther-

apy is not necessary. Yet in case of complexities, the disease is treated by antifungal

agents like ketoconazole and amphotericin B; in immunocompromised patients,

itraconazole is more effective.

10.1.4.2 Coccidioidomycosis

Coccidioidomycosis infection is caused by dimorphic fungi known as Coccidioides

immitis. This disease is sometimes mentioned as valley fever because it is endemic

to the San Joaquin Valley of California. Same infection is found in arid and semi-

arid area of southwestern United states, central and South America, and Mexico.

Coccidioidomycotic infection is caused by inhalation of fungal spores. In epidemi-

ology of this disease, the arthospores are produced when the fungal hyphae breaks

intofragments. When fungus gets entry in host cells, it is distinguished into spher-

ules lled with endospore. Some C. immitis infections are self-limiting and asymp-

tomatic. Yet, the infection can be chronic for immunocompromised patients

(Fig. 10.1). Endospore may be elated in the blood, spreading the infection and

formed granulomatous lesions on the nose and face. In chronic situation some other

organs can be infected and cause serious complex diseases such as untreatable men-

ingitis. This disease can be diagnosed by isolation of fungal pathogens from clinical

specimen. C. immitis can be cultured on Sabouraud Dextrose Agar when incubated

10 Impact ofAerial Fungal Spores onHuman Health

226

at 35°C.It is very dangerous to grow in laboratory environment because it is the

most infectious mycopathogens capable of surpassing human immune system in the

laboratory. This pathogen is rendered as Risk Group 3 agent and can be experi-

mented only in BSL-3 lab facility. The serology of patient may be utilized for its

diagnosis through presence of antibody against the pathogen in the patient serum.

Though minor cases do not require thorough treatment, but severe pathologies can

be treated with amphotericin B.

10.1.4.3 Blastomycosis

Another dimorphic fungus Blastomyces dermatitidis causes disease termed as blas-

tomycosis. Like Coccidioides and Histoplasma, Blastomyces spread through soil,

and fungal spores can be breathed with dust from eroded soil. Symptoms and signs

of blastomycosis are mild u-like and treat with time without medication. It can

spread in immunocompromised people and is able to produce severe cutaneous dis-

ease with underlying skin lesions on the hand and face. These abrasions are ulti-

mately converted into discolored and crusty surface and can cause deforming scars

on skin. Systemic blastomycosis is uncommon, but when it is left untreated, it

always results in fatality. Urine antigen tests are now available for diagnosis of pul-

monary blastomycosis. Further tests include serological assays such as EIA or

immunodiffusion tests. Ketoconazole or amphotericin B are used for the treatment

of blastomycosis.

Fig. 10.1 (a) The patients have facial lesion due to Coccidioides infection. (b) The uorescent

micrograph shows a spherule(Source: http://www.cdc.gov/fungal/diseases/coccidioidomycosis/

index.html)

S. Alam etal.

227

10.1.4.4 Mucormycosis

The diversity of fungi in the order Mucorales causes disease termed as mucormy-

cosis, uncommon mold infection. These include bread molds, like Mucor and

Rhizopus, generally related species is Rhizopus arrhizus (oryzae). In immunocom-

promised patients, these fungi can establish itself in many different organs but cause

infection in the sinuses, respiratory organs, and human dermal region. From the

environment the spores enter through breathing in spore-laden air, but spore can

also infect the derma layer through gastrointestinal tract if ingested or wound. Sever

infection can occur in immunocompromised individuals such as a patient who had

a transplant or with cancer. When spores are inhaled into the host’s tissue, the fungi

grow by spreading hyphae. Infection causes disease in both lower and upper respira-

tory tracts. In some severe cases the host brain and sinuses are also affected, and the

disease is rhinocerebral mucormycosis. Its pathological manifestations are pyretic

response, headache, congestion, and tissue death resulting in formation of black

lesions in the oral cavity and facial swelling. Infection of the lungs is termed as

pulmonary mucormycosis; symptoms include shortness of breath, fever, chest pain,

and cough. In chronic cases, the pathogen may disperse to the central nervous sys-

tem paralyzing the patient in coma and cause death. Currently, for diagnosis there

are no PCR-based or ELISA available for detection of pathogens in medical speci-

mens. Tissue biopsy specimens is the only detection strategy to assess the presence

of the fungal pathogens. Infections are treated by intravenous administration of

amphotericin B, and surgical procedures are utilized for removal of supercial

infections.

10.1.4.5 Aspergillosis

Aspergillus is a fungus having a mycelial mat comprising of large laments found

in organic debris and soils. This fungus is the most common fungal pathogens; how-

ever rarely people become sick. Aspergillus may colonize the hostandcause infec-

tion called aspergillosis. In immunocompromised patients, when its spores are

inhaled, the patient can develop allergic asthma-like reactions. Clinical manifesta-

tions commonly include wheezing, ue, coughing, headaches, and shortness of

breath. Aspergilloma or fungal balls are formed when colonies of hyphae are accu-

mulated in the lungs (Fig.10.2). In the lungs the Aspergillus mycelium damages the

host tissues and causes pulmonary hemorrhage and bloody cough. When the infec-

tion worsens, the disease becomes fatal because of disseminated fungal mycelium,

and it may take the patient to unrecoverable stage of brain hemorrhages and pneu-

monia. Laboratory diagnosis mostly requires radiography of chest and microscopic

testing of tissues and respiratory samples of uid. Aspergillus antigens are identied

from serological test. If a person is exposed to fungus, skin test can also be per-

formed for its determination. These tests are similar to that performed for

tuberculosis.

10 Impact ofAerial Fungal Spores onHuman Health

228

10.1.4.6 Pneumocystis Pneumonia

Pneumocystis pneumonia (PCP) is a type of pneumonia caused by Pneumocystis

jirovecii. Initially supposed to be a protozoan, this microbe was previously classi-

ed as P. carinii, but after genetic analyses and biochemical tests it is regrouped as

a fungus (Pneumocystis jirovecii) (Fig.10.3). Immunodeciency syndrome (AIDS)

patients acquire Pneumocystis pneumonia, and some of premature infants may get

infected also. When lungs are infected shortness of breath is inevitable with cough

and fever. These infections are difcult to diagnose. The pathogen is normally iden-

tied by slide identication under microscope. Usually uid and tissue samples

from the infected organ are used. Molecular detection may also be used using PCR

assay to probe P. jirovecii in symptomless patients with immunodeciency disease.

A combo drug trimethoprim-sulfamethoxazole is successfully utilized for treat-

ment of the disease.

10.1.4.7 Cryptococcosis

Cryptococcosis infection caused by encapsulated yeast termed as Cryptococcus

neoformans. This fungus mostly resides in soil and can be detected in avian feces. If

inhaled basidiospores found in air the spores may cause disease in infected

Fig. 10.2 An

Aspergilloma (fungal ball)

can be observed in the

upper lobe of the right lung

in this chest radiograph of

patients with

aspergilloma(Source:

Modied image byCenters

for Disease Control and

Prevention)

S. Alam etal.

229

immunocompromised patients. This microbe is surrounded by thick polysaccharide

capsule and enables them to evade the response of alveolar macrophages. Early

manifestations of infection include a dry cough, malaise, and fever. Pulmonary

infection is often disseminated to the brain in immunocompromised patients. The

resultant meningitis produces confusion, sensitivity to light, and headaches. This

infection is diagnosed on the basis of microscopic examination of cerebrospinal

uids or lung tissues. Indian ink can be used to locate the capsules bordering outer

wall of the fungal pathogen. ELISA technique is also performed to endorse the

detection. For the initial treatment of pulmonary infection, ucytosine combina-

tion with Amphotericin B can be used. Amphotericin B is a broad-spectrum drug

against fungus that targets cell membranes of fungus. In immunocompromised and

those with AIDS patients, cryptococcal infections are more common.

10.1.4.8 Dermatophytes

Dermatophytes are fungi able to cause contagious diseases of the skin, hair, and

nails. The disease is termed as dermatophytosis. Dermatophytes have enzymes that

can degrade keratin proteins of the scalp, hair, nails, feathers, horns, and hooves.

Dermatophytes are mostly soil resident microorganisms and decompose the organic

matter. The decomposing ability also enables these microbes to infect hosts when

alive. Some dermatophytes (anthropophilic species) are habituated and are trans-

missible to person to person. When dermatophytes are habituated to animals, these

are zoophilic species. A few (geophilic) species frequently reside in the environ-

ment and can be parasitic when these get the opportunity. Zoonotic transfer of some

of the zoophilic and geophilic species may also occur. There is also evidence of

Fig. 10.3 A light micrograph of smear containing Pneumocystis jirovecii obtained from human

lungs tissue(Source: Modied image byCenters for Disease Control and Prevention)

10 Impact ofAerial Fungal Spores onHuman Health

230

reverse zoonosis, i.e., human to animals route of disease transmission is also noted.

The epidermis, nails, and hair of living host are the target residing areas for derma-

tophytes. The infection may limit itself, but sometimes the illness may cause facial

or tissue impairment and discomfort, when spread widely. Economic effects, such

as damage to obnubilate, are additionally consequential in livestock. Infrequently,

dermatophytes may invade subcutaneous tissues and (very infrequently) other sites,

especially in immunocompromised hosts (Cafarchia etal. 2004).

Tinea capitis Most often children get infection on the scalp and hair, and it is

known as tinea capitis. The disease is caused by diverse groups of pathogens like

M. canis, a zoophilic species causing the same infection in continental Europe,

while T. tonsurans is mostly associated anthropophilic infection in human popula-

tion of the USA and the UK.Variable pathogenic organisms have been isolated and

include T. violaceum, M. audouinii, T. schoenleinii, and T. soudanense. Some fungi

are zoophilic only and include T. mentagrophytes, T. verrucosum, and M. persi-

color. M. gypseum and M. nanum (uncommonly)have been detected as geophilic

species in some the infection in some area. Tinea capitis is manifested when scaly,

erythema and baldness grow rapidly on the scalp. Some human-residing dermato-

phytic species may result in bald crusts with slight inamed tissue at follicle point.

Dermatophytes associated with animals are able to cause swelling in the infected

area called kerions. “Favus” is an infective manifestation of anthropophilic

T. schoenleinii. This a chronic infection and hairs are surrounded by yellow crusts.

When untreated the disease may last up to years (Nweze and Okafor 2005).

Tinea corporis or ringworm occurs on the main body and in extreme parts of the

body including face sometimes. Neck and hand wrists also get infected more often

from children to adults. Human-infecting microbes are T. rubrum and E. occosum.

Both of these infect the skin only. The other causative agents are M. audouinii,

T. schoenleinii, T. tonsurans, and T. violaceum. The fungal pathogens causing this

dermatophytic infections in animals are mostly M. canis, T. verrucosum, T. equi-

num, T. mentagrophytes, and M. persicolor. The geophilic pathogenic ora com-

prised of M. gypseum and M. nanum. Tinea corporis may be characterized by one or

more lesions of pink or red or even scaly with annular ring appearance. The ring

borders may have follicular papules or vesicles mostly when the infecting pathogen

is zoophilic or geophilic in origin. The zoophilic fungus Trichophyton quinckeanum

can form yellow crusts on the skin called scutulae. Itching gets started in lesions.

The remedial measures include treatment with corticosteroids. Tinea corporis may

take few months to be cured naturally if left untreated.

Tinea faciei and tinea barbae are dermatophytic face infections, and the caus-

ative agents are usually acquired from pets or livestock. The target area for fungal

pathogenesis includes the scalp or torso. Tinea barbae include fungal infection in

hair and skin of beard or mustache. The victims are usually men. Trichophyton

rubrum is the causing agent, and follicular pustules are formed along with scaling

and redness of skin. The cattle associated pathogen T. verrucosum and T. mentagro-

phytes may have a large inammation of infected area with pustular folliculitis or

kerions. The other fungal species involved include M. canis, T. tonsurans, T. megn-

ini, and T. violaceum. Tinea barbae is sometimes considered as a similar condition

S. Alam etal.

231

as tinea faciei by some researchers. Tinea faciei is visually perceived on the hairless

facial area. The causing pathogens are T. rubrum, T. tonsurans, T. schoenleinii,

T. mentagrophytes, M. canis, and T. erinacei. The itching sensation increases when

skin is exposed to sunlight and even burning starts. In some cases this condition

resembles tinea corporis.

Tinea cruris Anthropophilic fungal dermatophytes infect groin and groin asso-

ciated area. T. rubrum, T. mentagrophytes var. interdigitale, and E. occosum are

common causative agents. The clinical manifestations include itching, burning, pru-

ritus, and formation of red lesions with clear centers. The edges of the ring are sharp

and raised. Vesicles or pustules may be formed that may exude out and are moist

when macerated. The moist acute cases may resemble eczema while dry pustular

forms of lesions are chronic in nature. As the lesion increases, in size hyperpigmen-

tation occurs in the central part. Both tinea cruris and tinea pedis are conditions

caused by the same fungal pathogen and can occur simultaneously.

Tinea pedis and tinea manuum T. rubrum, T. mentagrophytes var. interdigitale,

and E. occosum cause tinea pedis infection mostly, and these pathogens are anthro-

pophilic. Interdigital tinea pedis (athlete’s foot) is an infection of the foot, character-

ized either by dryness, ssures, and scales or white, moist macerated lesions in

some or all of the spaces between the toes. Tinea pedis also exists in the chronic,

erythematosquamous type. This condition is evident when scales appear on the feet;

swelling and dryness are also visible on the feet. Another form of tinea pedis appears

on feet soles and manifests itself in the form of redness and withdrawal of foot nails.

Tinea manuum is a dermatophytic fungal pathologic reaction condition on human

hands. When these fungi infect hands, palms become dry; red coloration due to

erythematous response and scaling also occurs. Anthropophilic dermatophytes are

mostly isolated for tinea manuum condition (T. rubrum), zoophilic fungi M. canis,

T. mentagrophytes, T. verrucosum, and T. erinacei, or the geophilic organism

M. gypseum are also isolated in some cases. Tinea unguium (or onychomycosis) is

a condition when nails are infected with dermatophytic fungus. Its manifestation is

evident when nail shape is distorted and the color is changed (Microsporum 2004).

10.1.4.9 Allergen inRespiratory Allergic Patients

At the start of the eighteenth century, it was detected that fungi in air environment

cause many respiratory ailments (Huber 2006). Sir Floyer in 1726 has mentioned a

patient with an astringent asthmatic attack who visited a brewery where fermenta-

tion was going on. After a century, Blackley detected that chest tightness and bron-

chial catarrh were caused by Penicillium glaucum spores were inhaled (Blackley

1873). Storm van Leeuwen was the scientist who declared that asthma is also caused

by fungal spore inhalation. The initial discovery of fungi as respiratory allergen was

made 300 years ago, but the disease could not be studied much (Crameri etal.

2014). Presently enormous data is available where fungi as respiratory allergen have

caused several ailments both in indoor and outdoor environments. Many asthmatic

patients are prone to aeromycoora and develop infections when exposed to fungal

10 Impact ofAerial Fungal Spores onHuman Health

232

spores, and some patients may become asthmatic even if they were previously not

(Jo etal. 2014). Home dampness, visible mold magnication, and moldy odor are

indication of huge fungal load inside homes and are the main causes of asthmatic

reactions in children and elderly (Meng etal. 2012). A correlation exists between

fungal spores load and asthmatic reactions in patients. Mortality may be caused

when asthma patients are not treated within time. It was noted in Chicago that dou-

ble deaths from asthma occurred on days when fungal spores in air were more as

compared to days when fungal spores load was less (Targonski etal. 1995). In rural

areas when crops ripen the spores load in air is also increased. This increase is fur-

ther augmented when crops are harvested and stored (RodrÍGuez-Rajo etal. 2005).

Respiratory ailments associated with fungi mostly belong to Ascomycota and

Basidiomycota group (Pulimood etal. 2007).

The allergic response was indicated in experiment when IgE-mediated reactions

were increased. The histamines in basophils were released in sensitive patients. This

was detected by skin testing (Fadel etal. 1992). Earlier bronchial and nasal chal-

lenge experiments for spores and mycelia inhalation concluded that it may produce

rhinitis, asthma, and eosinophilic inltration reactions (Licorish etal. 1985). There

is evidence that fungal spores and mycelium both have certain components that can

cause allergic reactions. Alternaria alternata allergen (Alt a 1) is present in both

spores and mycelium of fungus and detected by electron microscopy (Twaroch etal.

2016). Fungi have the ability to activate further the innate immune system which

may result in inammation enhancement by other allergens like pollens.

It is a prerequisite if patients are tested in hospital environment for sensitization

against fungal allergens. Air is always laden with fungal spores, and it is almost

unavoidable to nd a fungal spore-free environment. Different sizes of fungal air

contamination have been investigated in recent years, and several fungal species

have been identied (Oh etal. 2014). DNA sequence analysis of different fungal

abundant species in air and dust particles in different seasons were studied. It was

found that ne particles contain more fungal allergens than coarse particle which in

turn harbored more human pathogens (Oh etal. 2014). There are certain other fac-

tors that inuence fungal allergen presence in air. These include climatic factors like

temperature, precipitation, wind, and moisture content in air. Sunlight is also an

important factor that affects fungal spore presence in air (Kilic etal. 2010). The

spores level increases in hot months and autumn season and greatly reduces when

winter approaches. If we note daily variation in spores count early evening and

afternoon have more spores load.

Collectively the human body is exposed to fungal spores through air inhalation,

skin exposure, or when ingested with contaminated food. The lungs route is most

prominent route for getting fungal allergens of various shapes and sizes. Usually

2–250 μm spores are able to cause respiratory allergic reactions. Certain small

spores get entry to the lower respiratory part of lungs. The threshold level for each

allergen is different to start sensitizing symptoms like in Alternaria 100 spores/m3

are able to induce allergic manifestations, whereas in Cladosporium 3000 spores/m3

are needed to create allergic symptoms. Halogen Immunoassay (HIA) is used to

quantify fungal fragments and submicron fungal particles (Green etal. 2006). It is

S. Alam etal.

233

generally found that large fungal fragments and submicron particles colonize air

more than spores. It is also detected that air allergens are not necessarily dependent

on spores number or fragments count (Brito etal. 2012). Major Alternaria allergen

Alt concentration varies with developmental stage of producing pathogen.

10.1.5 Prevalence ofSensitization

Fungi are omnipresent in all types of environment, and this characteristic creates

fungal sensitization everywhere in the earth environment. A range of 3–10% popu-

lation is affected by fungal sensitivity reactions globally. Similarly atopic patients’

response to the atmospheric fungus was found magnied (Park etal. 2014). A study

conducted in different European countries indicated Alternaria and Cladosporium

sensitive allergy in a population of children and adults of 5–60years of age with

rhinitis and/or asthma. A estimate of 9.5% patients were sensitive to either

Alternaria or Cladosporium speciesas detected by skin prick method. Spain had

maximum sensitization (20%) while Portugal had minimum values (3%) (D’amato

etal. 1997). Rivera-Mariani etal. (2011) reported that Early Aversion of Asthma in

Atopic Children (EPAAC) surveyed infant population of 10 European countries,

Australia, and South Africa, for IgE antibodies against aeroallergens. Data from the

USA indicated 12.9% of the population developed Alternaria alternata sensitivity.

Another study showed allergic response against Ganoderma applanatum with the

prevalence of 30%. On the basis of different studies conducted, it is evident that

fungal sensitivity is also an age-dependent phenomenon and individual immunity

plays a main role. Children particularly infants are more susceptible to get aeromy-

coora infection (Moral etal. 2008). IgE antibody levels against Alternaria increase

with age, and after a certain age their titer in blood is decreased with growing age.

Fungi do not cause monosensitization, and polysensitization is observed usually. A

study by Cantani and Ciaschi (2004) has revealed involvement of genetic factors in

population for molds sensitization. Aeromycoora is usually identied on the basis

of spore morphology as time consuming and an expert is required for the identica-

tion. IgE level and skin tests of allergic patients do not sufciently depict exact

prevalence of aeromycoora inuence on respiratory allergies. Fungal allergens

extraction is also a bit difcult task as pure form of the allergen is seldom extracted

(Kespohl etal. 2013).

10.1.6 Fungal Detection inAir

Usually culture techniques are used to isolate air fungus. Different fungal media are

used to isolate on Potato Dextrose Agar and Sabouraud Dextrose Agar. Czapek dox

agar is also utilized to grow air fungus. The petri dish containing sterilized medium

is exposed for 5 minutes in air and then closed with lid and incubated. These

10 Impact ofAerial Fungal Spores onHuman Health

234

cultured fungi are identied through microscopy. This method is time consuming,

and a special expert is required to identify the culture. DNA sequencing is another

method to detect exact species through molecular technique using 18srRNA analy-

sis. This technique is quite expensive and lengthy. Present-day researchers identify

fungal species in air samples or clinical samples on the basis of molecular analysis.

Suchorab etal. (2019) have devised an E nose containing gas two sensors for detec-

tion of fungi in air. The air samples are collected through polyamide tubes. Clinical

diagnosis of fungal allergen is usually symptoms based and clinical manifestations

are categorized. Skin test and invitro tests (particularly the RAST) are utilized to

assess fungal allergens. Usually people are allergic to different allergens along with

the fungal allergens. This makes it difcult to exactly identify the fungal allergens.

It is different to extract the fungal allergen in pure form, but still Alternaria alter-

nata, Aspergillus fumigatus, and Cladosporium herbarum have been characterized

and can be utilized for rapid detection of fungal allergy. Further studies should be

conducted to characterize different fungal allergens.

10.1.7 Prevention andControl ofFungal Ailments

Microclimate plays a signicant role in fungal growth on walls of the buildings,

bio-deterioration, and contamination of indoor environments. Fungal contamination

of buildings not only deteriorate buildings and their indoor environment but also

poses serious health risks to the inhabitants as they produce both allergens and tox-

ins. About 200,000 species of fungi and microbes are known, but 60–100 are signi-

cant pathogens in indoor environment. Among these pathogens, mold is the most

important contaminant having relation with sick building syndrome symptoms

which is mostly present in water leakage and areas having relative humidity above

70% or condensation (Straus, 2009). Fungi have some useful or benecial impacts

(Hyde etal. 2019), but due to infections and damaging impacts, it’s important to

control the fungal growth in the environment. It has been observed that tensile

strength and weight loss/durability of building may decrease more than 80% which

can increase the biodeterioration of buildings (Kazemian etal. 2019). It is important

to address the fungal growth on both indoors and outdoors of buildings to minimize

the general public health, occupational health, and economic loss. Prevention and

control of molds and mycotoxins in food can be minimized by adopting the various

preventive measures which depend on the type of food, storage time, and techniques

(Northolt and Bullerman 1982). There is no direct method to completely eliminate

fungi from the environment, but surveillance methods on regular intervals and ster-

ilization methods can inhibit the fungal growth and can decrease the chances of

infections in the medical environment (Araujo and Cabral 2010; Caggiano etal.

2014). However, correlation between fungal infections and fungal contamination

through genetic analysis is suggested (Caggiano etal. 2014). Molecular techniques

can be helpful in differentiating the medical and environmental strains and their

S. Alam etal.

235

pathogenicity. Preventive measures include early detection of different body parts

by routine cultural through direct microscopy, histopathology, antigen detection,

and serological tests (Rodrigues and Nosanchuk 2020; Seeliger and Schroter 1984).

Different types of measures are adopted to control the fungus-related ailments and

allergies including environmental, meteorological, and chemical treatments which

are discussed in more detail:

10.1.7.1 Environmental Controls

Virtuous air quality can help in controlling the fungal growth in the more important

environments like hospitals where chances of fungal growth are more, kitchens in

the homes, and humid ofces (Munoz etal. 2001). High Efciency Particulate Air

(HEPA) lters are recommended to install at the incoming air to maintain good

quality of air. Similarly, surveillance at regular time interval for maintaining good

air quality can help in controlling the fungal infections.

10.1.7.2 Meteorological Factors

Climatic factors like temperature and humidity play an important role in growth of

fungi and spreading infections in the different environments. Fungi can easily adopt

themselves with the changing climate, and it is important to understand the mecha-

nism at molecular level as highlighted earlier (Hernandez and Martinez 2018). For

safety and durability of food, both water activity and moisture contents are impor-

tant. Water activity (aW) is dened as the ratio of the water vapor pressure of sample

to be tested to the water vapor pressure of pure water under the same conditions.

Water activity is important for the growth of microbes as they will not grow below

a certainlimit (Northolt and Bullerman 1982). For example, awof0.70is required

for mold spoilage and 0.60 for all othermicroorganisms. Similarly, pH, tempera-

ture, oxygen contents, and many other factors can also inuence the growth of

microbes (Mermelstein 2009). Another study reported aW for different molds

ranges between 0.6 and 0.95 like xerophilic molds have aW 0.6 and most molds

0.80 and some yeasts have 0.95 (Stanaszek-Tomal 2020).

10.1.7.3 Chemical Use

Cleaning of kitchen sinks, cabinets, and showers with detergents is recommended as

these areas in homes, ofces, and especially in the hospital environment can cause

the growth of A. niger, A. terreus, and Fusarium spp. Paints can play important role

in the growth of fungus as they prevent the growth of Aureobasidium pullulans,

while Aspergillus and Penicillium species can grow quickly on paints (Nielsen

2003). In some cases, depending on the nature of the solvents, fungi may grow on

10 Impact ofAerial Fungal Spores onHuman Health

236

water-based or solvent-based paints. Natural preservatives like chitin, chitosan, and

its derivatives are recommended for food preservatives alternative to chemical pre-

servatives like fungicides to control the growth of post-harvest fungus. It is reported

that chitosan has triple effect (De Oliveira Junior 2016). Similarly, pH, O2, and CO2

have inuence on growth of molds but extent varies. CO2 at 20% in air depresses

mold growth and aatoxin production and markedly depresses mold growth

(Northolt and Bullerman 1982). Hot water with temperature of 70°C for 1h contact

time is an effective disinfectant as reported. Use of hot water and steams requires no

chemical for fungal growth control. Other chemical treatments include hydrogen

peroxide, sodium hypochlorite, and peracetic acid, and quaternary ammonium com-

pounds (quats) at concentration of more than 0.5% are effective against bacteria and

fungi (Wolf etal. 2021). Different fungicides are also used to inhibit and kill the

fungus by damaging cell membranes or by stopping energy production mechanism

(NPIC 2019).

Diverse range of products are used as fungicides like ethanol, vinegar, tea tree

oil, etc. A study reported that tea tree oil has the greatest inhibitor effect against

Aspergillus fumigatus and Penicillium chrysogenum isolated from air samples

while vinegar inhibited against P. chrysogenum and no inhibitory effect has been

observed against 70% ethanol (Rogawansamy etal. 2015). Herbal medicine treat-

ment is effective against the control of skin infection, e.g., mustard oil is effective

against dermatophytes. A study reported mustard essential oil effectiveness against

molds by inhibiting their growth (Mejia-Garibay etal. 2015). Similarly, another

study reported the effectiveness of natural oil like cinnamon leaf, bay, clove, mus-

tard, lemongrass, thyme, orange, sage, and rosemary and concluded that effective-

ness depends on method of application (Suhr and Nielsen 2003). Nonchemical

method includes genetically modied and resistant crop varieties that can combat

fungal and other diseases (The Bichel Committee 1999).

10.1.7.4 Public Awareness

Fungal infections are moresevere and difcult to managebecause boththe host

cells and fungiare Eukaryotes. Public awareness about the growth and related

infections is highly important to address the issues. As most of the people are

unaware about the causes, spread, and control of infections (Brandt and Park

2013), public awareness about the types of fungus, their pathogenicity, and con-

trol of its spread is mandatory to save both health and food. Fungal diseases are

seldomely reported ontheTV talk shows or print media. Althoughmost ofthe

food is spoiled by growth of Aspergillus and other fungal genera, public aware-

ness is scanty. It is treated as neglected disease as compared to other infections. It

is recommended to allocate more funding for the control of fungal infections

(Rodrigues and Nosanchuk 2020).

S. Alam etal.

237

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T. Ahmed, M. Z. Hashmi (eds.), Hazardous Environmental Micro-pollutants,

Health Impacts and Allied Treatment Technologies, Emerging Contaminants and

Associated Treatment Technologies, https://doi.org/10.1007/978-3-030-96523-5_11

Chapter 11

Health Risks Associated withArsenic

Contamination andIts Biotransformation

Mechanisms inEnvironment: AReview

MuhammadHamza, SadiaAlam, MuhammadRizwan, andAliaNaz

Abstract Contamination is the presence of specic or nonspecic substances in

high concentration in a given environment which may or may not be harmful for

society. Pollution is the slow and continuous introduction of toxic elements into the

environment which may lead to toxicity. A survey conducted by World Health

Organization reported that more than one billion people lack healthy air to breath

and only air pollution is responsible for annual three million deaths globally. Among

pollutants, arsenic is the most toxic element detrimental to multicellular living

organisms in contrast to many single-cell or unicellular microorganisms as these

utilize arsenic as a respiratory metabolite. In the periodic table, arsenic is placed in

group 15 and has atomic number 33. Arsenic toxicity depends on its physical and

chemical forms, valence state, route of transmission to body, toxicity dose, and

duration of exposure of body to arsenic. Arsenic toxicity leads to carcinogenicity

and mutagenicity. The Agency for Toxic Substances and Disease Registry Priority

List of Hazardous Substances has placed arsenic as group 1 human carcinogenic

element. Humans are exposed to arsenic through drinking water contaminated with

arsenic; the water from the wells, which are drilled into arsenic-rich ground strata;

or leaked water pipes or wells orby industrial or agrochemical waste. Humans may

come in contact with arsenic by inhalation of dusts, fumes, or mists contaminated

with arsenic. Food with pesticides residues and grown in arsenic rich soil or irri-

gated with contaminated water also harbour arsenic. The order for toxicity of

M. Hamza · S. Alam (*)

Department of Microbiology, The University of Haripur,

Haripur, Khyberpukhtunkhwa, Pakistan

e-mail: sadia.alam1@uoh.edu.pk

M. Rizwan

US-Pak Center for Advanced Studies, Mehran University of Engineering and Technology,

Jamshoro, Sindh, Pakistan

A. Naz

Department of Environmental Sciences, The University of Haripur,

Haripur, Khyberpukhtunkhwa, Pakistan

242

arsenicals is: MMA (lll) > Arsenite (lll) > Arsenate (V) > MMA (V) = DMA (V).

Arsenic is an agent that induces mutation and affect the genetic makeup of human

being; it also increases the risk of cancer in multiple organs including the skin, kid-

ney, lung, and urinary bladder. Earth crust has 2–5mg/kg arsenic richly deposited

in igneous and sedimentary rocks like shale and coal. Arsenic exists as organic and

inorganic forms. Organic As (V) are relatively less toxic than inorganic arsenicals.

Microorganisms have the ability to bioremediate the arsenic by active uptake (bio-

accumulation) and or passive uptake (adsorption), an enzymatic process in which

organic arsenicals are converted into inorganic arsenicals and in result form volatile

arsenic. In this process, As (V) is reduced into As (III) in which a series of methyla-

tion reactions involve. Arsenic contamination risk should be assessed on a regular

basis and management measures should be implemented accordingly.

11.1 Introduction

11.1.1 Pollution andContamination

Contamination is the presence of specic or nonspecic substances in high concen-

tration in a given environment that may be detrimental to the community or other-

wise. While pollution is the slow and continuous addition of toxic elements into the

environment, the addition takes place as a result of human activity which may lead

to toxicity. Contaminants are produced through various natural and anthropogenic

activities, such as production of chemicals in a larger scale, the methods of handling

and other processingtechniques also add up the contaminants release in surround-

ings. The level of pollution throughout the globe is gradually increasing, and it gives

a red light indicator to all the developed and developing countries.

Pollution is a worldwide problem and disseminates everywhere regardless of

political borders and geographical boundaries.

11.1.2 Pollutants andTheir Impact onEnvironmentalHealth

According to the World Health Organization survey, more than 1 billion people all

over the world do not breathe fresh air, and the annual death rate due to air pollution

is 3 million (WHO 2006; Schwela etal. 2006).

Each year due to pollution, more than 1 million seabirds and thousands of sea

mammals become extinct around the globe. In the United States, about 1.2 trillion

gallons of unprocessed industrial and sewage wastes are thrown in the water bodies.

Due to various environmental pollutions, more than 3 million infants are killed

annually (USEPA 2006).

Accelerated population rate, human-induced activities, and a shift from rural to

urban areas are the factors which increased the pollutant level to its peak.

M. Hamza et al.

243

Industrialization has brought about daily use of more than 60,000 chemicals in the

form of fuels, consumer products, industrial solvent drugs, pesticides, fertilizers,

and food products. Microorganisms are ubiquitous and act as the backbone for the

entire biosphere. Microorganisms play a key role in extreme environmental condi-

tions (such as frozen environment, acidic lakes, ssures of the earth’s surface, deep

sea beds) to the small intestine of animals and also regulate the biogeochemical

cycles. Global biogeochemical cycles include carbon cycle, nitrogen cycle, methane

metabolism, and sulfur metabolism, which are regulated by microorganisms (Das

etal. 2006). Microorganisms are able to produce metabolic enzymes that are respon-

sible for specic and safe removal of contaminants or toxic materials, through dif-

ferent processes, such as degradation or destruction of chemicals or through indirect

transformation into another safe or less toxic compound (Dash etal. 2013).

11.2 Heavy Metals

All heavy metals are toxic, having little benecial characteristics. Metal toxicity

leads to serious health conditions and causes high morbidity and mortality in the

community.

Salts of heavy metal are soluble in wastewater, and as a result, they contaminate

the soil and drinking water. Through ordinary physical methods of separation, the

soluble heavy metals are not separated or isolated (Hussein etal. 2004). When the

concentration of heavy metals is very low, in such case the physicochemical meth-

ods are ineffective and cost-effective. At low concentration the effective and cheap

methods applied for its removalare biological methods such as bioaccumulation

and biosorption (Kapoor and Viraraghavan 1995; Hansda and Kumar 2016).

For safe removal of heavy metals and to re-establish the natural condition of soil,

remediation agents like microorganisms and plants are used. Modication occurs in

the microbial community when soil is exposed to heavy metals. The growth of

microorganisms is extremely important when the concentration on heavy metal is

low in soil (Jansen etal. 1994).Microbial communities respond against the heavy

metalsvariably. Their responseis based on several factors, such as concentration

and availability of heavy metals. It is a complex process which is controlled and

regulated by multiple factors, including the kind of metal, nature of the medium

used for processing, and microbial species, which is a key factor (Coblenz and Wolf

1994). Rocks and soils have abundant concentration of elements like iron, arsenic,

and manganese and ions like chloride, uoride, sulfates, and radionuclides. These

compounds pollute water when diffused in it and affect the quality of the groundwa-

ter (Hashim etal. 2011). The natural sources of pollutants which are able to release

are volcanic eruptions, forest re, and cosmetic dusts. They are also a key source for

many noxious heavy metals like cadmium, lead, mercury, etc. (Timmreck 2012).

Several man-made activities such as quarrying, energy release, combustible produc-

tion, lamination, handling of aqueous waste refuse, nuclear fuels, and agriculture

waste are responsible for the release of heavy metals into the environment and

become an environmental pollutant.

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

244

11.3 Arsenic

Arsenic (As) is a conspicuously noxious metalliform element abundant in aqueous

and soil medium naturally. Human-induced ventures like drilling, use of pesticides

or herbicides that contain arsenic, and elds ushing with arsenic-polluted water

add up to heavy contamination of arable land (Williams etal. 2009).

Arsenic is contemplated as the most widely distributed element found in the

environment. It is known to be as the twentieth most commonly available trace ele-

ment in the earth’s crust, and 14thin seawater, while in the human body, itis twelfth.

As75 is the stable isotope of arsenic found in natural form. Several other radioiso-

topes were synthesized (Jomova etal. 2011).

The most common environmental toxic substance is arsenic; it enters into the

environment through geologic and chemical derivation on earth and also through

human-induced activities. The Agency for Toxic Substances and Disease Registry

Priority List of Hazardous Substances places arsenic as group 1 human carcino-

genic element (Abadin 2013). Arsenic transformation by microorganism generates

a global arsenic bio-geocycle (Zhu etal. 2014). Both environmental and human

health are the main factors that raise the importance of arsenic. Humans getexposed

to arsenicthrough contaminateddrinking water, the water taken from the wells that

are drilled into soil horizons rich in arsenic, or throughleaked water pipes or wells

polluted with industrial efuents orchemicals used for agricultural purposes(Hughes

etal. 1988). Arsenic may be inhaled when in dust, fumes, and mists. Arsenic based

pesticidesalso add this contagion to the food grown thus contaminating the food

chain.Arsenic exposure can occur when people consume food contaminated with

pesticides orthe food grown in arsenic-rich soils or water contaminated with arsenic

(Nriagu 1990). Arsenic is known as protoplastic poison because it affects the sul-

phydryl group of living cells which directly disturbed the function of enzymes in the

cell, cell respiration, and its somatic division known as mitosis.

Arsenic is toxic to multicellular living organisms but many single cell or unicel-

lular microorganisms utilize this element as a respiratory metabolite. Key pollution

issues related to arsenic are groundwater contamination. Arsenic toxicity depends

upon several properties such as its physical and chemical forms, valency, transmis-

sion pathway to the human body, toxic concentration, and exposure duration to

arsenic (Hughes etal. 2011). Arsenic is the major toxic element that affects the

water quality throughout the world (Nordstrom 2002; Smedley and Kinniburgh

2002). Many commercial uses of arsenic lead to the magnication of a toxic envi-

ronmental pollutant. They are mainly used as alloying agents in lead solder, lead

shot, grids of battery, sheath of cables, and in the pipes of boiler. The waste of paints

and pharmaceutical industries highly discharge arsenic which directly meets the

oceanic and groundwater. Report on seawater shows the concentration of arsenic is

about 0.002ppm (Maher and Butler 1988).

M. Hamza et al.

245

Toxicity of arsenic mainly leads to carcinogenicity and mutagenicity

(Ratnaike 2003).

Arsenic has ionic characteristics, which make it complex than other heavy met-

als. Arsenic form compounds like cationic and ionic and also transform ion into

neutral atoms. Many oxidation states of arsenic are found in the natural system, like

2III, 0, 1III, 1V, 1III, and 1V, which are the most prevalent arsenic states in nature.

The most commonly available valence states of arsenic are Arsine (−3), elemen-

tal arsenic (0), arsenite (+3), and arsenate (+5). Arsenite (AIII) is the dominated form

under reducing condition, while oxygenated state support to dominate arsenate

(AsV) in various environments.

Formation of elemental arsenic occurred in hydrothermal deposits at low tem-

perature (50–200 °C) and oxygen-deprived soils, and a bit sulfur conditions are

required to complete its formation.

Physical characteristics such as brittleness, non-ductile, and water insolubility

are adopted by solid elemental arsenic.

Arsenic adversely affects human health more than any other contagion.

Consumption of arsenic-contaminated water affects vital organs and causes differ-

ent types of cancers (IARC 2004; Yuan etal. 2010). Chronic respiratory ailment

results from arsenic exposure of lungs (Smith etal. 2006; Von Ehrenstein etal.

2005), and reproductive aberrations and fetal developmental anomalies have also

been observed (Smith and Steinmaus 2009; Vahter 2009).

Based on the toxicity of arsenic, 2III is the extremely toxic state of arsenic and

rarely found in nature. Due to the use of arsenic in various industries and in agricul-

ture sectors, it enhances its toxicity to the environment and becomes toxic environ-

mental pollutant. Currently, it is a hot topic to understand the natural transformation

of arsenic, its migration, and circulation cycle in the natural system to protect the

environment from contamination of arsenic. Natural and anthropogenic activities

are the main sources that elevate arsenic level in aquifers. In the earth’s crust, the

average abundance of arsenic is between 2 and 5mg/kg and is richly deposited in

igneous and sedimentary rocks like shale and coal.

Not only geological sources are responsible for the contamination of groundwa-

ter, but also environmental conditions which control the chemical and biological

conversion of the material play an important role to contaminate groundwater.

Inorganic arsenic is also known as Class 1 carcinogen agent most likely to induce

cancer in living cells. Geological horizons of Asian continent contain elevated

Arseniclevels in drinking water. The regions includethe densely populated ood-

plains and South and Southeast Asia deltas (Tripathi etal. 2007; Zhao etal. 2010).

Chronic and epidemic complications on the health of humans, animals, and

plants are the highlighted factor which increases the importance of arsenic day by

day (Hughes etal. 2011). The uptake of arsenic by many plants such as rice pollutes

and disturbs the food chain (Zhao etal. 2009, 2010).

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

246

11.3.1 History ofArsenic Use

11.3.1.1 Origin ofArsenic

In 1250, Albertus Magnus was the rst to document the element arsenic (Jomova

etal. 2011).

The name Arsenic is basically derived from the Persian word az-zamikhor, and

there are several other modications of the root word “Zar,” which means yellow or

golden orpiment (like deep yellow-orange color) (Jomova et al. 2011; Meharg

2005). In Syria, ancient people used the term zamika for arsenic. In contrast, the

Greeks gave the name Arsenikon, which is translated as Arsenicum, and they

believed that metals and other substances have gender-specic properties. So they

regarded arsenic as Arrsenikos Orarsenikos (masculine) as it had yellow- orange

orpiment pigment characteristics (Meharg 2005).

The word arsenic is rst used by Latin and French, while in other languages like

Russian, Spanish, and Chinese, arsenic is named as Ars’enico; in German it is Arsen

and in Italian it is Arsenico. As European chemists began to differentiate elements

and compounds, the name arsenic was strictly referred to element no. 33. Arsenic is

the twentieth most abundant element on the surface of the earth, and it has adverse

effects on human health, and also it affected the natural environment (Cullen and

Reimer 1989; Adriano 2001).

11.3.2 History ofArsenic

Arsenic is also known as “poison of kings,” a name that describes its historical use

and hazardous effect. In the past, it has affected human lives more than any other

noxious element. As a result, ratios of death in human civilization are drastically

associated with arsenic. The historical poisoning epidemicsincluded arsenic use in

most of the cases.Its use in present day life is also threatening and it is suspected to

continue in future if not restricted (Kretsinger etal. 2013).

11.3.3 An Old Remedy

The elemental form of arsenic was isolated about seven centuries ago. Chinese and

Greek healers used and utilized compounds of arsenic as medicines for more than

2400years ago. Besides the poisonous and carcinogenic effects of arsenic, physi-

cians and scientists used arsenic to treat various diseases and conditions success-

fully (Chen etal. 2011; Zhu etal. 2002).

M. Hamza et al.

247

Hippocrates (460–370 BC) was the pioneer who used arsenical such as realgar

and pastes of orpiment to treat ulcers. Chinese Nei Jing Treaty (263 BC) reported

the use of arsenic pills to cure the periodic fever associated with malaria.

Centuries ago (100 BC), realgar-containing pastes were used to cure certain der-

mal complications like carbuncle. From 40 to 90 AD, Dioscorides analyzed that use

of arsenicals can cause loss of hair, but on the other hand, it would also clear lice,

scabies, and many skin outgrowth. Malaria was treated by using medicine which is

composed of realgar, arsenic trioxide, and orpiment, and the drug was formulated

by Si-Miao Sun (581–682 AD). Pharmacopoeia of Shi-Zhen Li in the Ming Dynasty

(from 1518 to 1593 AD) reported that various diseases were successfully treated by

using arsenic trioxide (As2O3). In Europe Avicenna (980–1037 AD) and Paracelsus

(1493–1541 AD) introduced therapy based on using arsenic (Kretsinger etal. 2013).

From the eighteenth to twentieth century, compounds of arsenic such as neosal-

varsan, arsphenamine, and arsenic trioxide were used as drugs (Antman 2001; Zhu

etal. 2002).

Lefebure in 1700 discovered a paste-containing arsenic which is used as a rem-

edy to treat all kinds of cancer. Fowler’s solution, invented by English scientist

Thomas Fowler, consists of arsenic trioxide and potassium bicarbonate (KH2AsO3,

1%w/v) that may be used to treat asthma, cholera, eczema, pemphigus, and psoria-

sis. In the nineteenth century, ulcers and cancer were treated by using external

pastes of arsenides and arsenic salts; it may also be applied as antiperiodics, antife-

brile, disinfectant, spasmolytics, scathing agent, stomachic carminative, depilato-

ries, iron-increasing agent, tranquillizers, and stimulants. Administration of drugs is

done through different manners such inhalation of drug vapors and muscular and

intravenous injections. In 1887, chronic myelogenous leukemia (CML) is treated

using Fowler’s solution through which white blood cellscount was reduced. In 1931

studies reported the remarkable effectiveness of Fowler’s solution while treating

nine patients of chronic myelogenous leukemia (CML) successfully. Chronic effects

of arsenic, such as busulfan (drug used in chemotherapy), was reported in the 1950s.

In 1910, Paul Ehrlich, a physician, Noble laureate, and father of chemotherapy,

discovered salvarsan, also known as arsphenamine, an arsenic-based organic com-

pound which was effective against syphilis and tuberculosis and was screened from

almost 500 organic arsenic compounds. Some arsenic-based compounds were used

to cure sleeping sickness or trypanosomiasis such as melarsoprol. The Discovery of

novel drugs and the toxic effect of arsenic are the key factors which cause decline in

the usage of arsenic (Kretsinger etal. 2013).

11.4 Occurrence ofArsenic

Arsenic is counted as one of the most abundant elements on the earth’s crust. It is

found in more than 320 various minerals more likely in arsenopyrite (Foster 2003).

Windblown dust is the source which contaminates air, water, and soil with arse-

nic; also it may enter into water through leaching. The most common and prominent

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

248

atmospheric source of arsenic is volcanic eruptions. Arsenic also enters into the

environment through smelting and mining of ores containing arsenic as co-element.

Studies reported that igneous activities are the ultimate source of arsenic on the

earth’s crust (Nriagu 1994).

The earth crust surfacecontain very lowconcentration of arsenic ranging, from

0.1 to 1000 ppm (mg kg−1), or more. The range of arsenic in atmospheric dust is

503,400 ppm. Marine water harbors a mean of 2.6 ppb, while in stream water, the

range may get reduce to 0.4 ppb. A sufcient level of arsenic is circulating us

through different sources (Mukhopadhyay etal. 2002).

Anthropogenic activities play a key role in the distribution and contamination of

arsenic because a variety of arsenic compounds, that is, both inorganic and organic,

are supplied into the atmosphere and environment via anthropogenic and geogenic

sources (Nordstrom 2002).

Different biogenic or biological sources also play an important role to distribute

a small amount of arsenic in the soil and water. Recent studies on arsenic ground-

water contamination in Bangladesh and West Bengal acknowledge that geological

activity is the source for the arsenic dissemination. The sedimentary rocks of

Himalayas have dispersed it the time span of ten thousand years. In oxidizing condi-

tions, at low pH, arsenate is dominant, while at high pH arsenite is dominant. Under

reducing environment uncharged arsenite As(OH)3 is predominant, and it is highly

hazardous and quite strenuous to remediate (Smedley and Kinniburgh 2002). It is

associated with some noncorrosive minerals, such as sulde mineral and release

into the environment in large amounts (Duker etal. 2005). Some key sources which

increase the level of arsenic on land are coal ash (22%), commercial wastes (40%),

mining industry (16%), and steel industry (13%) (Eisler 2004).

Some arsenic compounds such as arsenic trioxide (As2O3) are frequently used in

the synthesis of different items like ceramic, glass, electronics, antifouling agent

and pigment production, cosmetics, reworks, and copper-based alloys

(Leonard 1991).

Arsenic in combination with copper and chromium is used for the preservation

of wood, such chromated copper arsenate (CCA). Sodium arsenite is used to control

the growth of aquatic weeds, which has contaminated ponds and lakes in many

regions of the United States (Adriano 2001).

Studies reported that soil is probably contaminated by the usage of arsenical

pesticides to control the growth and production of tick, eas, and lice in sheep and

cattle dips (McLaren etal. 1998).

A New South Wales studyindicated 11 dip sites containingsignicant amount of

arsenic in the soil. The study results depictedthat top 0 to 10 cm soil contains

37–3542mg/kgof Arsenic. Variation was observed in down soil proleas aresenic

concentrationwas 57–2282mg.kg at 20–40cm depth(McLaren etal. 1998).

Phosphatic fertilizers are also source of arseniccontamination in soilthatmay

indirectly contaminate the food chain via uptake by plants (Peng etal. 2011).

Efuents of timber treatment in New Zealand are key in contaminating aquatic

and terrestrial environments with arsenic (Bolan and Thiagarajan 2011). Ores of

sulde such as Pb, zinc, Au, and copper contain a rich concentration of arsenic

M. Hamza et al.

249

which can be released into the environment during the process of mining and

smelting.

Dust particles stuck with the dress of smelters can also contaminate the nearby

ecosystems with toxic metals or metalloids such as arsenic (Adriano 2001). Gaseous

arsenic as well as bottom and y ash containing a signicant amount of arsenic are

the products of coal combustion. Dust banning of these toxic materials containing

arsenic can lead to soil and water contamination (Beretka and Nelson 1994). Many

herbicides, pesticides, and fertilizers contain arsenic.

Agricultural soil may be contaminated through a variety of agricultural practices

and fertilizers containing arsenic as a key component, such as pesticides, herbicides

containing arsenic, manure of pig, and phosphorous fertilizers, can raise the level of

arsenic in soil, thus endangering human health (Li etal.2016).

Solid wastes released from industries like pesticide- and herbicide-

manufacturerscontain arsenic leading to contaminate the soil and water reserves.

Chatterjee and Mukherjee (1999) reported that the release of industrial efuents of

the product name Paris green pesticide [Cu(CH3COO)2⋅3Cu(AsO2)2] increases the

level of arsenic in groundwater and soil of urban areas of Calcutta, India. Pesticides

such as lead arsenate (PbAsO4), Paris green [Cu(CH3COO)2⋅3Cu(AsO2)2], zinc

arsenite (ZnAsO4), magnesium arsenate (MgAsO4), and calcium arsenate (CaAsO4)

are used as horticultural pesticides and have great part in contaminating soil all over

the world (Peryea and Creger 1994).

Studies reported that organoarsenical herbicides such as disodium methanear-

sonate (DSMA) and monosodium methanearsonate (MSMA) also increase the level

of arsenic and the chance to contaminate the soil (Peryea and Creger 1994).

Agriculture soil containing arsenic is also distributed in some soil components

like iron (Fe), organic component matter, manganese oxide carbonates, and suldes

also, and such kind of distribution can disturb characteristics such as mobility, bio-

availability, and toxicity of arsenic (Islam etal. 2004; deLemos etal. 2006).

Microorganisms can take part in the process of distribution and redistribution of

arsenic; they can perform arsenic transformation and act as arsenic absorbents

(Oremland and Stolz 2003, 2005; Islam etal. 2004).

Studies reported that some microorganisms induce the release of arsenic to the

groundwater, which can increase the risk of diseases in millions of people of

Bangladesh, West Bengal, and some parts of China (Smith etal. 2006).

Groundwater contaminated with arsenic can also transferit into crops and aquatic

ecosystems through the irrigation system. Arsenic-contaminated irrigationwater

can reduce crops yieldand mayhave a negative impacton health when such crops

are consumed as food source. Limited studies were reported on agricultural soil

contaminated with arsenic as compared to that of contaminated groundwater, but

only some studies explained the mechanism of uptake of arsenic in different plants

(Correll etal. 2006).

Qualitative and quantitative effects of arsenic on crops such as rice, which is

irrigated mostly by groundwater are becoming a major issue confronted by the

world nowadays (Meharg and Rahman 2003).

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

250

A study conducted by the British Geological Survey and Department of Public

Health Engineering (2001) groundwater and the area under shallow tube well irriga-

tion concluded that every dry season of each year, about 1000mg of arsenic is

cycled with irrigation water (BADC 2005; Saha and Ali 2007).

Annually 1 kg/ha of arsenic is donated to the agriculture soil fed with 1000mm

of water contaminated with arsenic (100ppb). Studies concluded that the range of

arsenic in soil from 25 to 50mg/kg is the safe limit for rice cultivation (Saha and Ali

2007). The ability to release the arsenic into the environment through anthropogenic

activities is greatly dependent upon chemical nature and bioavailability in nature.

Ore dressing, smelting, mining, smelting of non-ferrous metals, production of

arsenic and manufacturing of arsenic-based compounds, petro-chemical industries,

pesticides, beer, table salt, tap water, paints, pigments, cosmetics, glass, manufac-

turing of mirror, antifungal compounds, insecticides, treated wood and contami-

nated food, dye stuff, and tanning industryuse arsenic in different concentrations

(Hasanuzzaman and Fujita 2012).

Arsenic compounds especially orpiment (As2S3), realgar (As4S4), and arsenolite

(As2O3) were consumed and utilized by humans in different forms of domestics and

daily usage of products such as pigments, medicines, manufacturing of alloys, pes-

ticides, herbicides, glassware, embalming uids, and as a depilatory in leather man-

ufacturing (Eisler 2004).

11.4.1 Soil Microorganisms andArsenic

Soil microbes can convert arsenic into volatile derivatives and thus wipe it away

from the surface of the earth. Microoras of soil and bacterial species isolated from

the soil are reported which show the characteristic of biological volatilization. The

phenomenon of arsenic volatilization is done by both oxic and anoxic microorgan-

isms including bacteria and unicellular mycoora (Edvantoro etal. 2004; Meyer

etal. 2008).

In the United States, both types of organic and inorganic arsenic are used in agri-

culture. Inorganic arsenic is converted into methylated arsenic, such as monoso-

dium methyl arsenate (MSMA) and are still used as pesticides/herbicides.

Monosodium methyl arsenate (MSMA) is used to maintain the turf of golf courses

and is also used in sod farms and in cotton elds to control weed production

(Matteson etal. 2014).

The pentavalent aromatic arsenicals like roxarsone [4-hydroxy-3-

nitrophenylarsonic acid, Rox (V)] are used to control coccidioides infection and

improve weight gain, feed efciency, and also meat pigmentation in poultry and in

swine. It is used as an antimicrobial growth promoter (Bednar etal. 2004; Stolz

etal. 2007).

M. Hamza et al.

251

11.4.2 In Rock

Volcanic and industrial activities with arsenic pollute the environment. Some of the

major anthropogenic activities such as mining and smelting of nonferrous metals

and combustion of fossil fuels increased the level of arsenic contamination in soil,

air, and water. Pesticides containing arsenic increase the arsenic amount in agricul-

tural soil. Use of arsenic as a preservative for timber can also pollute the environ-

ment (WHO 2000, 2001). Naturally, arsenic occurs mostly in sulde form and is

associated with certain minerals, such as silver, copper, lead, nickel, antimony,

cobalt, and iron. More than 200 species of minerals contain arsenic. High concen-

tration of arsenic is mostly associated with deposits of sulde, while terrestrial

abundance is about 5mg/kg.

The level of arsenic is detected approximately 2900 mg/kg in sedimentary iron,

manganese ores, and phosphate rock deposits (WHO 2001). Both natural and

anthropogenic activities are the key sources that release arsenic into the atmosphere.

Natural sources accompanied about 1/3 of the world’s arsenic atmospheric ux

(7900 tons/year).

Soil and sediments contain different ratios of arsenic ranging from 1 mg/kg to as

high as 40 mg/kg. Human activities may contribute to several grams of arsenic in

soil. According to WHO (2001), arsenic concentrations may vary from 5 to 3000

mg/kg contributed by anthropogenic activities.

11.4.3 In Groundwater

Through water, arsenic is transported from anthropogenic and natural sources.

Factors that affect the form and concentration of arsenic are as follows (WHO

2000, 2001):

• Conditions of water such as reducing promote the predomination of arsenites.

• Level of biological reactions like biological conversion of inorganic arsenic to

methylated arsenic acids.

• Water type such as seawater to that of freshwater versus groundwater.

• Reservoirs of water near sources such as soil and rocks contain a high level of

arsenic and also anthropogenic sources.

Studies reported that less than 10 μg/L of arsenic is detected in freshwater sources

such as river and lakes, while this concentration varied up to 5mg/L when water

source is located near high anthropogenic sources which carry rich content of

arsenic.

Comparative studies concluded that an average concentration of arsenic in sea-

water and groundwater is 1–2 μg/L, while concentration of arsenic is detected up to

3mg/L in those areas that have volcanic rock and where high deposits of sulde

mineral are found (WHO 2001).

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

252

11.4.4 Arsenic inOverall Environment

About 24,000 tons per year of arsenic has been added into environment through

anthropogenic activities such as mining and smelting of parent metals and burning

of fuel (brown coal) and pesticides containing arsenic. Volcanic activity may also

boost up the level of arsenic in the environment through different ways such as low

temperature volatilization, vegetative exudates, and dusts containing arsenic ele-

ments blown by the wind (WHO 2000, 2001).

Inorganic arsenic (a mixture of both Asiii and Asv, predominant by pentavalent) is

present in the atmosphere of urban, suburban, and industrial areas. Methylated arse-

nic is considered as the smaller component of arsenic in the atmosphere (WHO

2000). In remote and rural areas, the concentration of arsenic in air ranges from 0.02

to 4 ng/m3, while in urban areas this concentration exceeded up to 3–200 n3g/m3.

More than 1000ng/m3 of arsenic has been reported from industrial sources such as

smelting of nonferrous metals and burning of coal containing a high concentration

of arsenic in power plants (WHO 2001). Many decades have witnessed groundwater

pollution with arsenic particularly in China, Taiwan, and some Central and South

American countries. The natural geological formations that have reservoir of arse-

nic exist in West Bengal (India), Bangladesh, some parts of Argentina, Chile,

Mexico, Thailand, Brazil, etc. Groundwater generally has As (V). Methylated arse-

nic compounds also exist in groundwater (IARC 2004).

11.5 Applications of Arsenic

11.5.1 Arsenic Used asBiotic Weapon

The United States released more than 1.2 million gallons of DMAs (V) during

Vietnam War. It is also known as agent blue and is one of the rainbow herbicides

used to destroy crops such as rice bamboo, and banana (Stellman 2003).

Recently in the United States, agent blue was used as herbicides on the cotton

eld and courses of golf. In Florida, diphenylated arsenic compounds such as Clark

I (diphenylchloroarsine) and Clark II (diphenylcyanoarsine) were synthesized and

used in World War I and World War II.After the war these chemicals are deposited

in land and seawater. After that, deposited arsenic compounds are degraded by bac-

teria into inorganic forms, and the species of bacteria were isolated from the con-

taminated sites (Harada etal. 2010).

Different processes of various industries contributed to elevate the level of arse-

nic in water, soil, and air. Uses of various chemicals and agricultural pesticides

which contain arsenic as a major constituent can increase the chances of environ-

mental contamination.

Decades ago, inorganic arsenic compounds were excessively consumed as wood

anti-decay agents, pesticides, weedicides, and colorants, and now its use is

M. Hamza et al.

253

abandoned in agriculture for its hazardous effects. Some arsenic (organic) com-

pounds are used as pesticides such as disodium methyl arsenate (DSMA), monoso-

dium methyl arsenate (MSMA), and cacodylic acid, while some are used as additives

in the feed of animals. To improve the properties of a mixture of metals or alloy, a

small amount of elemental arsenic was added to it and used in certain product,s such

as lead-acid batteries, light-releasing/light-emitting diodes, and semiconductor

(Oremland and Stolz 2003)

11.5.2 Useful Effects ofArsenic

In oral administration, arsenic was used as Fowler’s solution in curing mixtures and

also used for the treatment of certain diseases like asthma and leukemia and differ-

ent malignancies (Leslie and Smith 1978). In the past, arsenic was used as a remedy

to treat syphilis, topical eosinophilia, trypanosomiasis, lichen planus, verruca pla-

num, and psoriasis. Arsenic is used for domestic, industrial, and agriculture pur-

poses such as in the form of insecticides, weed killers, and rodenticides (Thorburn

1983; Antman 2001; Çöl etal. 1999; Saha etal. 1999). Arsenic is also used as wood

preservative and also utilized as an active ingredient of anti-spirochetal and anti-

protozoa medicines. Chromated copper arsenate was used in residential wood fur-

niture but is banned since 2003 in the United States and Canada. Disodium

methanearsonate in small amounts was applied as herbicides in cotton elds, but the

Environmental Protection Agency banned its use since 2009. Roxarsone, arsanilic

acid, and derivatives are commercially utilized in poultry feed to increase biomass,

improve feed efciencies, and cure poultry disease (FDA 2008). Arsenic along with

lead is used to make an alloy. Alloys are used in lead-acid batteries. Electronic

industries also use arsenic in making conductors and semiconductors as gallium

arsenide. It is also utilized in making microwave and milliwave devices. Arsenic is

used in making ber optics and computer chip crystals (IARC 2006). Pigments,

antifungal compounds in wall paints, different soaps, ceramics, and electrophotog-

raphy have arsenic as a prime ingredient. Arsenic is also used as a foul smell remov-

ing agent in wall paints.

11.6 Organic andInorganic Arsenic

11.6.1 Arsenic inPeriodic Table

Arsenic is an element found in the periodic table. It is placed in group 15 and has

atomic number 33. In elemental form, arsenic is symbolized as (Adriano 2001).

Group XV contain semimetallic element, but here arsenic was also reported as

metal contaminant. Along with arsenic, other elements such as nitrogen, phospho-

rus, antimony, and bismuth are also placed in the same group.

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

254

Arsenic has four valence states:

1. 3 (arsenides)

2. 0 (elemental)

3. +3 (trivalent, arsenites)

4. +5 (pentavalent, arsenates)

The atomic mass of arsenic is 74.921 and has 60 atomic mass units (amu), and

its atomic number is 33, denoted by Z, which shows the number of protons present

in nucleus of each atom of arsenic (Carter etal. 2003).

11.7 Physical Characteristics ofArsenic

11.7.1 Arsenic Forms

Arsenic is metallic gray and yellow in color. Metallic gray is the stable form of

arsenic. Precipitation occurs whenever arsenate (AsO43−) and its various protonation

types such as H3AsO4, H2AsO4, HAsO42−, and AsO43− were exposed to metal cat-

ions. Under acidic or moderate reducing conditions, arsenate coprecipitate or absorb

into the iron oxyhydroxides. Mobility of coprecipitation is reducing under acidic

and moderate reducing conditions. pH is directly proportional to arsenic mobility,

so as pH increases mobility of arsenic is also increased (Evanko and Dzombak

1997). Arsenic is predominantly present in anionic form because it does not create

complexes with other anionic elements and compounds such as Cl− and SO42

(Evanko and Dzombak 1997). Absorptive ability of arsenic is privileged to soils,

and therefore in groundwater and surface water, they may travel very limited dis-

tance. Arsenite (AsO33−) and its protonated form such as H3AsO3, H2AsO3−, and

HAsO32− are dominated in high reducing conditions. Arsenite has strong binding

afnity to sulfur compounds and can absorb or coprecipitate with metal suldes

(Evanko and Dzombak 1997). Methylation of arsenic may result to the generation

of methylated compounds of arsine such as trimethyl arsenic acid (CH3) and dimeth-

ylarsine HAs (CH3)2, AsO2H2, and dimethylarsenic acid (CH3)2 AsO2H.The phe-

nomenon is named as biotransformation (Evanko and Dzombak 1997). Previous

studies suggested that arsenic load can be reduced through absorption and copre-

cipitation with hydrous iron oxides, and the suggested techniques are very effective

to remove these hazardous materials. Arsenate can be leached from the soil having

a low amount of reactive metals (Evanko and Dzombak 1997). Generation of arse-

nite (AsIII) can be promoted in the presence of organic and reducing conditions,

that is, alkaline and saline. These two factors create compound units with arsenic

(Evanko and Dzombak 1997). Arsenide binds to gallium and forms gallium arse-

nide. Gallium arsenide has alloy-like or intermetallic-like characteristic which is

further used in semiconductor industry (Carter etal. 2003). Arsine has −3 valence

state, found in the form of a colorless gas. Arsine is used in several industrial pro-

cesses and is harmful to humans because it is a potential hemolytic agent (Carter

M. Hamza et al.

255

etal. 2003; Klimecki and Carter 1995). Arsenic makes covalent bond with hydro-

gen, sulfur, and oxygen, and it self-creates inorganic arsenicals. When it binds with

carbon, it forms organoarsenicals.

11.8 Arsenic Toxicity

11.8.1 Division ofArsenic According toTheir Toxicity

The biotransformations such as redox cycles occur between the harmless or less

toxic pentavalent arsenate As (V) and highly toxic and carcinogenic trivalent arse-

nite As (III) (Oremland and Stolz 2003).

Inorganic arsenite (As III) is less toxic than MAs(III), and it generates variation

in the hepatocytes of hamsters and humans (Petrick etal. 2000, 2001).

Biological methylation is the initial process through which various toxic arsenic

species are detoxied or deactivated. MMA (V) and DMA (V) are the end product

of methylation which act as biological marker for chronic arsenic exposure, and

excluding MMA (III), others are excreted through urine. The intermediate product

of methylation is MMA (III).

The leakage level of lactate dehydrogenase, leakage level of potassium, and

mitochondrial metabolism of tetrazolium salt in human hepatocyte cells determined

the species and toxicity of the arsenicals like arsenite (III), arsenate (V), MMA (V),

DMA (V), and MMA (I) (Petrick etal. 2000, 2001).

The following order determined the toxicity of arsenicals according to their

species:

MMA (lll) > Arsenite (lll) > Arsenate (V) > MMA (V) = DMA (V)

The MMA (III) (monomethylarsonic acid) is the intermediate product of biologi-

cal transformation of arsenic. MMA (III) is more toxic with respect to other arseni-

cal species, and it is the only species of arsenic responsible to induce cancer and

other health problems. So methylation is the process that activates the toxicity of

arsenic, and it is not being considered as the detoxication process (Styblo

etal. 2000).

11.8.2 Effect ofArsenic onLiving Cells

Arsenic is an agent that induced mutation and affects the genetic makeup of human

beings; it also increases the risk of cancer in multiple organs, including the skin,

kidney, lung, and urinary bladder (Karagas etal. 1998). Arsenic is accumulated

inside the different parts of plants; whenever the same plant is consumed, arsenic is

transmitted to the human or animal body and causes serious health-related compli-

cations (Peng etal. 1994; Abedin etal. 2002).

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

256

More than 200 enzymes were hunted by arsenic, but mostly it will affect cell

metabolic pathways, DNA replication, and repairing, and also it replaces phosphate

in high compound, that is, adenosine triphosphate. Peroxidation of lipid and dam-

age to DNA are caused by induction of reactive oxygen intermediates, during redox

cycling and activation of metabolic pathways (Cobo and Castiñeira 1997). Arsenite

binds to thiol or sulfhydryl groups present in tissue proteins of organs such as the

liver, spleen, lungs, kidney, lungs, GIT mucosa, and keratin-rich tissues such as the

skin, hair, and nails (Ratnaike 2003).

Cellular biochemical functioning is disturbed when arsenic reacts actively with

proteins and enzymes. Several processes such as photosynthesis, transcription, res-

piration, and metabolism of plants were heavily affected by the toxicity of arsenic

(Meharg and Hartley-Whitaker 2002).

Arsenic creates reactive oxygen species (ROS) generation inside the cell and

oxidizes proteins. Lipid peroxidation also occurs, and cell organelles are damaged.

DNA is also harmed through ROS (Finnegan and Chen 2012).

11.8.3 Arsenic Exposure

11.8.3.1 Biogeochemical Cycle andArsenic

The process in which three different systems (geological, biological, and chemical)

interact for an element is known as the biogeochemical cycles of that element. The

biogeochemical cycle includes mobilization and transport of elements in different

systems from living to nonliving and vice versa or ability of a living organism to

degrade or increase the concentration of elements in an environment. Volatilization

of the element is a rapid and faster method, in which the element directly evaporates

from soil or water and enters the atmosphere (Brown 2008; Bundschuh and

Bhattacharya 2009).

Under steady-state conditions, the ratio of total mass of a chemical in a specic

system to that of total emission rate or total removal rate is known as atmospheric

residence. Heavy metals such as mercury and lead have a higher residence time in

the atmosphere to that of other heavy metals. Microbial diversity plays a key role in

biogeochemical cycles because microbes are able to change the residence time and

half-life time of chemicals, a phenomenon known as acclimatization, “in which

certain kind of microbial population are continuously exposed to specic chemical,

which results, rapid transformation or degradation or detoxication of that chemi-

cal.” Two antagonistic processes are bioconcentration and biodegradation in which

the living organisms especially microorganisms are involved. A bioconcentration is

a process in which the concentration of living organism (microorganism) is higher

to that of chemical in the environment or atmosphere, while biodegradation is a

process in which biological transformation of a substance occurs into a new sub-

stance or compound by the help of microorganisms (Centeno etal. 2006).

M. Hamza et al.

257

11.8.3.2 Exposure Pathway

Sources of Exposure

Food and water are the major route for arsenic exposure to human, animals, and

plants. Exposure to arsenic also occurs through air by inhaling contaminated air or

through dermal contact when the skin encounters or is exposed to arsenic-

contaminated accessories.

Rocks are the main natural source, from which arsenic is released and added to

environmental assets like food and groundwater. Arsenic contamination is a major

global issue, and US EPS enlisted arsenic as one of the most toxic elements in the

world. Humans and especially animal models are used to study the complete metab-

olism (i.e., oxidation, reduction, and alkylation) of inorganic arsenic. Under certain

enzymatic processes, the As (III) is converted into As (V). Monomethylarsonate

(MMA) or dimethylarsinate (DMA) is formed by a process known as methylation.

Various arsenic formsexistinside the human body; out of the total arsenic, 20% is

methylated arsenic (in which 14% is MMA and 6% DMA). 78% of As (III), and at

last 2% of As (V). Level of methylated arsenic is increased, when the body is

exposed to As (III) and As (V) for long term (Aposhian etal. 2004). There are many

sources through which arsenic is exposed to a body (living or nonliving); they may

be natural, industrial, and administrated or accidental source. Self-administered and

unintentional or accidental consumption of arsenic occurs in adults or children.

Adults mainly consume arsenic for suicidal or homicidal purposes, and in that case,

arsenic causes acute poisoning (Fuortes 1988). Humans are exposed to arsenic

whenever they consume water contaminated with arsenic. The water may be taken

from the wells that are drilled into arsenic-rich ground strata or water pipes that are

contaminated by industrial or agrochemical wastes or efuents (Hughes etal. 1988).

Arsenic contaminated dusts, fumes, and mists, food contaminated with arsenical

pesticides or the food grown with arsenic contaminated water or soil rich in arse-

nicare the hazard sources for humans (Nriagu 1990). Community-based study was

conducted and reported that children poorly metabolize arsenic than women. The

arsenic metabolism ratein children isDMA (47%) and inorganic As (49%)while

women are able to metabolize DMA (66%) and inorganic As (32%) (Concha etal.

1998). Aromatic arsenicals are exposed and introduced to environment when

chicken litter is applied as fertilizer to farmlands (Bednar etal. 2004).

Organic As (V) are relatively less toxic than inorganic arsenicals (Bednar etal.

2004; Stolz etal. 2007). Degradation of aromatic and methylated arsenicals results

in the production of more toxic inorganic arsenicals (Feng etal. 2005). Microorganism

is able to degrade or bioremediate the arsenic which gives possible advantage and

importance to microorganism. Microorganism provides a cost-effective technology

and environmentally friendly way to remove heavy and toxic metal from the envi-

ronment (Valls and De Lorenzo 2002). A natural process known as bio- volatilization

is applied to remove arsenic from soil and water, which is also considered as a tool

of bioremediation. Several factors are involved in the volatilization of arsenic from

the soil or water; these factors are arsenicvalence forms,its concentration, moisture

content in soil, temperature, organic materials, several other elements, growth rate

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

258

of microbes, and volatilization capacity of arsenic (Edvantoro etal. 2004; Gao and

Burau 1997).

Arsenic is one of the natural elements present in sediment, soil, and rock. Human

may happenstance with arsenic from two sources that may be natural or anthropo-

genic or both. The quantity as well as quality of arsenic is mainly dependent upon

geological antiquity of the area (Fowler 2013; Nordberg etal. 2014).

In the United States level of air contaminated with arsenic in rural areas ranges

from <1–3 ngm−3, while in urban areas the level is quite deviated and ranges from

20–30 ngm−3 (ATSDR 2007).

According to the World Health Organization, the level of inorganic arsenic con-

tamination in fresh water such as surface water and groundwater ranges from 1 to

10 gL−1 (WHO 2001).

Nordstrom in 2002 revealed that in some areas of the globe, the level of arsenic

in drinking water is high as >100 gL−1 (Nordstrom 2002).

11.9 Transfer ofArsenic toBody

Arsenic is an ordinary element of the human body. The soluble form of arsenic is

absorbed through the gastrointestinal tract. About 40–100% for arsenic was

absorbed by humans. Due to low reactivity with the epithelial membrane of GIT, the

absorptive ability of both inorganic and organic arsenate (As V) is higher than arse-

nite. Arsenate is the most common form of arsenic that is present and contaminates

the drinking water. Arsenic absorbs through intestine and becomes part of the blood.

The disseminated form of arsenic is MMA which is distributed into the whole body.

Concentration of arsenic in the blood and soft tissue of nonexposed individual is

1–5 μg/L and 0.01–0.1μg/L.Arsenic accumulates in nails and hairs, and highest

recorded level is from 0.1 to 1μg As/g. The metabolic pathway of arsenic in humans

is divided into two processes.

The reduction process can reduce arsenate into arsenite when it enters into the

periphery of the cell. Inside the liver cells, arsenite is methylated and forms MMA

and DMA. The mechanism of trimethylarsine oxide production is not yet observed

in the human body. Mechanism of actions of both inorganic arsenate and arsenite

acts differently (Abernathy etal. 1999). Arsenate acts like phosphate because it

replaces phosphate during cellular reactions. Arsenite may react with thiol (-SH)

groups that are present inside proteins and lead to inactivate a variety of enzymes.

Cellular processes convert arsenate into arsenite. Arsenate induces similar biologi-

cal effects as arsenite inside drinking water. Inorganic arsenic makes a strong bond

with molecules of humans. Acute toxicity of MMA and DMA is less that in inor-

ganic arsenic form. Toxicity of inorganic arsenate is quite higher than MMA and

DMA, and one-tenth is the ratio of toxicity between inorganic arsenate and arsenite.

Direct absorption or excretion of inorganic arsenic is not done immediately, but

there are several types of detoxication mechanisms that occur through the process

of methylation. The actual chronic effects of DMA and MMA are not known yet,

M. Hamza et al.

259

but still some studies evaluate that the toxic mechanism of DMA induces due to

chronic exposure. The rate of arsenic excretion can signicantly dene the type of

arsenic to which the body is exposed. Kidneys lter some types of inorganic arsenic

and release it into urine. DMA and MMA generated after the process of methylation

can also be excreted through urine. In two to four days, about 50–90% of arsenic is

removed from blood containing arsenic, and the remaining were removed very

slowly with the passage of time.

11.9.1 Acute Toxicity

11.9.1.1 Acute Poisoning

Acute poisoning mostly occurs by accidental ingestion of insecticides or pesticides

and mostly in the case of suicide attempt. Vomiting and diarrhea may occur when a

small amount, less than 5mg, of arsenic is ingested, but complications may resolve

in 12h, and no treatment prescription is reported for this condition (Kingston etal.

1993). For arsenic the lethal dose for acute illness ranges from 100mg to 300mg.

According to Risk Assessment Information System Database, 0.6mg/kg/day of

inorganic arsenic is denoted as acute lethal dose for humans. Here are some exam-

ples of acute lethal dose which may lead to death of individual: A 23-year-old young

male ingested 8gm of arsenic, and he survived for only eight days.

The American Association of Poison Control Centers reported 898 cases of non-

pesticidal and pesticidal exposure of arsenic, of which 21 were intentionally

exposed. This case resulted in death of one affected. Frequency of pesticidal expo-

sure is lower as compared to non-pesticidal; here 338 cases were reported out of

which two cases were intentionally exposed to arsenic and no mortality was reported

(Bronstein etal. 2007).

A student got a dose of 30gm of arsenic; after 15h of ingestion, he was treated

with British anti-lewisite (an arsenic antidote) and hemodialysis, but he expired

within 48h. The severity of illness depends upon the dose of ingestion, but death

usually occurs within 24h to 4days. Primary complication of acute poisoning is

mostly related to the gastrointestinal system, such as nausea, vomiting, colicky

abdominal pain, excessive salivation, and watery diarrhea. The abdominal pain is

severe. Acute psychosis, diffuse skin rashes, toxic cardiomyopathy, and seizures are

other complications related with ingestion of arsenic. Diarrhea is one of the promi-

nent illnesses which enhances the permeability of blood vessels. Stools in cholera

are described as rice water, but in the case of acute arsenic poisoning, the blood has

also been released with stool, so they are known as bloody rice watery diarrhea. Due

to massive uid loss from the gastrointestinal tract, reduction in blood volume

occurs, and circulatory collapse may lead a person to death. Esophagitis, gastritis,

and hepatic steatosis are some of severe complications which were detected by post-

mortem examination. Other complication such as hemoglobinuria, intravascular

coagulation, bone marrow depression, severe pancytopenia, normocytic

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

260

normochromic anemia, and basophilic stippling are listed as hematological abnor-

malities. Four to eight sailors were exposed to arsenic and developed renal failure.

Some other complications such as respiratory failure, pulmonary edema, and

peripheral neuropathy (which may last for two years) were also observed in acute

poisoning. Long-term peripheral neuropathy leads to conditions like severe ascend-

ing weakness as in Guillain-Barré syndrome which requires mechanical ventilation.

The most common neurological disorder due to exposure of arsenic is encephalopa-

thy, which is mostly caused when arsphenamine is administrated intravenously, and

the encephalopathy is thought to be due to hemorrhage complications. Other com-

plications related to acute poisoning of arsenic are metabolic disturbance, hypogly-

cemia, and acidosis which has also been reported in a single patient (Hughes and

Kitchin 2006).

Some other laboratory tests such as blood count and comprehensive metabolic

panel may also be recommended for arsenic quantication. Removal of the source

of exposure, loss of uids, and use of chelators such as dimercaprol or

2,3- dimercaptosuccinic acid were recommended to treat acute poisoning.

Hemodialysis is recommended in the case of renal failure (Morales etal. 2006;

B’hymer and Caruso 2004; Flora and Pachauri 2010; Kalia and Flora 2005).

11.9.2 Chronic Toxicity

11.9.2.1 Chronic Poisoning

Multiple organ defect is mainly caused due to chronic ingestion of inorganic arse-

nic. High level of arsenic in drinking water causes serious health-related complica-

tions including skin ailments, vascular disease including arteriosclerosis, peripheral

vascular disease, ischemic heart disease (ISHD), renal disease, neurological effects,

cardiovascular disease, chronic lung disease, cerebrovascular disease, reproductive

effects, and cancers of the skin, lungs, liver, kidney, and bladder. Non-insulin-

dependent diabetes mellitus is associated when the body is exposed to high concen-

tration of arsenic (Wang etal. 2003; WHO 2001).

11.9.2.2 Respiratory Effects

Both occupational and tubewell-contaminated water exposure were reported to

cause disease of the respiratory system. Occupational inhalation of arsenic from

different sources such as mining and milling ores and from several industrial pro-

cesses induces severe clinical complications such as irritation of mucus membrane

which further leads to laryngitis, bronchitis, rhinitis, tracheobronchitis, stuffy nose,

sore throat, hoarseness, and prolong cough. Highly and unprotected occupational

exposure causes perforated nasal septum within 1–3 weeks of exposure. Clinical

complications such as tracheobronchial mucosal and submucosal hemorrhages with

M. Hamza et al.

261

sloughing mucus, hemorrhages of alveoli, and pulmonary edema are caused due to

inhalation of arsenite. Other complications such as chronic asthmatic bronchitis and

asthma was caused due to consumption of arsenic-contaminated groundwater.

Studies conducted in West Bengal, India, report diseases such as restrictive and

obstructive lung disease. Skin lesions are an associated disease with respiratory

disorder caused due to chronic arsenic exposure. The same disease association was

found among children of Chile. In Taiwan, blackfoot disease is the most common

with bronchitis.

11.9.3 Gastrointestinal Effect

GIT effects were mostly observed during acute exposure of arsenic. Nausea, vomit-

ing, and diarrhea were observed in occupational exposure to dust or fume contain-

ing arsenic.

Complications such as burning of lips, painful swallowing, thirst, and severe

abdominal colic were observed due to acute poisoning of arsenic. Pathogenic mech-

anism of arsenic affects the epithelial cells of GI tract and leads to irritation.

Efciency of water solubility of arsenic was detected in the absorption of inorganic

arsenic through GI tract.

11.9.4 Cardiovascular Effects

Prolonged exposure of arsenic through drinking water leads to induce cardiovascu-

lar complication (Wang etal. 2007). Several epidemiological studies suggested that

mortality rate of cardiovascular diseases due to inhalation of arsenic trioxide

increases day by day. Antofagasta, Chile, witnessed a causality of 17 deaths under

40in 1980 due to myocardial infarction, and it was linked with arsenic- contaminated

water use. Food and water contaminated with arsenic are the only sources for con-

suming arsenic which affects cardiovascular system (main paper). Cardiovascular

disease is enlisted as the major leading cause of death throughout the world.

Epidemiological analysis shows that dose-response relationship is the way to induce

cardiovascular disease (Balakumar and Kaur 2009). Atherosclerosis and abnormali-

ties of electrocardiogram were enlisted as subclinical disorders and caused to pro-

long exposure of arsenic-contaminated drinking water (Wang etal. 2007). Damaging

of blood vessels or the heart is caused due prolonged exposure to inorganic arsenic

(paper reference). Children who are exposed to drinking water contaminated with

arsenic concentration of 0.6 mg/L were followed by myocardial infarction and

thickening of arterial walls. Voluntary consumption of arsenic causes acute poison-

ing, and the following complications were observed: hypercontracted bers in mus-

cles, myobrillar disruption, and mitochondrial abnormalities and vacuole formation

inside the cytoplasm. Myocardial depolarization and cardiac arrhythmias are caused

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

262

due to both acute and chronic exposure to arsenic which leads to failure of the heart.

Peripheral vascular disease (PVD), ischemic heart disease (IHD), and cerebrovas-

cular disease (CVD) are the clinical complications due to chronic exposure of arse-

nic. Diseases are discussed below.

11.9.4.1 Peripheral Vascular Disease

An ecological study was conducted in southwest Taiwan, and the aim of that study

was to show the relationship between mortality rate of PVD and arsenic exposure in

drinking water. The standard mortality rate shows that male (3.56) is greater than

that of female (2.3) (Tsai etal. 1999). Reduction in mortality rate was observed

when study population were exposed to drinking water that have a low level of arse-

nic (Yang 2006). The peripheral vascular system is affected by blackfoot disease

(BFD), and in the southwest coast of Taiwan, the disease adopts the shape of

endemic (Tseng etal. 2005). Progressive arterial occlusion is mostly observed in

lower extremities. Initial symptoms include numbness and coldness in the highly

affected areas of the body; also the absence of peripheral pulsation was detected.

These symptoms further progress into ulceration, gangrene, and spontaneous ampu-

tation of high affected areas of the body. In the mid-twentieth century, the level of

incidence increased and ranged from 6.5 to 18.9 out of 1000 individuals (Tseng 2008).

11.9.4.2 Ischemic Heart Disease

Deprived supply of oxygen to myocardium may lead to develop ischemic heart

disease. Ecological studies were conducted in several arsenic endemic villages of

Taiwan which show that mortality rate of IHD may increase with increasing level of

arsenic exposure. Relationship between level of arsenic exposure and mortality rate

is shown as that the rate of mortality is 3.5% when range of exposure is <0.1 mg/L

and the mortality rate is 6.6% when level of exposure is >0.6 mg/L (Chen etal.

1996). A cohort study was designed by Chen etal. (1996) in which a comparison of

cumulative mortality due to IHD was found out between two residents such as

affected and unaffected by this disease, but both were living in the same area. The

annual increase in arsenic exposure can increase the mortality rate due to IHD

(Thurston etal. 2016).

11.9.4.3 Cerebrovascular Disease

Areas of Taiwan have a high level of arsenic in drinking water in which the risk of

cerebrovascular disease is ranging from 1.2 to 2.7in 1000 exposed versus nonex-

posed individuals (Navas-Acien etal. 2006). An ecological study was conducted by

Tsai etal. (1999) in southwest Taiwan in which relative risk for cerebrovascular

M. Hamza et al.

263

disease was determined between male and female. The risk of CVD in male (1.14)

is relatively lower than that of female (1.24).

11.9.4.4 Atherosclerosis

Atherosclerosis is a pathogenic response of the tunica intima of the arterial vessel

walls to noxious stimuli. Atherosclerosis is characterized by the deposition of lipids

in the walls of vessel, due to which the wall of vessels becomes narrowing. The

above complication at the end leads to IHD.The prevalence of carotid atherosclero-

sis is increasing as the level exposure of arsenic in drinking water increases. It is

also a dose-response relationship. A cross-sectional study was conducted by Wang

etal. (2002) on a population of southwest Taiwan that lives in an arsenic endemic

area. Individuals were screened by using duplex ultrasonography, and results show

increase in prevalence of carotid atherosclerosis. After adjusting other risk factors

(smoking, alcohol consumption, serum cholesterol, and others), the risk of athero-

sclerosis was measured as 1.8 and 3.1.

11.9.4.5 Hypertension

Hypertension is associated with chronic exposure of arsenic (Chen etal. 2007). A

cross-sectional study was conducted by Chen etal. (1995) which shows that fre-

quency of hypertension was increased in two relative population such as 5% increase

in control population and 29% increase in the population that have highest cumula-

tive exposure to arsenic (18mg/L/year). Chen etal. (2007) performed an occupa-

tional study which shows that prevalence of arsenic is quiet low in the population,

which are not exposed to high level of arsenic. A cross-sectional study in China was

conducted by Kwok etal. (2007) in which 8790 pregnant women were exposed to

arsenic-contaminated drinking water, but the level was not equal to that drinking

water consumed by the localities of arsenic endemic areas of southwest Taiwan.

After controlling other relative factors (age, body weight, etc.), rise in systolic blood

pressure has note as 1.9mm mercury at arsenic level 12–50g/L, 3.9mm mercury at

arsenic level 51–100g/L, and 6.8mm mercury at arsenic level 51–100g/L.Variation

in systolic blood pressure is due to exposing body to different concentrations of

arsenic. So it has also effect on diastolic blood pressure but in little extent.

11.9.5 Endocrine

Type 2 diabetes (insulin independent) is a clinical complication that arose due to

chronic exposure of arsenic (Chen et al. 2007). Several epidemiological studies

were conducted and reported this disease in Taiwan and Bangladesh (Lai etal. 1994;

Tseng etal. 2000). The frequency of diabetes mellitus is twice higher in the villages

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

264

ingesting contaminated water with inorganic arsenic than that of consuming water

free of arsenic contamination (Lai etal. 1994). The relative risk of diabetes mellitus

was found with multivariate adjusted ratio between some risk factors like exposure

to arsenic, BMI, and physical activity. Results indicatedthat risk factor BMI and

Physical activity show 6.6 and 10 relative risk for diabetes while in case of arse-

nicexposure (more than 15mg/L/year) the relative risk for diabetes is0.1–15. A

cohort study was conducted on the occurrence of diabetes which shows that the

disease was associated with BMI, age, and continuous exposure to arsenic (Tseng

et al. 2000). The relative risk of diabetes due to cumulative arsenic exposure

(>17mg/L/year) was 2.1, when other factors such BMI and age were adjusted. In

2006, a systematic review of experimental and epidemiological data of Bangladesh

and Taiwan shows that the risk for the development of diabetes mellitus due to

cumulative exposure of arsenic is 2.5 (Navas-Acien etal. 2006).

11.9.6 Hepatic

The hepatic complication arises due to arsenic exposure that is known for over a

century. Use of arsenic in therapeutics may develop ascites in patients. Prolonged

use of Fowler’s solution (used as tonic containing 1% potassium arsenite) may lead

to complications such as noncirrhotic portal hypertension (Huet et al. 1975).

Arsenicosis was reported in the localities of West Bengal, India, because of con-

sumption of water contaminated with arsenic, and about 77% of patients may also

develop hepatomegaly (Mazumder 2005).

It was the rst chemical agent which caused liver disease in humans. Due to

multiple times of exposure for months or years, arsenic accumulation starts and

induces chronic complication. Initial symptoms are bleeding of esophageal varices,

ascites, jaundices, and at last hepatic lesions caused due to long time usage of medi-

cines containing arsenic (Sahaetal. 1999). Clinical symptoms indicated tender and

swollen liver.Blood tests show high level of hepatic enzymes. About 0.02–0.1mg/

kg/day is enough to generate chronic clinical complication. Arsenic disturbed mito-

chondrial functionality and also affects the metabolism of porphyrin. Studies sug-

gested that patients use Fowler’s solution face following clinical complications such

as cirrhosis and hepatic fatty inltration of the liver (Sahaetal. 1999). Final stage

clinical complications include noncirrhotic portal brosis and cirrhosis with liver

failure which results to jaundice, ascites, and coma (Sahaetal. 1999).

After liver function tests, serum enzyme elevation was observed in patients who

have hepatomegaly. The results of Mazumder’s (2005) epidemiological survey indi-

catedthatpopulationdeveloped hepatomegaly when consumedarsenic concentra-

tion of 50g/L or more. The incidence of hepatomegaly was higher in male than in

female, and also study shows dose-response relationship (Abdul etal. 2015).

M. Hamza et al.

265

11.9.7 Neurological

Neurological disorders such as impaired intellectual functions, peripheral neuritis,

and neuropathy are caused due to lifelong exposure to arsenic. Several nervous dis-

orders were observed in smelter workers, beer consumer in England, and children in

Bangladesh consuming arsenic-contaminated water (Wasserman et al. 2004).

Sensory and motor bers are counted in peripheral neuropathy, and illustrious char-

acteristics are axon dying back with segmental demyelination. In the nineteenth

century, a case of peripheral neuritis was observed due to consumption of beer con-

taminated with arsenic. Sulfuric acid was used to prepare sugar for the process of

brewing, and that acid was originated from arsenical pyrites. Initial complications

include needling in the nger and toes, painful walking, pain, and weakness in

highly exposed parts of the body. The intelligence ability of children of Bangladesh

was decreased due to consumption of drinking water contaminated with arsenic that

have concentration greater than 50g/L (Wasserman etal. 2004). As mentioned in

the cardiovascular section, arsenic can damage both peripheral and central parts of

the nervous system. Encephalopathy is due to exposure to arsenic at a concentration

of 1mg/kg/day. Other symptoms related to encephalopathy are headache, lethargy,

mental confusion or hallucination, seizures, and coma. Continuous and repeated

exposure to arsenic induces complications such as contract sensorimotor polyneu-

ropathy and a systematic disorder which resembles Landry-Guillain-Barre syn-

drome. Axonal degeneration was observed within 1–5weeks of acute exposure to

arsenic. The neurological disorders include persistent headache, short-term memory

loss, memory disorders, distractibility, irregular irritability, tired sleep, loss of libido

and increasedurgency of urine. A detecting technique known as electromyography

was used which shows variation in the velocity of nerve signal.

11.9.8 Skin

Skin lesions are the primary and harsh effects of the body associated with exposure

of arsenic. In the late eighteenth century appearance of lesions due exposure to

arsenic was observed by physicians (Yoshida etal. 2004). Appearances of lesions

were due to usage of inorganic arsenic for various ailments after that their effect was

observed in patients (Yoshida etal. 2004).

Hyperpigmentation is a most common skin-related complication caused due to

exposure to arsenic or arsenic-contaminated water. The appearance of pigmentation

is due to hyper melanin production in the melanocytes. Body parts such as areola or

groin have hyperpigmentation, and in some individuals the appearance of hypopig-

mentation (like raindrops) has also been observed on the face, neck, and back.

Hyperkeratotic papules, warts, or corns are formed on the palms and soles of people

who consumed arsenic-contaminated water. Other complications such as hyperker-

atotic papules are observed in patients’ palm and sole, who consume water

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

266

contaminated with inorganic arsenic. White horizontal lines in the nails, called

Mees’ lines, are also observed (Rossman etal. 2004).

11.9.9 Developmental Disorders

Inorganicarsenic can create developmental abnormalities in the fetus when trans-

mitted from mother (Vahter 2008). Administration of inorganic arsenic to female

rodents can transmit to offspring through placenta and generate serious complica-

tions in newborns, such as malformations, principally tube effects. Malformation

was not observed in the rodent and rabbits that were orally administered (Desesso

2001). Recent studies show that exposure of pregnant rats to nontoxic doses of arse-

nite through contaminated drinking water leads to certain clinical complication like

fetal brain developmental defects and behavioral changes (Chattopadhyay etal.

2002). Adverse effects such as spontaneous abortion, stillbirths, premature births,

low bodyweight, and high mortality rate were induced whenever pregnant women

were exposed to water contaminated with arsenic (Ahmad etal. 2001). In Bangladesh

a cross-sectional study was conducted to evaluate the effect of arsenic on pregnant

women. The results indicated adverse pregnancy effects at concentration level

>0.05mg/L for maximum ve year (Ahmad etal. 2001). Previous studies show the

relationship between arsenic and infant mortality.

Miscarriages were reported in several pregnant women working in semiconduc-

tor industries.

11.9.10 Hematological Disorders

Long- and short-term exposure of arsenic affects the hematopoietic system. Clinical

abnormalities including anemia and leukopenia are caused due to acute, intermedi-

ate, and chronic oral exposure to arsenic. These effects were induced by arsenic due

to direct cytotoxic or hemolytic effects on blood cells and also due to erythropoiesis

suppression. Other complications such as depression of bone marrow has also been

observed due to consumption of high dose of arsenic-contaminated drinking water.

Anemia and leucopenia were observed in the adults consuming arsenic- contaminated

soya sauce that has concentration of 3mg As/day. Death occurred within hours

when individual consumed arsine (10ppm).The red blood cells lysis occurred at

this concentration. If concentration is slightly lower such 0.5–5.0 ppm then the

above complications will approach in a few weeks and in working place the accept-

able concentration for arsine is 0.5ppm/L. Renal disorder was counted as a second-

ary complication in which the clogging occurs between nephrons and hemolytic

debris. Arsine shows more hemolytic activity than that of mono-, di-, and tri-methyl

arsines. In the absence of proper therapy, exposure of body to arsine becomes fatal

M. Hamza et al.

267

because inside the body arsine is converted into inorganic and methylated deriva-

tives of arsenic.

The invivo study on mice and rats revealed the actual mechanism behind the

hemolysis that whenever blood is exposed to arsenic it reduced the level of intracel-

lular GHS.It results in sulfhydryl groupoxidation of hemoglobin and conversion of

ferrous into ferric. The capability of cells to uptake oxygen was reduced when

hemocyanin is combined with arsenic (Sahaetal. 1999).

11.10 Genotoxicity Effects

Smelter workers may inhale arsenite, which may lead to increase in the prevalence

of chromosomal aberrations in the peripheral lymphocytes. During the gestation of

female mouse, the same effects were also observed on its liver that was exposed to

high concentration 22mg As/m. These studies determined the clustogenic effects of

arsenic. Arsenic cannot cause point mutation in the cellular system. A study shows

that arsenic induces inhibition of DNA repair system after incision step in the cells

of Chinese hamster V79.

11.10.1 Mutagenic Effects

Mutagenesis is known as damage to chemical and structural properties of DNA and

alteration of genetic material that may be categorized into form base pair mutation

to whole chromosomal deletions or clastogenesis. Some genetic changes may be

transmitted to the next generations and become a hereditary disorder. Some of these

induce cancer. Direct genetic mutation was not observed due to arsenic. Basic

mechanism for comutagenicity and co-carcinogenicity of arsenic was caused due

inhibition of DNA repair system. Comparative analysis between pentavalent and

trivalent was done which is needed to evaluate the prevalence of chromosomal aber-

ration and also to check more potential and genotoxic species of arsenic. Resultant

of this comparative analysis shows that trivalent is more potential toxic than pen-

tavalent. Dismutase and catalase are the enzymes that hunt free radical oxygen

which may directly help to protect DNA damage induced due to arsenic.

11.10.2 Biochemical Effects

In both animals and humans, outsized important enzymes were inhibited by arsenic

compounds. The activity of glucose transport is blocked by phenylarsine oxide

(PAO), which can affect the uptake of glucose by inhibition of insulin activation and

also inhibit the signal transmission by blocking vicinal thiol which is present ion

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

268

3T3-L1 adipocytes. The mechanism was observed inside muscles of rats. Rapid

accumulations of arsenite in the liver of body cause inhibition of NAD-linked oxi-

dation of pyruvate or a-ketoglutarate.

11.10.3 Renal Effects

The kidney is the main organ that detoxies the blood and removes toxic material.

Renal complications were generated due to repeated exposure to arsenic. Kidneys

are the main and only organ of the human body that covert arsenate from low to high

toxic and less soluble form of arsenite. Capillaries and glomeruli tubules were

mainly affected due to arsenic exposure. A severe condition proteinuria and casts

are induced when proximal tubular cells were damaged. In case of severe acute

arsenic exposure, the risk to renal failure increases. Destruction of mitochondria

was observed in tubular cells. Dialysis is the only effective way to overcome these

effects. Arsenic-induced hemolysis occurred which leads to a sever complication

known as tubular necrosis and at the end complete renal failure. Hemodialysis is

used to remove hemoglobin-bound arsenic.

11.10.4 Other Human Health Effects

Visual perception of children is affected when they consume drinking water having

high concentration of arsenic, and it will not affect visual motor integration. It was

conrmed by two diagnostic methods: visual motor integration test (VMIT) and

motor visual perception test (MVPT) (Siripitayakunkit etal. 2000). In Bangladesh,

a study reported that children exposed to high level of arsenic in drinking water will

have a reduced intellectual function. A comparative study shows the dose-response

in two groups of children: Children who consumed water containing high concen-

tration of arsenic (>50 g/l) had low intellectual function than thosewho consumed

water with less amount of arsenic (>5.5 g/l) (Wasserman etal. 2004). Growth retar-

dation in children is also associated with arsenic. Children’s height isreducedwhen

drinking water is polluted with arsenic. Results of a comparative study between two

groups show that children having high concentration of arsenic in hair have height

less than those children having less concentration of arsenic in their hair

(Siripitayakunkit etal. 2000). Birth defects such as spontaneous abortion, stillbirth,

and infant mortality are also associated with drinking water contaminated with

arsenic.

Consuming high concentration of inorganic arsenic-contaminated water can

affect the respiratory system and cause bronchiectasis (Mazumder 2005).

Bronchiectasis is a clinical complication which is characterized as dilation of bron-

chi and bronchioles due to obstruction. Other complications such as hematological,

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269

reproductive, and immunological disorders were also reported (ATSDR 2007;

WHO 2001).

11.10.5 Carcinogenic Effect

Different public health and regulatory organizations all around the world catego-

rized inorganic arsenic as carcinogen to humans. Epidemiological data act as a base

for such classication. Generalized and occupational studies conducted in Taiwan

show that localities of Taiwan were exposed to high concentrations of arsenic.

Recent studies which were conducted in particular countries such as Bangladesh,

Mexico, and Chile show that the most common source of arsenic to which humans

were exposed is drinking water, which is naturally contaminated with high concen-

tration of arsenic. Skin, lung, and bladder are the most sophisticated organs of

human which tend to induce tumor after exposure to high concentration of arsenic.

Liver, kidney, and prostrate are enlisted as related organs which were also affected

(Agency for Toxic Substances and Disease Registry (ATSDR) 2007; World Health

Organization (WHO) 2001. Studies show that arsenic induces leukemia and lung

cancer in model or experimental animals. Humans exposed to water or wine/beer

naturally or intentionally contaminated with high concentrations of arsenic can

induce skin complications such as precancerous dermal keratosis, epidermoid car-

cinoma, and lung cancer. Diseases like blackfoot disease, Bowen’s disease, and skin

cancer show correlation with arsenic-contaminated drinking water, and they were

reported in countries such as Argentina, Chile, and Canada.

Cancer of the Skin

Bowen’s disease and squamous and basal cell carcinoma are the most common

arsenic exposure-associated skin cancers (Maloney 1996). An exposure of 6–20

years with a mean latent period of 14 years causes these ailments. The most com-

mon form of skin carcinoma induced by arsenic is known as Bowen’s disease or

carcinoma in situ (Maloney 1996). Appearance of lesions is solitary, randomly dis-

tributed, and has multifocal opening. Lesions are mostly from 1mm to 10cm in size

and have sharp demarcated round or irregular plaque-like appearance (Shannon and

Strayer 1989). Arsenical keratosis may lead to developing squamous cell carcino-

mas. These cells show more aggression than hyperkeratotic cells. The development

of squamous cell carcinoma is mostly observed on extremities or highly exposed

areas (Shannon and Strayer 1989). Basal cell carcinoma is induced due to arsenic

exposure. Skin cancer is more prevalent in males than females. Prevalence of skin

cancer is directly proportional to age. Studies also reported the dose-response rela-

tionship in skin cancer patients. Duration of exposure to contaminated drinking

water, cumulative exposure to arsenic, average exposure of arsenic, and period of

localities living in the endemic areas are main factors that contribute to increase in

the prevalence of skin cancer.

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

270

Cancer of the Lung

Several studies claimed that inhalation of inorganic arsenic increases the chance of

lung cancer (Agency for Toxic Substances and Disease Registry (ATSDR) 2007;

World Health Organization (WHO) 2001). Occupational exposures to arsenite are

mostly reported in most studies. Process of ore smelting contaminated air with arse-

nic trioxide. Some other studies reported that lung cancer is developed in workers

who work with arsenic-containing pesticides.

Not a specic type of cellular carcinoma is induced in the worker exposed to

arsenic. Several kinds of cellular carcinomas were observed due to arsenic inhala-

tion such as epidermoid carcinoma, small carcinomas, and adenocarcinoma workers

(Agency for Toxic Substances and Disease Registry (ATSDR) 2007; Arain

etal. 2009).

Individuals working on smelting of nonferrous metals, pesticides sprayproduc-

tion, and gold miningworkers inhale inorganic arsenicthat induce cancer of respira-

tory systems.

Body Enzymatic System

Compounds of arsenite are mainly absorbed through the elementary canal of the

human body, and these compounds start their deposition in various cells of the body.

The deposition of arsenic in body cells disturbs the body's enzymatic system, after

which cell death occurs.

11.11 Mechanism ofArsenate Toxicity

Step 1

The rst step starts with the breakdown of pyruvic acid (obtained from glucose

inside the mitochondria of cell) through a specialized type of enzyme. A complex of

pyruvate oxidase is needed for oxidation decarbonylation of pyruvate, which pro-

duced acetyl coenzyme A and carbon dioxide before entering to TCA cycle (tricar-

boxylic acid cycle). Several enzymes and cofactor collectively create an enzyme

system. Single protein molecules of an enzyme contain one lipoic acid, and there

are two sulfhydryl or thiol groups present in one lipoic acid. They are essential to

maintain proper workability of cell. If the body cell is exposed to arsenite (trivalent

arsenic), then attached to it are two hydrogen of thiol group with sulfur molecule

that create dihydrolipoyl-arsenite chelate complex. This complex prevents reoxida-

tion of dihydrolipoyl group, which is necessary for the continuation of enzymatic

activities. So, enzymatic activity stops. As a result of this enzymatic inactivation,

the level of pyruvate increases in the blood, while in contrast cellular energy

becomes lower, which leads to death of cell. Arsenic can also affect workability of

another enzyme name as succinyl coenzyme A, which may reduce the level of cel-

lular energy (ATP) (Saha etal. 1999).

M. Hamza et al.

271

Step 2

The inorganic form of arsenate is available in the environment. It blocks the mito-

chondrial enzymatic activity of eukaryotic cells but in different manner. In the pro-

cess of oxidative phosphorylation, phosphate-decient ADP gets inorganic

phosphate and becomes ATP. This inorganic phosphate is replaced by arsenate.

Arsenate is attached with ADP and forms an unstable arsenate ester bond that rap-

idly hydrolysates. As a result, the level of ATP inside the cell is continuously

reduced, and it also disturbs the transfer of electron between inorganic phosphorus

and ATP.In the presence of arsenate, the high energy bond of ATP cannot be con-

served, and the process is called arsenolysis. Two different ways that were adopted

by arsenic to affect the functionality of mitochondria:

• Trivalent arsenic seize the reduction of nicotinamide adenine dinucleotide by

deactivating enzymes in Krebs cycle.

• Pentavalent arsenic breaks the chain of oxidative phosphorylation by a process of

arsenolysis.

Compounds of arsenate also disturbed the reaction of succinate and succinic acid

during the generation of ATP (Saha etal. 1999).

11.11.1 Mechanism ofTrivalent Arsenic Toxicity

The activity of trivalent arsenic is mostly related with enzymes loaded with special-

ized functional groups like thiols or vicinal sulfhydryls. In vitro study shows that

trivalent arsenic reacted with thiol which contains GSH and cysteine (Scott etal.

1993; Delnomdedieu etal. 1993). The afnity of trivalent arsenic is higher toward

dithiols than monothiols, and arsenite may transfer from (GSH)3- arsenic complex

and combine with dithiol 2,3 dimercaptosuccinic acid. Toxicity caused by arsenite

is induced when it builds complex with thiol groups and leads to blocking important

biochemical processes.

A multiple subunit complex such as pyruvate dehydrogenase (PDH) requires

cofactor lipoic acid (dithiol) to perform enzymatic reaction appropriately. Now

arsenite binds with moiety of lipoic acid and inhibits the functionality of pyruvate

dehydrogenase (PDH) (Hu etal. 1998). Pyruvate dehydrogenase has a key role in

the generation of ATP because it converts pyruvate into acetyl CoA, which acts as a

precursor molecule in the citric acid cycle and also as an electron transporter. Due

to inactivation of PDH, reduction is observed in the production of ATP.Methylated

trivalent arsenicals are highly active than arsenite MMAV and DMAV (source refer-

ence). Arsenite bind to sulfhydryl group and reduce the metabolic activities such as

glucose uptake, gluconeogenesis, fatty acid oxidation, and glutathione production.

These activities were induced by inhibiting relevant enzymes of each metabolic

process, after that the cellular redox status is reduced and generates cell

cytotoxicity.

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

272

Metabolism

The valence state of arsenic determines its metabolic pattern in mammals. As (III)

and As (V) are the two most common inorganic arsenic valence forms responsible

for human exposure. These two forms are readily interconvertible. Arsenic is meth-

ylated in the body by alternating reduction of pentavalent arsenic to trivalent and

addition of a methyl group from S-adenosylmethionine (toxic and widely distrib-

uted in the environment. Most microorganisms have evolved mechanisms to use

methylarsenicals as weapons in microbial warfare (Zhang etal. 2015; Chen and

Rosen 2020).

11.12 Arsenic Removal Technologies

1. Adsorption

2. Electrocoagulation

3. Ion exchange

4. Membrane technologies

5. Phytoremediation

11.12.1 Adsorption

Adsorption is the accumulation of adsorbate (liquid) on the surface of adsorbent

(solid), and there is the formation of a lm. Adsorption is of two types, that is, phy-

sisorption (physical) and chemisorption (chemical). Physisorption is the adsorption

in which van der Waals forces are involved. Chemisorption creates a strong chemi-

cal bond (ionic or covalent) between adsorbent and adsorbate. Physical adsorption

is weak and reversible, while chemisorption is strong and irreversible; the heat

range (kJ/mol) for physisorption is low, and chemisorption is high (Singh and Gupta

2016). Adsorption is an effective and low-cost technique for heavy metal removal

for wastewater. The adsorption technique is simple and exible, capable of high-

quality treatment. Adsorption is reversible which can regenerate adsorbents as well

(Fu and Wang 2011). There are some important factors which inuence the heavy

metals adsorption process, for example, adsorbent dosage, initial concentration of

heavy metals, temperature, pH, mixing speed, and contact time. Adsorption gener-

ally increases with the increase in the above factors (Agarwal and Singh 2017; Sahu

etal. 2009).

Some recent studies on adsorption of arsenic from water are shown in Table11.1.

Uppal etal. (2019) synthesized zinc oxysulde (ZnOxS1−x) for arsenic removal by

using facile chemical method. The adsorbent was highly effective in arsenic removal

with maximum removal efciency of up to 99.9%. The maximum removal capacity

of arsenic was 299.4mg/g. ZnOxS1−x was found to be highly stable and was reused

successfully up to ve cycles (Uppal etal. 2019). The zirconium metal- organic

M. Hamza et al.

273

frameworks (UiO-66 and UiO-66(NH2)) were used for the removal of arsenic (III

and V) from polluted water. The framework effectively removed both Ar III and V

from wastewater. The maximum removal capacity for As III and V was 205.0 and

68.21mg/g, respectively. This framework is highly stable and low cost and had high

adsorption capacity for arsenic (He et al. 2019). Coprecipitation-hydrothermal

method was used by Yin etal. (2019) for the synthesis of activated charcoal-coated

zirconium-manganese nanocomposite. The novel nanocomposite effectively

removed arsenic III and V from synthetic wastewater. The maximum adsorption

capacity of arsenic III and V was 132.28 and 95.60mg/g, respectively. The Zr/Mn/C

nanocomposite emerged as a green, low-cost adsorbent capable of effectively

removing arsenic from wastewater (Yin et al. 2019). Kang etal. (2019) removed

arsenic from synthetic wastewater using adsorbent powder trapped in alginate

beads. These beads were further calcined. The surface area of adsorbent was

enhanced by 100 times after calcination. The calcined beads proved to be effective

in arsenic removal within a short period of time (Kang etal. 2019). A composite of

alum sludge and melamine was co-pyrolyzed and used for arsenic removal. The

composite effectively oxidizes arsenic III to arsenic V.This green composite effec-

tively oxidized arsenic and also adsorbs arsenic from wastewater in the presence of

light. The mechanism behind adsorption was chemisorption (Kim etal. 2020).

11.12.2 Electrocoagulation

Electrocoagulation (EC) is a highly effective and simple process used for the treat-

ment of different types of wastewaters. EC effectively removed pollutants from

industries such as poultry slaughterhouse (Kobya et al. 2006), electroplating

(Adhoum et al. 2004), restaurant (Chen et al. 2000), and laundry wastewater

(Janpoor etal. 2011). EC when combined with other treatment technologies can

effectively remove pollutants from wastewater. EC is 100 times a more effective

adsorbent than the conventional coagulation technique (Mollah etal. 2004). The

ocs formed during EC are highly stable and can be easily removed by ltration. EC

is a low-cost and highly efcient process. It requires simple equipment and can be

used for treatment of wastewater at the industrial scale. This process does not

require any chemicals; therefore there are no secondary pollutants that are produced

during EC process. EC process can operate at low current, so its sustainability can

be achieved by combining it with renewable energy sources, for example, solar,

wind, and biofuels (Zaroual etal. 2006). The process does not require additional

reagent and chemicals which make this process environment friendly. The absence

of chemicals in EC process also reduces the quantity of sludge produced.

Table 11.1 shows a few recent studies on electrocoagulation of arsenic from dif-

ferent water systems. López-Guzmán etal. (2019) simultaneously removed arsenic

and uoride from well water using electrocoagulation process. Iron and aluminum

electrodes were used during electrocoagulation. The process was highly effective

for the removal of both arsenic and uoride. The maximum arsenic and uoride

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

274

Table 11.1 Technologies used for arsenic removal

Technology Type Mechanism

Removal

efciency

Adsorption

capacity Medium References

Adsorption Zinc oxysulde (ZnOxS1−x) Electrostatic interaction 99.9% 299.4 mg/g Aqueous Uppal etal.

(2019)

Zirconium metal- organic

frameworks (UiO-66 and

UiO-66(NH2))

Chemisorption – 205.0 mg/g Wastewater He etal. (2019)

Activated charcoal-coated

zirconium-manganese

nanocomposite

Chemisorption and

physisorption

– 132.28 mg/g Synthetic

wastewater

Yin etal. (2019)

Calcination of sodium alginate

and polyvinyl alcohol

Chemisorption – – Synthetic

wastewater

Kang etal.

(2019))

One-step fabrication of alum

sludge and graphitic carbon nitride

(g-C3N4)

Outer sphere

complexation and

physisorption

– – Synthetic

wastewater

Kim etal. (2020)

Electrocoagulation Iron and aluminum Oxidation 100% – Well water López-Guzmán

etal. (2019)

Iron electrodes Oxidation – – Drinking water Banerji and

Chaudhari

(2016)

Aluminum electrodes – ≥90% – Drinking water Silva etal.

(2018)

Iron (Fe) plate bipolar electrodes Oxidation 96% – Raw

groundwater

Mohora etal.

(2018)

Fe(0)-based Electrochemical

technology

Reactive Fe(III)

precipitates to bind As

≥90% – Groundwater Roy etal. (2020)

M. Hamza et al.

275

Technology Type Mechanism

Removal

efciency

Adsorption

capacity Medium References

Ion exchange Novel chelating ion exchange

resins

63.5% – Saline

geothermal water

Çermikli etal.

(2020)

Amine-doped acrylic ion-exchange

ber

Pseudo-rst-order

kinetics

83% 205.3±3.6mg/g Synthetic water Lee etal. (2017)

Ion exchange/electrodialysis

(IXED) process

As(V) ions in the solution

are exchanged by OH_

– – Synthetic water Ortega etal.

(2017)

Fe3O4/halloysite nanocomposite chemical process 99.62% 427.72 mg/g Synthetic water Song etal.

(2019)

La(III)-montmorillonite hydrogel

beads

Hydrogen-bond and

electrostatic interactions

– 58.75 mg/g Synthetic water Yan etal. (2020)

Membrane

ltration

Novel adsorptive nanocomposite

membrane

Chemisorption and

Physisorption

– 41.09 mg/g Water system Nasir etal.

(2019)

High-ux ultraltration membrane – – – Contaminated

water

Bahmani etal.

(2017)

Composite membranes Bayerite arsenic

adsorption

60% – Synthetic water Salazar etal.

(2016)

Ultraltration hollow ber

membranes

– 41% – Synthetic water Kumar etal.

(2019)

Hydrophobic kaolin hollow ber

membrane

– 100% – Synthetic water Hubadillah etal.

(2019)

(continued)

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

276

Table 11.1 (continued)

Technology Type Mechanism

Removal

efciency

Adsorption

capacity Medium References

Phytoremediation Pteris vittata Absorption ≥95% – Groundwater Yang etal.

(2017)

Lemna valdiviana Absorption 82% 1190 mg/kg Synthetic water de Souza etal.

(2019)

Vallisneria natans Oxidation, methylation,

absorption

73.24% – Synthetic water Li etal. (2018)

Echinodorus cordifolius,

Arthrobacter creatinolyticus

– 96±3% – Synthetic water Prum etal.

(2018)

M. Hamza et al.

277

removal was 100% and 85.68%, respectively. Electrocoagulation using iron elec-

trodes (ECFe) was used for the removal of arsenic from drinking water. Iron elec-

trodes caused the oxidation of arsenic which resulted in high arsenic removal. The

presence of phosphate in drinking water had negative impact on arsenic oxidation

and adsorption. The maximum removal of arsenic was achieved at low current and

pH7 (Banerji and Chaudhari 2016). Silva etal. (2018) removed arsenic, uoride,

and iron from drinking water using the electrocoagulation process. There was posi-

tive effect on arsenic removal in the presence of iron. However, uoride had a slight

negative effect on arsenic removal. The arsenic removal was above 90% in the pres-

ence of iron. All three pollutants were completely removed within 1h (Silva etal.

2018). Horizontal continuous ow EC reactor was used for arsenic removal from

raw groundwater. The reactor used bipolar iron electrodes. The optimum current

density, ow rate, and charge loading for the EC reactor were 1.98A/m2, 12L/h,

and 54C/L, respectively. The maximum arsenic removal was 96% (Mohora etal.

2018). Roy etal. (2020) recently developed integrated system consisting of arsenic

oxidizing bacteria and iron electrocoagulation (bio-FeEC). The bio-FeEC effec-

tively reduced arsenic from 150 to 10μg/L.This integrated system produces less

sludge and also consumes less energy than the conventional FeEC. The bio-FeEC

emerged as a promising technology for arsenic removal (Roy etal. 2020).

11.12.3 Ion exchange

Ion-exchange technology is proved to be effective in treating water polluted with

heavy metals. The major advantages of ion-exchange technology include high

removal efciency, fast kinetic rate, and high treatment capacity (Kang etal. 2004).

Ion- exchange resin is capable of replacing the cations with the targeted heavy met-

als in the wastewater. Ion-exchange resins are either natural or synthetic. Most com-

monly synthetic resins are used due to their high efciency and wide range (Alyüz

and Veli 2009). The cationic exchange resins mostly used for heavy metals removal

are either strongly acidic resins containing sulfonic acid groups or weak acid resins

having carboxylic acid groups. These strongly acidic and weak acid resins have

hydrogen ions which are exchanged with the metal ions. When the metal ion solu-

tion is passed through the ion-exchange column, the hydrogen ions on the resin are

exchanged with the metal ions.

Recent ion-exchange technologies used for arsenic removal from water are sum-

marized in Table11.1. Çermikli et al. (2020) used novel chelating ion-exchange

resins for the removal of arsenic and boron from geothermal wastewater. They used

a hybrid method (adsorption-membrane ltration) for this treatment. The hybrid

process was effective in boron removal; however arsenic removal was also good.

The maximum arsenic and boron removal were 63.5% and 86%, respectively

(Çermikli etal. 2020). The ion-exchange acrylic ber was doped in amine for the

removal of arsenic (V) from water. The novel ber was efcient in arsenic removal.

The maximum adsorption capacity for arsenic was 205.3±3.6mg/g. The maximum

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

278

removal efciency of arsenic was 83%. The ber can be used as a low-cost and reus-

able ion-exchange medium (Lee etal. 2017). A hybrid anion exchange electrodialy-

sis process was used for treating arsenic-polluted water. The OH- ions generated in

the electrodialysis process were replaced with arsenic ions. The hybrid process ef-

ciently removed arsenic at different concentrations ranging from 2.1 to 15mg L−1

(Ortega etal. 2017). A novel cactus-like Fe3O4/HNTs magnetic nanocomposite was

developed by Song etal. (2019) for the removal of arsenic (III and V) from waste-

water. The maximum removal efciency of cactus-like nanocomposite from arsenic

III and V was 98.56% and 99.62%, respectively. The maximum adsorption capacity

for arsenic III and V was 408.71mg/g and 427.72mg/g, respectively. The nanocom-

posite was highly reproducible (Song etal. 2019). In a recent study Yan etal. (2020)

removed arsenic from water using montmorillonite hydrogel beads containing lan-

thanum. The addition of lanthanum increased the surface area of hydrogel beads.

The major mechanism behind arsenic adsorption was ion exchange, complex chela-

tion, and electrostatic forces. The maximum adsorption capacity of hydrogel beads

was 58.75mg/g (Yan etal. 2020).

11.12.4 Membrane Technology

Different types of porous and thin-lm composite membranes are used for wastewa-

ter treatment. These membranes include those requiring low pressure, for example,

microltration, ultraltration, and distillation. Membranes requiring high pressure,

for example, nanoltration and reverse osmosis. Membrane derived by osmotic

pressure includes liquid membranes, forward osmosis, and electrodialysis. The

major factors effecting the efciency of different types of membranes in wastewater

treatment and heavy metal removal include pore size and their distribution, ow

rate, hydrophilicity, surface charge, and functional group presence (Abdullah

etal. 2019).

Recent membrane technologies for arsenic removal are given in Table 11.1. A

novel adsorptive nanocomposite membrane was used for arsenic removal from the

water system. The novel membrane was highly effective in arsenic removal from

water. The removal of arsenic was by both chemisorption and physisorption. The

maximum adsorption capacity of the nanocomposite membrane for arsenic was

41.90mg/g (Nasir etal. 2019). High-ux ultraltration membrane was used for the

removal of arsenic from aqueous solution. The membrane shows high ux

(172–520%) than the conventional ultraltration membrane. The efciency of this

membrane in rejecting arsenic was also higher (1.1–1.3 times) than the conventional

ultraltration membrane (Bahmani etal. 2017). Salazar etal. (2016) prepared com-

posite membrane by using solvent casting for arsenic removal from aqueous solu-

tion. The composite membrane was highly stable. The addition of bayerite particles

into the composite membrane improved arsenic adsorption. The maximum arsenic

rejection was 60% achieved within one hour (Salazar etal. 2016). Dry-wet phase

inversion technique was used for the synthesis of cellulose acetate/polyphenylsul-

fone ultraltration membrane. The fabricated membrane was used for arsenic

M. Hamza et al.

279

removal. The polyphenylsulfone ultraltration membrane was more effective in

arsenic removal as compared to conventional hollow ber membrane. The maxi-

mum removal percentage for arsenic was 41% (Kumar etal. 2019). Phase inversion/

sintering technique was used for the preparation of low-cost hydrophobic kaolin

hollow ber membrane. The low-cost membrane was used for arsenic removal from

synthetic wastewater. Fluoralkylsilane agent was used for the surface modication

of modied membrane. The modied membrane showed excellent arsenic removal

as the arsenic removal was 100% (Hubadillah etal. 2019).

11.12.5 Phytoremediation

Phytoremediation is the absorption of pollutants from water and soil by the roots of

green plants (Sharma etal. 2015). Phytoremediation can be used for the removal of

both organic and inorganic pollutants from water, soil, sediments, and sludge

(Bauddh etal. 2015; Bhatia and Goyal 2014). Several plant species were success-

fully used for the removal of pollutants from water and soil (Sharma etal. 2015).

The plant species used for phytoremediation should be native, have high growth

rate, and should be adaptable to different environments, strong root system, and

high pollutant accumulation (Valipour and Ahn 2016). The important factors which

affect plant growth and phytoremediation are temperature, light, pH, and salinity.

The availability of nutrients also affects plant growth and phytoremediation (Gupta

etal. 2012).

Table I summarizes a few recent arsenic phytoremediation studies.

Phytoremediation of arsenic from groundwater was done by using Pteris vittata.

The effect of phosphate mineral on arsenic remediation was also studied. The pres-

ence of phosphate enhanced the arsenic removal potential of P. vittata. Pteris vittata

has been able to reduce the concentration of arsenic from 200 μg L−1 to <10 μg L−1.

The maximum absorption of arsenic was ≥ 95% (Yang etal. 2017). de Souza etal.

2019 used Lemna valdiviana for arsenic phytoremediation from synthetic wastewa-

ter. The effect of pH, phosphorus, and nitrogen on the performance of L. valdiviana

was also studied. Optimum conditions for arsenic adsorption were pH 6.3–7.0,

phosphorus 0.0488mmolL−1 (P-PO4), and nitrogen 7.9 mmol L−1 (N-NO3). The

maximum arsenic accumulation was 1190mgkg−1. The maximum absorption of

arsenic was 82%. L. valdiviana was proved to be a promising macrophyte for arse-

nic phytoremediation (de Souza etal. 2019). Vallisneria natans was used for arsenic

removal from water. V. natans rst oxidized arsenic III to arsenic V and then meth-

ylated to dimethylarsinate (DMA). Maximum arsenic accumulation was in roots

((≥95.65 ± 0.10%). The maximum arsenic removal by V. natans was 73.24%.

V. natans showed great potential for phytoremediation of arsenic from contaminated

water (Li et al. 2018). In a study, Prum et al. (2018) used a combination of

Echinodorus cordifolius with Bacillus subtilis and Arthrobacter creatinolyticus for

arsenic removal from water. The combination of E. cordifolius and A. creatinolyti-

cus resulted in enhanced arsenic removal. The maximum arsenic removal was

96±3% (Prum etal. 2018).

11 Health Risks Associated with Arsenic Contamination and Its Biotransformation…

280

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Chapter 12

Mycotoxins inEnvironment andIts Health

Implications

SadiaAlam, SobiaNisa, andSajeelaDaud

Abstract Mycotoxins are secondary metabolites produced by toxigenic molds

under suitable conditions such as high temperature, moisture, etc. Stored foods are

more susceptible to fungal growth and subsequent mycotoxins contamination.

Mycotoxins are mutagenic, carcinogenic, immune-suppressive, and make the host

susceptible to infectious diseases. Several methods can be used for mycotoxin

detection, but enzyme-linked immunosorbent assay (ELISA) is proved to be the

cost-effective method. Management strategies are very important in reducing the

mycotoxicosis risk. This threat can be reduced by mitigation measures such as

chemical methods, antagonistic activities, biodegradation, irradiation, heat, etc.

Aatoxin is one of the most hazardous and widespread mycotoxins contaminating

foodstuffs. It is produced by different strains of Aspergillus species in a variety of

products, such as cereals, pulses, coffee, wine, grape juice, and dried fruits.

Mycotoxins monitoring in food and feed stuff fruits has become an important issue

worldwide because of both the impact on human health and the high economic

losses that is associated with crop production. Mold growth of A. avus and A. para-

siticus is stimulated to produce aatoxins in conditions of high temperature, high

humidity level, pest invasion, drought, high water activity, and adverse weather con-

ditions in eld as well as in storage godowns. Food commodities susceptible to

mycotoxins contamination include wheat, rice, barley, maize, milk, peanuts,

almonds, gs, pistachios, dried apricots, mulberries, dates, walnuts, spices, meat,

etc. These toxins may persist in cereals even after mold destruction. However, the

amount of toxin is reduced by several processes up to 20% including thermal food

processing. Exposure to these chemicals causes wide variety of human disorders

such as birth defects, reproductive disorders, mental problems, kidney and liver

S. Alam (*) · S. Nisa

Department of Microbiology, The University of Haripur, Haripur, Pakistan

e-mail: sadia.alam1@uoh.edu.pk; sobia@uoh.edu.pk

S. Daud

Department of Biological Sciences, COMSATS University of Science and Technology,

Islamabad, Pakistan

290

dysfunction, and immune system suppression. Diet is one of the main routes of

exposure to these toxic chemicals. Mycotoxin contaminates the food commodities

which is the major public health threat. These toxins are usually transferred during

the processing of contaminated ingredients or seeds. So they bind to the plasma

proteins of human body and persist there.

12.1 Introduction

12.1.1 Turkey X Disease andDiscovery ofMycotoxins

The term mycotoxicology refers to the toxic effects caused by fungal mycotoxins.

Modern mycotoxicology started with the discovery of aatoxins in the early 1960s

when the peanut-based feed caused the Turkey X disease and more than 10,000

turkeys and chickens were found dead in England (Blount 1961). It was then named

as Turkey X disease and is considered as a turning point for the use of the term

mycotoxins. Early investigations on Turkey X disease revealed neurological symp-

toms followed by coma and nally death in chickens intoxicated by eating

mycotoxin- contaminated meals (Wannop 1961). The original description of Turkey

“X” disease by Blount (1961) was that the turkeys in England dying of intoxication

exhibited both clinical and gross pathologic signs. Catarrhal and hemorrhagic enter-

itis was a major sign along with the characteristic position assumed by poults dying,

as described by Blount (1961), that the neck of poult would be tilted and the head

own back (opisthotonus) and legs would be sprawled completely toward the back

(Richards 2008).

As studies were carried out to identify the etiology of Turkey “X” disease in

England, no signicant organisms were isolated from Brazilian groundnut meal;

instead, microscopic examination revealed the presence of some fungal elements.

However, a similar outbreak like Turkey “X” disease was reported from Kenya

shortly thereafter by eating Ugandan groundnut meal. Investigations on Ugandan

groundnut resulted in isolation of Aspergillus species that later on identied as

Aspergillus avus. The causative agent of Turkey X disease was then determined as

aatoxin. There is an array of highly cogent carcinogens being produced by the

most abundant fungi like A. avus and Aspergillus parasiticus. Further studies

revealed isolation and identication of major aatoxins, B1, B2, G1, and G2, using

thin-layer chromatography (Armbrecht etal. 1963).

Afterward, many new fungal contagions were identied and characterized.

Mycotoxins are secondary metabolites of fungi. Many genera of fungi have the

potential to produce mycotoxins like Aspergillus, Penicillium, and Fusarium spp.

Mycotoxins contaminate about 25% of agricultural commodities globally.

Mycotoxin contamination is a worldwide issue occurring in both tropical and tem-

perate regions of the world. Mycotoxigenic fungi colonize cereals in the eld and

after harvest; thus, they harbor a mixture of many toxins. Crops when kept for

S. Alam etal.

291

storage are also prone to fungal attack and may be polluted with mycotoxins during

storage. Major food crops being infected by fungi and then intoxicated by mycotox-

ins include cocoa, coffee, cereals, oil seeds, spices, nuts, dried fruit, dried peas,

beans, and fruits. The production of mycotoxins also depends on environmental

factors during plant growth and then on the storage conditions of food (Fiers etal.

2013; Ameye etal. 2015). Mycotoxins can exhibit acute and chronic toxicity, muta-

genic, and teratogenic effects. Humans may encounter severe health hazards or high

mortality rates in countries with poor management programs. Toxic effects of

mycotoxins depends on the nature of mycotoxins and their mode of action ranging

from deterioration of the liver or kidney function and interference with protein syn-

thesis leading to extreme immunodeciency. Some mycotoxins are neurotoxic, and

higher doses can lead to brain damage and death.

12.2 Origin andChemical Nature ofMycotoxins

Mycotoxins are fungal metabolic compounds produced secondarily, capable of

causing disease and death in humans and other animals. During ancient times, many

major epidemics have been observed in humans and animals due to mycotoxin

intoxication. Alimentary toxic aleukia (ATA) and ergotism are examples of dreadful

mycotoxicosis instances that resulted in the death of thousands of people in Europe

and Russia.

Mycotoxicosis is the term used to describe the toxic effects caused by mycotox-

ins. The toxic effects of mycotoxins depend on the duration of the exposure, health,

age, and sex of the exposed individual. On the other hand, many factors like alcohol

abuse, vitamin deciency, and dietary status can also effect the severity of myco-

toxin poisoning. Mycotoxins are manufactured from some general metabolic com-

pounds and through a channel of various pathways (Bennett and Bentley 1989). The

chemical nature of mycotoxins varies from alkaloids, sesquiterpenes, polyketides,

derivatives of phenylalanine, and macrocyclic acid lactones (Ibrahim and Menkovska

2019). A wide variety of mycotoxins are known today, but most concerns are those

causing severe health risk to both human and animals. They also impact nutrition

and food security due to lack of access to safety and healthy foods (Bryden 2012).

12.3 The Mycotoxins

Filamentous fungi are common in the environment and can produce thousands of

toxic compounds. However, mycotoxins produced by fungi are important as they

are toxic at low concentration.

Exposure to mycotoxins in diet can cause vomiting, abdominal cramps, pulmo-

nary edema, convulsions, coma, and death. Aspergillus, Penicillium, Fusarium, and

Claviceps are the common species that produce more important toxins. From

12 Mycotoxins inEnvironment andIts Health Implications

292

toxicity and clinical manifestations point of view, the mycotoxins of foremost sig-

nicance are aatoxins (AFs), ochratoxin A (OTA), deoxynivalenol (DON), nivale-

nol (NIV), fumonisin (FUM), ergot alkaloids, zearalenone, T-2 toxin, and patulin

(CAST 2003). The chemical nature and toxic impacts of different mycotoxins are

explained below in Fig.12.1.

12.3.1 Aatoxins andTypes ofAatoxins

Aatoxins are widely spread in food and feed supply chains. They are toxic chemi-

cals produced by different species of Aspergillus, especially from A. avus and

A. parasiticus (Cotty and Jaime-Garcia 2007). Fungi-producing aatoxins have

been found in corn, peanuts, peanut products, cotton seeds, peppers, rice, sunower

Fig. 12.1 Common types of mycotoxins (Source: https://www.ncbi.nlm.nih.gov/pmc/articles/

PMC164220/)

S. Alam etal.

293

seeds, pumpkin seeds, and tree nuts. Contamination of aatoxins is most common

in countries with warm and humid climates like Africa, Asia, and South America

and in temperate areas of Europe and North America. When agriculture crops con-

taminated with mycotoxins are used as green produce in foods and processing of

animal feed, it results in contamination of nal food products implicating severe

health hazards to both humans and animals.

There are about fourteen chemical structures of aatoxins being produced as

secondary metabolites by Aspergillus, and the major groups of aatoxins are aa-

toxins B1, B2, G1, G2, M1, and M2. The B-type aatoxins have distinct cyclopen-

tane ring. These compounds have a blue uorescence under long wavelength of

UV.Aatoxin B1 is the most toxic and potent carcinogen found to be correlated

with hepatotoxicity and liver cancer. On the other hand, aatoxin B1 has the ability

to penetrate through the skin and cause health risk (Boonen etal. 2012). G-type

aatoxins have a xanthone ring instead of the cyclopentane. These compounds pro-

duce green uorescence under UV.Other members of the aatoxin family are origi-

nally isolated from bovine milk. These include M1 and M2 which are hydroxylation

products of AFB1 and AFB2, respectively (Songsiriritthigul etal. 2010).

Poultry and farm animals fed on aatoxin-contaminated feed produce contami-

nated meat, eggs, milk, and milk products. Human intake of these aatoxin-

contaminated products may result in liver damage and cancer. Children are more

prone to develop toxicity to aatoxin contamination, whereas adults are affected

when doses exceed a certain amount (Gong etal. 2004). Aatoxins have been found

to be associated with changes in reproductive structures and hence the reproductive

potential of human males (Kasturiratne etal. 2008). In food and animal feed, accept-

able aatoxin levels ranged from 20 to 300 ppm to prevent toxicity from a higher

dose of aatoxins (Stoloff etal. 1991). Permissible levels of mycotoxins in different

food commodities as given by the FDA (Food and Drug Administration) are pro-

vided in Table12.1.

Table 12.1 FDA regulatory guidance for mycotoxins in food and food commodities for human

and animal use

Sr.

no Intended use Food or food commodities

Permissible level of

aatoxins

1 Human consumption Milk 0.5ppb

2 Human consumption Foods, peanuts, peanut

products, and nuts

20ppb

3 Immature animals Animal feed, peanut

products, and corn

20ppb

4 Dairy animals Corn, animal feed and

ingredients

20ppb

5 Breeding cattle and mature poultry Corn and peanut products 100ppb

6 Beef, cattle, and poultry, regardless of

the status of age or breeding

Corn and peanut products 300ppb

12 Mycotoxins inEnvironment andIts Health Implications

294

12.3.2 Ochratoxins

Ochratoxins are a group of compounds produced by a number of fungi like

Aspergillus and Penicillium species, particularly Aspergillus ochraceus and

Penicillium cyclopium. There are three types of ochratoxins, namely, A, B, and

C.All types of ochratoxin have same basic structure, but R side chains may be vari-

able. Ochratoxin A (OTA) is the most toxic and commonly detected as compared

with other types of ochratoxins. A. ochraceus, Aspergillus carbonarius, and

Penicillium verrucosum are major producers of ochratoxin A (Hassan and Mathesius

2012). These fungi are widespread in nature, as they can survive in a wide range of

conditions (temperature, substrate, pH, and moisture). A. ochraceus is widespread

in tropical regions, while P. verrucosum dominate temperate regions like Europe,

Canada, and South America (Ruan etal. 1995). OTA are common contaminants of

grains such as corn, oats, barley, rye, and wheat, whereas contamination of other

plant products like coffee beans, nuts, spices, olives, beans, grapes, and gs has also

been reported (Khan etal. 2003; Turra and Di Pietro 2015).

Investigations on the chemical structure of ochratoxin A revealed that it is a pen-

taketide derived by coupling of dihydrocoumarins family with β-phenylalanine. It

has been found to be associated with contamination of water and house heating

ducts, hence responsible for environmental and health hazards for human and ani-

mals (Hope and Hope 2012). Ochratoxin A can be absorbed by human and animal

bodies on ingesting food and animal feed contaminated with ochratoxin A.After

ingestion through food, it can be detected in host tissues, blood, organs, and breast

milk of human and animals. It can cause renal tumors and nephrotoxicity (Bui-

Klimke and Wu 2015).

Ochratoxin A is a stable molecule. It is fat soluble and cannot be readily excreted;

hence, its uptake means its deposition in tissues of infected organisms which is

directly proportional to the uptake of ochratoxin A.In animals, the main reason for

ochratoxin A contamination is feeding on mold-contaminated fodder.

12.3.3 Fumonisins

Fumonisins (Fm) are toxic secondary metabolites produced by Fusarium verticilli-

oides, Fusarium proliferatum, and some other Fusaria. Fungi producing fumonisins

are found in grains, such as rice, sorghum, etc. F. verticillioides and F. proliferatum

cause corn disease, namely, fusarium ear rot (Parsons and Munkvold 2012). More

than 28 fumonisins have been isolated and are classied into four groups (A, B, C,

and P). Fumonisin B1 (FB1) is the most abundant toxin contributing 70–80% to the

total fumonisin group.

The chemical structure of fumonisin indicated their polyketide nature. Fumonisins

consist of a 20-carbon aliphatic chain with two side chains which are linked to ester

and hydrophilic in nature. Thus, they resemble sphingosine that is an essential

S. Alam etal.

295

phospholipid in cell membranes. Gelderblom and coworkers were the rst persons

to isolate fumonisin B1 and fumonisin B2 from cultures of F. verticillioides

(Gelderblom etal. 1988). The discovery of fumonisins go back to late 1980s where

it is linked with many years of study on the disease known as equine leucoencepha-

lomalacia (ELEM). Equine leukoencephalomalacia (ELEM) is commonly known

as “moldy corn poisoning.” It is a disease of the central nervous system affecting

horses, mules, and donkeys with symptoms of blindness staggering, drowsiness,

and liquication of brain tissues (Wilson etal. 1990). Disease is linked with feeding

animals on moldy corns for a duration of several days to weeks.

Mycotoxin fumonisins specially produced by two species of Fusarium, that is,

F. verticillioides and F. proliferatum, can cause esophageal cancer in human.

Incidence of high rates of human esophageal cancer associated with fumonisins has

been reported from China, Southern Africa, and Italy (Li etal. 1980; Marasas 1996;

Franceschi etal. 1990). In other experimental studies, fumonisins were found to be

involved in the inhibition of cell growth and induction of apoptosis in vitro (Tolleson

etal. 1996). As per the directions of Food and Drug Administration (FDA), the per-

missible limit of fumonisins in human food should not exceed 4ppm/kg, whereas in

animal feed, the level of fumonisin should not be more than 5–100 ppm/kg depend-

ing upon different types of farm animals (FDA 2001). This level can be achieved by

good farming practices and better control of fungal growth.

12.3.4 Trichothecenes (TCTCS)

The term TCTCs is derived from trichothecin, the rst isolated compound in this

group. Many species of Fusarium produce TCTCs when infects corn, wheat, barley,

and rice. TCTCs are also produced by fungi such as Myrothecium, Trichoderma,

Trichothecium, Cephalosporium, Verticimonosporium, and Stachybotrys.

Toxicogenic Stachybotrys chartarum can proliferate in humid storage environment

and thus can cause environmental health hazard for residents (Hardin etal. 2003).

The Trichothecene family has been classied into A, B, C, and D types. All of the

types have common sesquiterpene nucleus with epoxide ring and side chains of

hydroxyl, methyl, or acetyl. All the types of trichothecenes are very stable and sur-

vive during various processes like milling or cooking and during storage of nished

products (Widestrand and Pettersson 2011). Types A and B of trichothecenes are of

utmost concern for consideration as causing harmful effects to both humans and

animals with type A being more hazardous than type B.Subclasses of type A tricho-

thecenes are Don, 3-ADon, 15-ADon, Niv, T-2, HT-2, and 4, 15 Das. These sub-

classes have same trichothecene nucleus but are varied in side chains. On the basis

of toxicity, of the type A subclasses, T-2 trichothecene is the most toxic and at a

concentration of 1mg/kg body weight can inhibit translation in eukaryotic cells,

thus leading to lethality (Ueno 1984). Dermal exposure to subclass T-2 trichothe-

cene can initiate skin burning pain, redness, and appearance of blisters. Oral inges-

tion of T-2 trichothecene can cause vomiting, diarrhea, nasal irritation, and cough.

12 Mycotoxins inEnvironment andIts Health Implications

296

It can also affect vision, leading to blurred vision (Adhikari etal. 2017). Due to its

high toxicity, this toxin is also produced by fungal fermentation and can possibly be

used as biological warfare agent (Venkataramana etal. 2014).

Trichothecene (type B) is further classied into deoxynivalenol (Don), nivalenol,

Fusarenon-X, and trichothecin. All have the same basic structure but vary in their

side chains. The most frequently found toxin from type B trichothecene is the

deoxynivalenol, also known as vomitoxin, due to the its ability to induce vomiting

episodes when ingested. F. graminearum and F. culmorusis are the main producers

of deoxynivalenol. They are plant pathogens causing fusarium corn blight in corn

and fusarium head blight in wheat (Kim etal. 2016). Mycotoxicoses caused by

trichothecenes affect many organs including the gastrointestinal tract and hemato-

poietic, cardiovascular, immune, and hepatobiliary systems. Initially, they can

inhibit protein synthesis by binding with eukaryotic ribosomes. On the other hand,

they can induce toxicity by deregulation of calcium homeostasis, impairing mem-

brane functions and thus altering intercellular interactions. Higher doses of trichot-

hecenes can cause rapid leukocyte apoptosis, leading to immunosuppression (Ueno

1983). They are also associated with reduced growth rate due to feed refusal and lost

reproductive potential (Table12.2).

12.3.5 Zearalenone (ZE)

A variety of Fusarium species, for example, F. graminearum, F. culmorum, F. cerea-

lis, F. equiseti, F. crookwellense, and F. semitectumcan, produce zearalenone (ZE).

These species of Fusarium are common inhabitants of soil and are also known as

Table 12.2 Toxic effects and permissible levels of most toxic groups of trichothecenes

Toxic groups of

trichothecenes

Subgroups of

most toxic

trichothecenes Toxicogenic fungi Toxic effects

Permissible

level

Trichothecenes

Type A

HT2

Fusarium

langsethiae,

Fusarium poae,

Fusarium

sporotrichioides,

Fusarium equiseti,

and Fusarium

acumninatum

Growth retardation,

myelotoxicity,

hematotoxicity,

necrotic lesions on

contact sites

100 ng/kg

b.w./day

Trichothecenes

Type B

Nivalenol

(NIV), DON

3-ADon

15-ADon

Fusarenon-X

Fusarium

graminearum and

Fusarium culmorum

Vomiting,

hemorrhagic diarrhea,

anorexia, suppression

of body weight gain,

hepatotoxicity,

dermatological

problems, and altered

nutritional efcacy

1μg/Kg b.w/

day to 1 mg/

kg b.w./day

for various

derivatives

S. Alam etal.

297

plant pathogens. High moisture contents and low temperature favor the growth of

Fusarium species and hence production of zearalenone (Bennett and Klich 2003).

ZE is resistant to high temperature treatment and can be detected in various cereal

crops like maize, barley, rice, oats, and sorghum (Tanaka etal. 1988).

The chemical structure of Zearalenone is a macrocyclic β-resorcylic acid lac-

tone, mimicking the reproductive hormone estrogen (Shier etal. 2001). This struc-

tural similarity to estrogen may cause early puberty in individuals. ZE binds with

estrogen receptor and stimulates protein synthesis. Therefore, it is called phytoes-

trogen due to its hyperestrogenic effects and premature onset of puberty in female

animals (Collins etal. 2006). ZE can also interact with immune system, resulting in

immunosuppression (Berek etal. 2001). Zearalenone and its analogues can indicate

clinical manifestations in both animals and human with major symptoms of enlarged

uterus and mammary glands, swelling of vulva and vagina, and abortion in some

cases. As zearalenone is heat stable and can withstand food processing like milling,

grinding, heating, and cooking, its presence in food and food commodities should

be controlled. As per FDA and WHO the maximum acceptable daily intake level of

zearalenone to human and animal should be below 0.5μg/kg body weight (Zinedine

etal. 2007).

12.3.6 Patulin

Various species of Penicillium, Aspergillus, and Byssochlamys can produce a toxic

metabolite named patulin (Ozsoy etal. 2008; Puel etal. 2010). Penicillium expan-

sum is a famous patulin-producing species that is commonly present in rotten apple.

It is also known as blue mold and attacks pear, cherry, grapes, and oranges.

Chemically, patulin is a water-soluble lactone and is classied as polyketide. It was

initially isolated in the 1940s as a broad-spectrum antifungal compound. It is known

by different names like clavacin, expansin, clavatin, and gigantic acid as it was co-

discovered by various groups who gave them different names (Goyaletal.2017).

Patulin can cause DNA damage and is known as immunotoxic, genotoxic, carci-

nogenic, neurotoxic, and teratogenic. It can affect cells by formation of free radi-

cals, leading to caspase-3 activation, leading to apoptosis (Saxena etal. 2009). Due

to associated health risks, FDA regulated the patulin levels as 50 μg/kg in all

squashes and 25μg/kg for natural unprocessed apples, and it should not exceed

10μg/kg in children’s apple food products (EC 2006; Unusan 2019).

12.3.7 Ergot toxin

Outbreak of ergotism was noticed earlier in Middle Ages and France. Ergotism was

then called St. Anthony’s re due to the burning sensation felt in limbs. It is caused

by eating grains of rye or wheat contaminated with ergotamine, that is, a mycotoxin

12 Mycotoxins inEnvironment andIts Health Implications

298

produced by fungus Claviceps purpurea. Ergotamine causes vasoconstriction. This

mycotoxin is extremely toxic. In recent years, different studies reported its toxic

effect on human including hallucinations, gangrene, and even loss of limbs in

humans or hooves in cattle (Klotz 2015). These toxic effects are induced by antago-

nism of neurotransmitters, like dopamine, norepinephrine, and serotonin, resulting

in long-term vasoconstriction, leading to reduction of blood ow and related side

effects. Ergot alkaloids have a number of applications in medicine from promoting

labor pain, reducing uterine hemorrhage to treating migraines and endocrine disor-

ders like parkinsonism (De Groot etal. 1998; Burn 2000; Crosignani 2006).

12.3.8 Sterigmatocystin

Sterigmatocystin (STE) is synthesized by many genera of fungi including

Aspergillus, Chaetomium, Bipolaris, Emericellai, Podospora, Fusarium, Farrowia,

Humicola, Moelleriella, Monocillium, and Eurotium (Rank etal. 2011). It was rst

time isolated in 1954 from cultures of Aspergillus versicolor (Castillo-Ureuta etal.,

2011). STE is an antecedent compound of aatoxin B1 (AFB1), and there is similar-

ity between chemical structures and properties of both STE and AFB1. STE also

exhibits hepatotoxic and carcinogenic effects like AFB1. STE is known to cause

several toxic effects by interacting with the cell cycle, leading to DNA damage and

cell cycle arrest. It can also induce apoptosis and hence cell death (Cui etal. 2017).

12.3.9 Nitropropionic acid (NPA)

A. avus, A. oryzae, and A. wentii produce nitropropionic acid, which causes fatal

food poisoning in human, congestion of liver and lungs, convulsion, and apnea.

NPA can cause poisoning of livestock when they are fed on plants contaminated

with NPA (Johnson etal. 2000). Consumption of contaminated foodstuffs can also

cause toxicity in human. Even low doses of NPA can lead to acute encephalopathy

and dystonia (Liu etal. 1992).

12.4 Other Mycotoxins

Penicillium also produces many other less common mycotoxins such as cyclochlo-

rotine, rugulosin (RS), and luteoskyrin (LS). These toxins mainly affect the liver.

Some other toxins produced by Penicillium are penicillic acid (PA), citrinin (CT),

xanthomegnin, citreoviridin, and cyclopiazonic acid (CPA). Alternaria species also

produce various toxins including alternariol, alternariol monomethyl ether (AME),

S. Alam etal.

299

altertoxin I, tenuazonic acid, alternaric acid, dehydroaltenusin, altenusin, and alte-

riusol that contaminate common edible items such as vegetables, fruits, etc.

12.5 Detection ofMycotoxins

To minimize the exposure of human beings and livestock to mycotoxins, efforts

should be directed to monitor and control the level of mycotoxins in foodstuff.

Various countries have launched surveillance programs for the detection of myco-

toxins to reduce their consumption risk.

Various techniques have been used for rapid detection of mycotoxins as a single

method cannot serve the purpose due to differences in chemical nature, molecular

mass, and functional groups of mycotoxins.

12.5.1 Traditional Techniques forDetection ofMycotoxins

Various chromatographic techniques are being used for detection and quantication

of mycotoxins from cereals. Thin-layer chromatography (TLC), ultraviolet coupled

with high-performance liquid chromatography, gas chromatography–mass spec-

trometry, and uorescence are some of common techniques that are used for detec-

tion of mycotoxins. In addition, immunometric assays like ELISAs and

membrane-based immunoassays are also commonly used to detect the presence of

mycotoxins. TLC method is simple and cost-effective for detection of mycotoxins,

but it has low sensitivity and accuracy. The limited length of TLC plate and the

effect of temperature and humidity on separation of mycotoxins are some other

limitations of TLC method; hence, modern methods involving quantication of

mycotoxins are preferred. Liquid chromatography coupled with mass spectrum and

uorescence detectors are benchmark methods to detect mycotoxins (Cirlini etal.

2012). Due to ion suppression and matrix effects, LC-MS can give unsatisfactory

results for the quantication of mycotoxins. In such cases, tandem mass spectrom-

etry is preferred over uorescence due to its ability to identify both nonuorescent

and uorescent toxins.

Immunological assays, like ELISA, gained popularity for the detection of myco-

toxins as they can directly be applied and no cleanup procedure is required. This

method provides rapid and economical measurements, but at low concentration, it

lacks precision. Other drawbacks in the method are time consumption, requirement

of specialist plate reader, and inability to be used for eld testing. Another immuno-

chromatographic method is lateral ow strip assay. Antigen–antibody reactions are

also used for quick analysis of mycotoxins with high specicity and sensitivity. This

assay has been developed on commercial basis for the detection of many mycotox-

ins like DON and aatoxins (Xu etal. 2010).

12 Mycotoxins inEnvironment andIts Health Implications

300

12.5.2 New Methods forDetection andQuantication

ofMycotoxins

With the advancement in technology, various detection technologies have been

developed for the detection and quantication of mycotoxins in recent years. Some

of these techniques are ultrafast liquid chromatography connected with tandem

mass spectrometry (UFLC-MS/MS), uorescence polarization immunoassay,

nanoparticle-based methods of detection, and implementation of chip-based method

for detection of mycotoxins in foods. Other techniques such as biosensor and capil-

lary electrophoresis are in progress. The presence of mycotoxicogenic fungi in food

can also be detected by PCR.In short, a number of sensitive techniques are available

for the detection of mycotoxins, but the selection of method should be based on

objective of detection, sample size, nature of sample, and facilities available in labo-

ratory (Singh and Mehta 2020).

12.5.3 Management ofMycotoxin Contamination

There are different ways which are developed for management of mycotoxin con-

tamination in crops. These methods are given below.

12.5.4 Control ofMycotoxin Production

Preharvest control involves growing fungus-resistant crops, crop rotation with resis-

tant varieties, control of insect pests using registered insecticides, and use of atoxi-

genic biocompetitives (such as control of aatoxin contamination in crops by using

native A. avus strains which compete with toxin-producing strains) (Magan etal.

1984). Humidity and temperature have great inuence on production of mycotoxins

by toxicogenic fungi. Storage practices also play important role in the production of

mycotoxins; hence, environmental factors like temperature, moisture level, and

humidity of warehouses play important role in mycotoxin production.

12.5.5 Removal ofSecreted Mycotoxins fromFood

Secreted mycotoxins in food and feed can be eliminated by a variety of ways such

as physical separation, ltration, and solvent extraction. Physical separation includes

removing mold damaged seed and mold-damaged kernel by air blowing and density

and oatation separation; that is, depending on the density of mycotoxins, they oat

and hence separated. Moreover, ltration involves using activated charcoal, clays,

S. Alam etal.

301

and lter pads on which mycotoxins are adsorbed and hence separated. Moreover,

solvent extraction, drying, washing, milling, boiling, irradiation, microwave heat-

ing, and peeling are also used as methods to remove secreted mycotoxins (Shi etal.

2018; Sarrocco and Vannacci 2018).

12.5.6 Detoxication ofMycotoxins

Different physical, chemical and biological methods have been designed to inacti-

vate mycotoxins in food crops and feed. Physical destruction includes processes

like gamma irradiation (World Health Organization, Food irradiation 1988). Some

chemicals are also suggested to inactivate mycotoxins from food. These chemicals

include acids, bases, aldehydes, and oxidizing gases. Biological methods that are

formulated to destroy mycotoxins include enzymatic digestion and fermentation.

Various reports are available regarding the use of microorganisms like bacteria and

yeast and to degrade mycotoxins in food (Ben Taheur etal. 2019; Xia etal. 2017;

Wang etal. 2019). Detoxication by biological means is considered as efcient

approach as fewer and nontoxic end products are obtained. In vitro studies involv-

ing the use of microbial strains for detoxication produced signicant results.

12.5.7 Elimination ofMycotoxins by Food Processing

Mycotoxins are usually not destroyed by cooking, but some mycotoxins may be

inactivated by other types of food processing. Processing techniques cannot com-

pletely destroy the mycotoxins but can reduce their concentration (Neme and

Mohammed 2017). Softening can be used to reduce the level of mycotoxins in food

commodities as fungi accumulate on the surface of the granules. Although myco-

toxins are compounds stable at higher temperature, still their concentrations can be

reduced by using frying and baking methods at above 100°C.Similarly, under cer-

tain conditions, fumonisin B1 is reduced by sugars such as fructose to lose its

hepatocarcinogenicity.

12.5.8 Dietary Modications

Metabolism, distribution, and adsorption of mycotoxin are greatly affected by

dietary modications. For example, carcinogenic effects of AFB1 are inhibited by

ascorbic acid and green tea. Similarly, toxic effects of ochratoxin A and fumonisin

B1 are inhibited by vitamin C and vitamin E (Atanda etal. 2013, Karlovsky etal.

2016). Mycotoxin binders can be used that inhibit the absorption of mycotoxins by

binding to mycotoxins. They do not allow mycotoxins to enter into the bloodstream

12 Mycotoxins inEnvironment andIts Health Implications

302

from the intestine. Commonly used adsorbent materials are activated carbon, com-

plex nondigestible carbohydrates, aluminosilicates, and cholesterol. Although

dietary modications can reduce the risk of mycotoxins, further studies are required

to ensure food safety.

12.6 Toxicology

Mycotoxins are known to cause several kinds of acute and chronic illnesses in

humans and animals (Beardall and Miller 1994). Toxic effects of mycotoxin expo-

sure in humans are associated with ingestion of contaminated food and water and

inhalation of aerosols (Babič etal. 2017; Kumar etal. 2017; Viegas etal. 2017).

Since a substantial number of agricultural products are contaminated throughout the

world, food ingestion is found to be the main route of exposure, especially in

humans, although inhalation of aerosolized particles is a conceivably important

route of exposure principally in certain working areas, such as product processing

plants, and spaces where there are chances of high airborne concentration (Hooper

etal. 2009; Ferri etal. 2017).

Comparable to all infectious agents, mycotoxin exposure can result in a spec-

trum of medical disorders, affecting organ systems and supercial skin and induc-

ing allergic reactions such as asthma, sinusitis, pneumonitis, and hypersensitivities

(Bossou et al. 2017). Mycotoxin exposure can also result in conditions such as

vomiting, abdominal cramps, edema, convulsions, and even death. Long-term toxic

effects of mycotoxins can cause physiologic decompensation for an individual such

as cancer and immune deciency (CAST 2003; Lewis etal. 2005).

The mycotoxins of foremost importance are “AFs, ochratoxin A (OTA), deoxyni-

valenol (DON), fumonisins (FUM), nivalenol (NIV), ergot alkaloids, T-2 toxin,

patulin and zearalenone” arranged in the order of severity of disease they cause

(CAST 2003). Co-occurrence of mycotoxins has also been observed. These myco-

toxins sometimes are exposed in combinations, for instance, AFs and FUMB1, and

vomitoxin and zearalenone are found to co-occur in the same corn. When more than

one mycotoxins are consumed in combination, response to such exposure can be

classied into following categories: (i) additive, when the interactive effect can be

measured by individual consideration of each mycotoxin; (ii) antagonist, if the

effect is lower than the anticipated from each mycotoxin individually; or (iii) syner-

gic, if the response of one toxin is augmented by the presence of second toxin;

synergistic effects are more pronounced than additive and antagonist (Paterson and

Lima 2010; Gil-Serna etal. 2014).

Potential toxicological effects of mycotoxins are acute, chronic, mutagenic,

hemorrhagic, hepatotoxic, nephrotoxic, and neurotoxic effects on multiple systems,

leading to death sometimes. These toxicological effects happen due to interference

in the vital processes like protein synthesis and DNA replication causing necrosis,

S. Alam etal.

303

lung infection, and weakened immunity and can also result in mutagenic and tera-

togenic effects (Omotayo etal. 2019).

12.6.1 Hepatic Effects

The liver is known to be a biologically active organ in performing vital activities:

metabolism, excretion, and detoxication (Surai 2005, Shaker etal. 2010). The liver

is known to be the foremost target organ for mycotoxin toxicity and carcinogenicity,

especially aatoxins. Aatoxins perform their mechanism of action by interrupting

the immune function. Aatoxins interfere with nucleic acids and protein synthesis,

causing toxicity in targeted organs (Afsah-Hejri etal. 2013). When mycotoxins are

absorbed in the digestive tract, they are transferred to the liver, thereby causing

damage to the liver (Dalezios etal. 1973).

Hepatocellular carcinoma is considered to be the most commonly occurring dis-

ease and is the fourth leading cause of deaths worldwide (Eaton and Groopman

1994). It was estimated that there is a high correlation between the incidence of

hepatocellular carcinoma and the presence of aatoxin B1 (Henry et al. 2001).

Notably, it is reported that aatoxin consumption is responsible for 530% of liver

cancer (Liu and Wu 2010). Incidence of carcinoma of liver cancer is estimated to be

around 40 percent. Approximately 80% carcinoma cases are reported from develop-

ing countries with the highest outbreak in Africa, approximately 40% cases and 55

% from China (Liu and Wu 2010; Chhonker etal. 2018). In this regard, as the level

of aatoxin intake is increased, the incidence of liver cancer is logarithmically ele-

vated (Henry etal. 2001). Several studies have suggested there is synergistic effect

of aatoxins and hepatitis B and C virus in the etiology of the liver cancer (Wu and

Santella 2012; Palliyaguru and Wu 2013).

Furthermore, several studies have demonstrated that mycotoxin exposure causes

changes in hepatic histopathology, including bile duct proliferation, periductal

brosis, and cholestasis (Javed etal. 1993). The effects of mycotoxins (aatoxins

and ochratoxins) on hepatic histopathology have been studied in broilers by Bakeer

etal. (2013). From that experiment, it was found that aatoxin exposure amplied

Kupffer cell activation, sinusoidal dilation, and periacinar hepatic necrosis and

hepatocellular vacuolations. Additionally, Ortatatli etal. (2005) reported that if the

concentration of aatoxins in diet is around 100 ppb, they can cause hydropic

degeneration and fatty vacuoles in hepatocytes. Also, Krishnamoorthy etal. (2007)

demonstrated that exposure of T-2 toxin results in enlargement of the liver, hepato-

cyte necrosis, and hyperplasia of the bile duct.

Furthermore, ochratoxin A has been estimated to be teratogenic in experimental

animals, where it interferes and inhibits hepatic mitochondrial transport systems

and causes injury to the liver, and various studies suggest that OTA is excreted in

milk of affected animals (Chhonker etal. 2018).

12 Mycotoxins inEnvironment andIts Health Implications

304

12.6.2 Neurotoxic Effect

Likewise, other organs mycotoxins induce etiology in neuronal tissue, but there are

only few surveys reported for such toxicity. Among several mycotoxins, T-2 toxin,

macrocyclic trichothecene, fumonisin B1 (FB1), and ochratoxin A (OTA) are con-

sidered to have the ability for causing neurotoxicity (Uetsuka 2011). During neuro-

toxicity, immune responses damage neurons, and the overall CNS damage is

amplied by astrocytes and endothelial cells (Karunasena etal. 2010). Low concen-

tration of T-2 toxin can cause alterations in the metabolism of brain biogenic mono-

amines in experimental model, and intake of T-2 toxin results in altered permeability

for amino acids. T-2 toxin if reaches the fetal brain causes fetal death and fetotoxic-

ity primarily in the CNS.Study suggests that T-2 toxin-induced effects may be the

outcome of oxidative stress (Uetsuka 2011).

Ergot exposure can induce convulsions and hallucinations. Neurologic effects

can be induced by volatile organic chemicals (VOCs). Kodua poisoning is caused

by cyclopiazonic acid and 3-nitropropionic acid produced by Arthrinium species

and Penicillium and Aspergillus species, respectively. Symptoms include dystonia,

convulsion, and carpopedal spasm.

Mycotoxins produced by Penicillium and Aspergillus species are “tremorgenic”

and known to cause tremors, ataxia, and convulsions (Fung and Clark 2004). FB1

has the potential to cause cerebral cortex neuronal degenerations, concurrent with

inhibition of ceramide synthesis. OTA induces acute deciency of striatal dopamine

and its metabolites, followed by substantia nigra, striatum, and hippocampus neuro-

nal cell apoptosis (Uetsuka 2011).

12.6.3 Renal Toxicity

Long-term exposure to mycotoxins causes nephropathies and urinary tract tumors

(Jahanian 2016). AFB1 is considered to be nephrotoxic because toxin targeting kid-

ney induces various effects (Madhavan and Rao 1967; Akao etal. 1971), and in

kidney, these mycotoxins reduced the rate of glomerular ltration, tubular reabsorp-

tion, and the tubular transport. But it increases the rate of excretion of Na and K and

gamma-glutamyltransferase (Grosman etal. 1983). Renal cortex of albino rats dem-

onstrated that AFB1 induces degeneration and necrotic changes and enlargement of

glomeruli (Grosman etal.1983).

Various renal cell lines were used to demonstrate renal toxicity. The renal toxic-

ity study established that cell multiplication was decreased in renal cell lines. Fetal

kidney cells were reported to be more sensitive to the cytotoxic effect (Yoneyama

etal. 1987). AFB1 and AFM1 toxicities were assessed on HEK293 cells and CD-1

mice. The two mycotoxins, individually or in combination, caused the formation of

ROS, leading to kidney damage with a considerable decrease in L-proline and pro-

line dehydrogenase (Li etal. 2018).

S. Alam etal.

305

Occurrence of ochratoxin A in the serum in high levels indicates chronic

nephropathy (Abid etal. 2003). Ochratoxin A binds to low molecular weight mac-

romolecule in serum inducing nephrotoxic effects when accumulated in the kidney

(Stojković etal. 1984; Ali and Abdu 2011), demonstrating ochratoxin A effects on

rats’ kidney. They reported that ochratoxin A treatment decreased kidney weight

and increased the levels of serum urea and creatinine. Furthermore, animal study

showed that ochratoxin A treatment induced proximal tubular atrophy and cortical

interstitial brosis (Bayman and Baker 2006).

12.6.4 Effect onGastrointestinal Tract

GI tract is the rst physiological barrier against contaminated food products and the

rst target for mycotoxins too. When intestinal mucosa is contracted by such con-

taminants and toxins, they exert their deleterious effects on gastrointestinal tract

(Pinton and Oswald 2014; Akbari etal. 2017). Ingestion of mold-contaminated food

items and beverages and potential mycotoxins exposure produce symptoms such as

nausea, vomiting, abdominal pain, and diarrhea. The mechanism of toxicity is asso-

ciated with direct toxic effects on gastrointestinal mucosal surfaces. Mushroom tox-

icity causes similar toxic effects on GIT (Fung and Clark 2004). Mycotoxins,

primarily aatoxins, ochratoxin, and deoxynivalenol (DON), have been demon-

strated to alter intestinal permeability in different species (Moldal etal. 2018).

The health and performance of an individual are correlated with intestinal micro-

biota. Intestinal microora competitively inhibits colonization of the intestinal epi-

thelium by foreign pathogens modulating the gut-associated lymphoid tissue

(GALT). Recent study revealed that ochratoxin A (OTA) occurrence in the colon

signicantly decreased concentrations of acetic, butyric, and total short-chain fatty

acid (SCFA), indicating that OTA can alter composition and metabolism of the

colonic microora (Broom 2015).

There is a correlation between the intestine and ingested mycotoxins and their

deleterious effects in an individual. Mycotoxins exert negative effect on intestinal

health, for instance, declined intestinal cell viability and decreased concentrations

of short-chain fatty acid (SCFA). Benecial bacteria are eliminated, and increased

expression of genes is increased related to inammatory response and counteracting

oxidative stress. These negative effects will lead to recurrent intestinal infections

and impaired digestion process and absorption of nutrients (Liew and Mohd-

Redzwan 2018).

12.6.5 Mutagenic Effects

Mycotoxins are considered to be mutagenic, carcinogenic, and teratogenic because

they interact with nucleic acid (DNA) and other macromolecules (Paterson 2008).

Mutagenic effects exerted by mycotoxins can be direct or indirect; these can either

12 Mycotoxins inEnvironment andIts Health Implications

306

change bases (direct) or inhibit enzymes (indirect) involved in stabilization of

nucleic acids (Paterson 2008; Paterson and Lima 2009). Carcinogenic mycotoxins

include AFs, sterigmatocystin, OTA, FUMs, zearalenone, citrinin, luteoskyrin, pat-

ulin, and penicillic acid. All of these function by damaging DNA except for FUMs,

which interferes in signal transduction pathways (Gacem etal. 2020).

High levels of ROS resulted in neuronal stress, when neuronal cell line (Neuro2a)

was exposed with OTA.Furthermore, other events also lead to mutagenic effects:

mitochondrial membrane lost, DNA damage, and higher gene expression of neuro-

nal biomarker inducing apoptotic cell death. In SH-SY5Y neuronal cells, OTA

increased dose-dependent cytotoxicity levels with concurrent caspase-9 and cas-

pase- 3 activation in rat embryonic midbrain cells (So etal. 2014).

Co-occurrence of T-2 toxins and aatoxin B1 makes them the strongest muta-

gens. Sehata etal studied the alterations in gene expression induced by T-2 toxin in

the fetal brain of pregnant rats. T-2 toxin treatment upregulated gene expression for

oxidative stress (heat shock protein) and apoptosis (caspase-2). In another study, it

was reported that deoxynivalenol treatment (2501000 ng/mL) could cause an

increase in interleukin-8 mRNA.It was indicatedthat the ochratoxin A treatment

increased gene expression for apoptosis, inammation, and oxidative stress in rat

kidney (Jahanian 2016).

12.6.6 Other Effects

Since ZEA are present in the air, they are thought to cause pulmonary and cardio-

vascular toxicity. In one study, human bronchial epithelial cells (BEAS-2B) were

treated with 40 mM ZEA; as a consequence, mycotoxin caused DNA damage, cell

cycle arrest, and downregulation of inammation (Ben Salem etal. 2017). Outcome

of ZEA interaction with H9c2 cardiac cells caused oxidative stress (Sharma 1993).

The immune system is known to be an important defensive system against for-

eign pathogens and invaders (Pestka 2008). Specialized immune cells interact with

each other to give off desired consequence (Turner etal. 2003). Mycotoxins either

exert suppressive or stimulatory effect on immune system (Girish and Smith 2008).

Previous study has reported that aatoxin exposure induces immunosuppression,

indicating that the susceptibility to infections is increased with AF intake. Girish

and Smith (2008) found that immunosuppression is induced by several mechanisms,

as depicted by the decreased antibody production, the delayed hypersensitivity

response, the decreased bacterial clearance from systemic route, the declined lym-

phocyte proliferation, the suppression of macrophage phagocyte ability, and the

changed CD4+/CD8+ ratio.

Aatoxin B1 exerts their action on biomolecules such as DNA, changing their

actions (Bhat etal. 2010). Mycotoxins always lead to inhibition of protein synthe-

sis; consequently, they impair immune cell proliferation. But mycotoxins are also

known to adversely affect the surface receptors of macrophages, neutrophils, and

S. Alam etal.

307

lymphocytes; consequently, miscommunication between defense cells led to

immunosuppression.

It has been also demonstrated that mycotoxins also cause suppression of humoral

immunity. In this concern, ochratoxin A is known to suppress natural killer cell

activity by inhibiting interferon production (So etal. 2014).

12.7 Mycotoxin Management andDegradation

Several factors inuence mycotoxin production from respective fungal species such

as temperature, moisture, existing nutrients, humidity, and some others (FAO 2002).

Fungal growth and mycotoxin production can be prevented by employing good

agricultural and manufacturing practices. Developing countries suffer more from

mycotoxin presence in agricultural products, whereas developed countries have

opted for modern technologies and good control (FAO 2002). The Hazard Analysis

and Critical Control Point (HACCP) system also has signicant role in mycotoxin

prevention and management (Kabak etal. 2006; Stove 2013), though several strate-

gies like good agricultural and manufacturing practices can prevent the mycotoxi-

genic fungal and mycotoxin development. However, once food has been

contaminated with mycotoxins, postharvest detoxifying strategies are needed to

manage contaminants in feed and food.

However, it is not possible to always avoid mycotoxin contamination during pre-

harvest, postharvest, and storage, requiring detoxication of feed and food.

Therefore, several detoxication processes are employed for prevention of myco-

toxin exposure and the effects produced by them. Detoxication of mycotoxins in

such cases can be accomplished by either removing or eliminating the contaminated

products or inactivating the mycotoxins present in food or feed by physical, chemi-

cal, or biological methods (Beretta etal. 2000).

12.7.1 Physical Methods

Several physical strategies are employed for elimination and inactivation of myco-

toxins in food commodities.

Sorting and Segregation Mycotoxins can be removed from food commodities by

means of sorting and removal. It has been found that patulin levels are reduced up

to 99% by sorting and segregation of rotten and poor-quality fruits or trimming of

decayed sections of fruits (Scudamore and Banks 2004; Broggli et al. 2002).

Fumonisin and aatoxin contamination in corn can be reduced by sorting and seg-

regation (Peraica etal. 2002).

12 Mycotoxins inEnvironment andIts Health Implications

308

Heat Treatment Many mycotoxins are heat stable so they are not easily destroyed

within normal temperature (80–121°C) range of food processing; boiling, frying,

and pasteurization. Factors such as moisture content, ionic strength, and pH of food

are known to affect the sensitivity of mycotoxins. Aatoxins are degraded within

temperatures range 237–306°C.Aatoxins can be decomposed when food com-

modities contain higher moisture content (Beretta etal. 2000).

Irradiation Radiation has been proven useful in control of aatoxins, T-2 toxin, or

deoxynivalenol in grains and was also found effective on OTA decontamination in

poultry feed which can be achieved by UV radiation for one hour (Gul Ameer etal.

2016; Avantaggiato etal. 2004).

Filtering and Adsorption Mycotoxin adsorption decreases aatoxin, patulin, ZEA,

DON, and nivalenol residues by activated charcoal addition due to its porous nature

(Liu et al. 2011; Magnoli et al. 2011). Mycotoxin adsorption by bentonite clay

effectively eliminates aatoxin B1 from aqueous environments, and it has been

found that bentonite clay helped in removing aatoxin M1 from milk (Venter 2014).

12.7.2 Chemical Methods

Several chemical agents have been proven to successfully decontaminate and inac-

tivate mycotoxins and have been investigated for their effectiveness in mycotoxin

decontamination, namely, bases, oxidizing agents, organic acids, and other agents.

Bases (Ammonia, Hydrated Oxide) Ammonization of grains helps mycotoxin

control, preventing fungal growth and reducing aatoxins, fumonisins, and OTA

levels. However, this detoxication method is not acceptable for human food in the

European Community (EC) (Peraica etal. 2002). Recently, a mixture of glycerol

and calcium hydroxide was shown to have a powerful detoxication effect for

mycotoxins. A mixture of 2% sodium bicarbonate solution and potassium carbonate

reduces OTA contamination in coco shells (Federal Register 2003).

Oxidizing Agents (Hydrogen Peroxide, Ozone) Ozone has been approved for

effective decontamination of mycotoxins (Agriopoulou etal. 2016). Ozone degraded

patulin, aatoxins, and zearalenone. The decontamination of aatoxins AFB1,

AFB2, AFG1, and AFG2 was achieved with ozone (Quintela etal. 2012).

Organic Acids Several organic acids successfully degraded ochratoxin OTA.Egg

albumin efciently reduced OTA levels without affecting total polyphenols

(San’Ana etal. 2008).

S. Alam etal.

309

12.7.3 Biological Methods

Various physical and chemical detoxication methods have been developed to con-

trol mycotoxin contamination and fungal growth. However, not all of them are not

permitted due to their biosafety concerns and high cost.

There is a need to devise appropriate biological detoxication strategies for

ensuring food safety (Walter etal. 2015; Petchkongkaew etal. 2008). Numerous

bacteria, molds, and yeasts can biodegrade mycotoxins in food for human

consumption.

Bacterial Strains Several scientists reported that Bacillus and Brevibacterium spe-

cies in their interaction with mycotoxins can detoxify them. Bacillus licheniformis

isolated from soybean removed OTA efciently, with efciency of 92% with 48h

treatment at 37°C (Cho etal. 2010).

Bacillus natto and Bacillus subtilis were shown to remove zearalenone from liq-

uid medium: up to 75% zearalenone could be degraded after incubation. In another

study, was degraded by this B. subtilis strain interaction biodegraded up to 99% of

zearalenone (Moss and Long 2002; Tinyiro etal. 2011).Recent studies have indi-

cated probiotic potential of different Lactobacilli to degrade fungal toxins (Zada

etal.2021).

Yeast Strains Yeasts can efciently inhibit mycotoxigenic fungal growth and to

prevent mycotoxin synthesis. Saccharomyces cerevisiae decreased patulin contami-

nation during fermentation of juices: patulin could be removed completely after 2

weeks’ yeast fermentation (Gromadzka etal. 2009).

Molds In addition to bacteria and yeasts, molds can also biocontrol mycotoxins;

molds such as Aspergillus, Rhizopus, and Penicillium spp. can also effectively

detoxify mycotoxins. Clonostachys rosea effectively detoxify mycotoxins in cere-

als (De Felice et al. 2008). OTA accumulation and aspergillosis occurrence are

inhibited by Aureobasidium pullulans and therefore used as a biocontrol agent in

fruits or in wine grapes (De Felice etal. 2008).

12.8 Climate Change andIncreased Mycotoxin Production

Climate change is an inevitable probability as assessed by prominent researchers.

Conducive temperature and water activity are pivotal for fungal growth and produc-

tion of noxious fungal metabolites. Climate change is depicted by three major fac-

tors: (i) temperature rise, (ii) increase in CO2 concentration, and (iii) drought stress

(Medina etal. 2016). The rise in global temperature will raise mycotoxin ratio in

temperate regions, and food security in these countries may become prone to

increased aatoxin production. Preharvest fungal infection of crops may prevail,

and the outcome may be increased mycotoxin production in the eld. There may be

12 Mycotoxins inEnvironment andIts Health Implications

310

increased incidence of ochratoxin A, patulin, and Fusarium toxins. The European

Food Safety Authority has reported that earlier ripening of crops in central and

southern Europe will enhance pests and occurrence of diseases. Conventional fun-

gal species may diminish in tropical regions; hence, mycotoxin production may

decrease (Paterson and Lima 2010).

It has been suggested that climate change may induce a 1/3 of yield variability in

major food commodities globally (Ray etal. 2015). It has been noted that Serbian

maize was devoid of any aatoxins during 2009–2011, but 69% maize was affected

by aatoxins in 2012 when temperature was increased (Kos etal. 2013). Dobolyi

etal. (2013) have also observed similar ndings in Hungary.

The estimates indicate increased atmospheric CO2 concentration in the coming

25 years up to 350–400 versus 650–1200 ppm (Medina etal. 2016). CO2 increase

with elevated temperature and water stress condition will modify the growth of

toxigenic fungi and pattern of mycotoxin production.

Studies are lacking in revealing the acclimatization ability of fungal species to

climate change. The optimum temperature required for growth of toxigenic fungus

differs from the temperature at which toxin is produced. The raised temperature

may induce production of different toxin as indicated in a study when Alternaria

alternata capable of producing alternariol (AOH), alternariol monomethyl ether

(AME), and altenuene (AE) produced AOH at 21°C at 0.95aw but at higher tem-

perature produced increased concentration of AME (Vaquera etal. 2017). Three-

factor interaction was investigated by Medina et al. (2016) under elevated

temperature, drought stress at 37°C, and increased CO2 concentrations (650 and

1000 ppm). Molecular studies related to aatoxin gene expression also concluded

same ndings.

12.9 Future Prospects

The presence of these noxious contagions in food, feed, and the environment is of

great concern due to their association with a multitude of detrimental health effects.

The human population is more exposed to other contaminants including pesticides,

heavy metals, and other pollutants. Recent studies have revealed their presence in

human blood and urine (Arce-López etal. 2020). Humans are often concurrently

exposed to heterogeneous mixtures of mycotoxins provoking a public health per-

spective. Actual exposure to mycotoxins based on food consumption is quite dif-

cult to assess, and detection of mycotoxins bound to organic molecules has also

become problematic. Climate change perspective urges for great concern on myco-

toxin increase in environment and food commodities, ultimately affecting human

health. These factors compel for managing the risk associated with mycotoxins and

taking preventing measures to control the growth of mycotoxigenic fungi. Some

novel approaches are need of time to combat the risk of increased mycotoxins in the

environment to assure food safety.

S. Alam etal.

311

12.10 Conclusion

Mycotoxin contamination is a worldwide problem as they are the most toxic and

dangerous toxins linked with food safety. They have diverse chemical structures

having various effects on human and animal health. They adversely affect the qual-

ity of agricultural products and are responsible for signicant economic losses.

Efforts should be made to control mycotoxin production at preharvest stage and

detoxify them to minimize their exposure. Effects of climate change on mycotoxin

production should also be studied in current scenario of elevated temperature,

increased CO2 concentration, and the expected drought in tropical region. There is

a need to constantly monitor the quantity of mycotoxins in food commodities to

cope with the demand for healthier foods.

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Chapter 13

Antibiotics: Multipronged Threat toOur

Environment

MuhammadZeeshanHyder, SaniyaAmjad, MuhammadShaq,

SadiaMehmood, SajidMehmood, AsimMushtaq, andToqeerAhmed

Abstract The use of antibiotics in different elds of human societies is increasing

since the discovery of penicillin, the rst antibiotic discovered in 1928. Initially,

they were used to treat human ailments; later, they found their way in industry, hor-

ticulture, animal husbandry, honey production, sh farming and aquaculture, etha-

nol production, antifouling paints, disinfectants, and food industry. This

unprecedented use of naturally occurring and synthetic antibiotics led to the devel-

opment of broad-spectrum resistance in the bacterial communities against the com-

monly used antibiotics. As the exposure of antibiotics to our environment is

increasing, so is the development of antibiotic-resistant bacterial communities not

only in the medical settings and industry but also in our environment. There is a

concern that increased presence of antibiotics in the environment can contribute to

the recruitment of resistance factors from the environmental resistome to human

pathogens which may further complicate the issue of resistant pathogens. In this

chapter, we will discuss about different routes and sources responsible for the anti-

biotic pollutants and their environmental consequences and evaluate different man-

agement strategies for their control to reduce the risk associated with the presence

of antibiotics in our environment.

M. Z. Hyder (*) · S. Amjad · M. Shaq

Department of Biosciences, COMSATS University Islamabad, Islamabad, Pakistan

e-mail: zeeshan_hyder@comsats.edu.pk

S. Mehmood · S. Mehmood · A. Mushtaq

Department of Biochemistry, Islam Medical and Dental College, Sialkot, Pakistan

T. Ahmed

Centre for Climate Research and Development (CCRD), COMSATS University Islamabad,

Islamabad, Pakistan

e-mail: toqeer.ahmed@comsats.edu.pk

320

13.1 Introduction

Antibiotics are undoubtedly one of the most effective drugs being utilized for human

and animal therapy. They are not only used for preventing and treating different

infectious diseases in humans and animals but also for agricultural and farming

purposes. There is an increasing concern over the past years about the effects of

irrational use of antibiotics and their disposal on both human and environment

health. Environmental media which include air, soil, and water act both as a trans-

mission medium and reservoir for antibiotic-resistant bacteria. The worrisome

aspects regarding the ever-increasing use of antibiotics in the environment are that

the drug-resistant bacteria may proliferate and make their way to the food chain and

that they may wipe out trophic levels entirely in some of the ecosystems. These

fears are being realized globally now, and since the awareness of the impacts of

antibiotic pollution in the environment, the scientic community has recognized the

importance of devising strategies to regulate this phenomenon. The coming sections

explain about our current knowledge of the presence of antibiotics in the environ-

ment and its widespread consequences and also highlight the measures to protect

human and environmental health.

13.2 Routes ofAntibiotics Contamination

totheEnvironment

Antibiotics enter the environment through different routes (Fig.13.1). Antibiotics

are usually partially metabolized in humans and animals after their administration

(Kümmerer etal. 2009b) and are excreted through urine, stool, and sweat and enter

into the sewerage system. Sewage treatment plants, hospital waste, inappropriate

disposal of unused and expired drugs, animal husbandry, and aquaculture are the

major sources that contribute to the environmental load of antibiotics (Harris etal.

2012). The active substances in these antibiotics end up in various environmental

compartments such as water and soil since most of them are water soluble and are

therefore not likely to be degraded (Jianan Li etal. 2015). Antibiotics used in human

medicines enter sewers from households and healthcare facilities. From there, they

enter wastewater treatment plant without any pre-treatment, and via treated waste-

water they nally enter drinking water. When sewage sludge gets applied to soil

from the wastewater treatment plants, active substances from antibiotics make their

way to elds. Antibiotics may enter groundwater through soil or from streams,

lakes, and rivers. Antibiotics may enter the environment directly via wastewater that

is discharged from the facility where antibiotics are formulated or indirectly through

the wastewater treatment plant (Küster and Adler 2018). The routes of antibiotics’

entry into the environment are linked with the excretion of manure from livestock

where a major portion of antibiotics is discharged into the environment in an active

form. The overuse of antibiotics as feed additives in aquaculture has aggravated the

M. Z. Hyder etal.

321

problem of antibiotics contamination in the environment. Antibiotics get orally

administered to the patients where they get partially metabolized along with their

misuse in the hospitals due to which huge amounts of antibiotics are released in the

hospital waste. Moreover, the detection of high concentrations of antibiotics in

efuents from antibiotics manufacturing facilities has contributed to environmental

contamination. The wastewater treatment plants represent a major source where

sludge as well as treated wastewater are prominent pathways. Mutual interactions

take place between all the entry routes that generate novel threats of spread of ARGs

and ARB to humans as well as animals.

13.2.1 Antibiotics fromPoultry, Veterinary, andAquaculture

It has been speculated that in Europe, nearly two-thirds of all the antibiotics present

are used in human medicine whereas one-third is employed for veterinary purposes.

Recent reports estimate that in the United States, livestock producers use antibiotics

nearly 11,200 tons for objectives other than therapy to promote growth of livestock

and poultry (Whitacre 2015). The administration of antimicrobials in livestock

depends on the reason of usage. Antibiotics are orally administered via drinking

water or feed, whereas they are administered through injections for therapy (Pareek

Fig. 13.1 Routes of antibiotic entry into the environment

13 Antibiotics: Multipronged Threat toOur Environment

322

etal. 2015). Antibiotics are used in the livestock to treat diseases, prophylactically

at subtherapeutic doses to alleviate infection by bacteria and to promote growth

(Chee-sanford etal. 2009). Antimicrobials are routinely added to drinking water as

well as animal feed as growth promoters and are an important part of swine produc-

tion since the 1950s (Cromwell LG 2001). Some antibiotics get sprayed on crops;

all the spray does not remain on the plant, but rather major portion is washed into

soil and thereby reaches groundwater (Pareek etal. 2015).

Coccidiostat are found in broiler rations that are broad-spectrum antimicrobials

like ionophores as well as sulfonamides. Antimicrobials such as chlortetracycline,

bambermycin, bacitracin, penicillin, and virginiamycin get incorporated in the food

of turkeys as well as broilers for increase in growth. Bacitracin is an antimicrobial

drug which is not only used for promoting growth but also to control necrotic enteri-

tis, which is an intestinal infection caused by Clostridium perfringens. Virginiamycin

is another such drug used for the same purpose. The old drugs like tetracyclines are

now unsuccessful due to the rapid increase in antibiotic resistance. Because of this,

modern antibiotics such as uoroquinolones are used for curing Escherichia coli

diseases that are frequently prevalent in poultry (Wiedner and Hunter 2013). For

controlling the mortality rate of the poultry, uoroquinolones are the only effective

drugs for the cure of some infections, specically the E. coli.

The application of antibiotics in animals causes their release into the environ-

ment since majority of these antibiotics are designed in a way that they get quickly

excreted from the treated animals (Burkholder etal. 2007). In 2006, the production

of agricultural waste in the United States exceeded 200 million tons (Graves etal.

2011). Antimicrobials can be excreted as urine or feces in both unchanged form of

the drug and parent form like drug metabolites, prodrug, and active compound

(Bártíková etal. 2016). Furthermore, antibiotic metabolites may be modied back

to the biologically active form even when they were excreted in an altered and inac-

tive form. For instance, N-4-acetylated sulfamethazine, which is in fact a sulfa-

methazine metabolite, gets easily converted to its active form in liquid manure

(Sarmah etal. 2006). Many different antibiotics have the ability to persist in the

environment, and their presence may be easily detected not only downstream of the

wastewater treatment plants but also in the adjacent elds receiving animal wastes.

Moreover, in spite of the antibiotic remains, even a huge number of antibiotic resis-

tant bacteria colonizing the gut of animals treated with antibiotics may be dis-

charged into the environment. Commensals being the important carriers of

antibiotic-resistant genes can act as a reservoir of such genes that ows across the

entire microbial ecosystem. These microbes particularly bacteria harbor ARG and

mobile genetic elements in agricultural efuents that promote it while exchanging

among bacteria (Finley etal. 2013).

The role of veterinary antibiotics for the risk in the environment needs to be

addressed. The burial of dead animals on the farm highly contaminates groundwater

by nitrogen species as well as dissolved organic matter. The extent of the risk it

poses to human and environmental health depends upon the quantity of dead ani-

mals buried as well as the site’s hydrogeological conditions (Feeds etal. 1980).

M. Z. Hyder etal.

323

Efuents from veterinary clinics also contribute to antibiotic pollution. Hotspots

for occurrence of ARB include livestock keeping and farms. From here, ARB gets

introduced to the environment through wastewater or via spread of sewage sludge or

fermentation residues. Aquaculture is another pathway where antibiotics are over-

used. When medicated foods are used by sheries, antibiotics are released directly

into the surface water (Whitacre 2015). Antibiotics may enter the environment by

animal farming when manure is used as a fertilizer.

It is known that antibiotics get poorly metabolized in animals’ guts. Consequently,

large amounts of active substances are excreted. Mainly excrements get stored as

slurry (mixture of urine and feces), and small amounts mixed with straw get stored

as manure. Antibiotics are indirectly incorporated when manure or slurry is used as

a fertilizer. Through runoff and leaching, the antibiotics get introduced to the soil

from slurry/manure storage. Antibiotic degradation takes place in the soil due to

which groundwater and surface water might contain antibiotic residues. This entry

of antibiotic residues in the soil affects soil microbiota (Van De Vijver etal. 2016).

Plants take up some of these compounds; thus humans and animals that consume

these plants get affected.

Development of the antibiotic-resistant bacteria is associated with indiscriminate

use of antibiotics. Livestock can carry antibiotic-resistant bacteria as a result of

antibiotics being directly administered and development of antibiotic resistance

after administration as well. Other ways of developing antibiotic resistance include

intake of the contaminated feed and breathing of the air containing resistant bacte-

ria. The natural reservoirs present in the environment can be a source of further

spread of antibiotic resistance.

13.2.2 Administration ofAntibiotics inHumans forCure

Antibiotics get administered in humans for treatment of several bacterial infections.

About 40–90% of the administered antibiotics get actively excreted as parent com-

pound in the urine and feces, ultimately reaching the environment, contaminating

soils and water (Polianciuc etal. 2020). The major classes of antibiotics used for the

treatment of bacterial infections worldwide are quinolones. These antimicrobials

are signicant for treatment against both gram-positive and gram-negative bacteria.

These antibiotics work much effectively against the anaerobic bacteria especially

the ones resistant to sulfonamides and β-lactams, making them important for ther-

apy. The therapeutic action of quinolones is critical in the infections by organisms

resistant to other antimicrobials. The most commonly used antimicrobials in human

medicine are ooxacin and ciprooxacin. They are widely used in treating tuber-

culosis, joint infection, typhoid fever, and sexually transmitted diseases. Recently

introduced antibiotics such as gemioxacin, gatioxacin, and moxioxacin are used

in treating chronic bronchitis, urinary infections, cystitis, acute sinusitis, pyelone-

phritis, and gonorrhea. Increased antibiotic consumption is considered to cause

treatment failures in human medicine thus leading to an increase in illness duration,

13 Antibiotics: Multipronged Threat toOur Environment

324

morbidity, as well as mortality (Merlin 2020). Unregulated antibiotic consumption

causes increased levels of antibiotic residues as well as transformation products in

the environment.

13.2.3 Antibiotics fromHospitals andOther Medical Settings

Hospitals are important sources for the discharge of antibiotics in municipal waste-

water. Hospitals are focal points for spread of many antibiotic-resistant bacteria.

The transmission occurs from patient to patient through contact with patients,

healthcare workers, and contaminated objects. Pathogens carrying antibiotic resis-

tance genes can epidemically spread between patients, or the genes can be transmit-

ted via horizontal gene transfer (Whitacre 2015). The transmission of

antibiotic-resistant bacteria in hospitals is further driven by antibiotic pressure

(Almagor etal. 2018). Selection density has an important inuence regarding anti-

biotic pressure in hospitals. Selection density refers to the amount of antibiotics

used per person in an area. The selection density is high in a hospital where the

number of antibiotics in the formulary is small and gathering of few patients in a

small space like ICU also contributes to high selection density. Colonization pres-

sure inuences the transmission of microorganisms in hospitals. Higher coloniza-

tion pressure increases the spread of multidrug-resistant organisms in the hospitals

(Cantón etal. 2013). Increasing use of antibiotics in the medical settings since the

last decade has been observed which has reached about 200,000 tons per year, mak-

ing them potential environmental contaminants because of their synergetic and pro-

longed effects when they enter into the environment (Wise 2002).

13.2.4 Medical Waste, Hospital Wastewater, andSpread

ofAntibiotic Resistance

Intensive care units and hospitals are signicant breeding grounds for the develop-

ment and dissemination of antibiotic-resistant bacteria. Around 10% of generated

hospital waste is pathogenic and infectious, which can cause great hazards to the

public (Chartier etal. 2014). Hospital wastewater acts as a rich reservoir for antibi-

otic resistance as well as other genetic inuences that foster the extension of antimi-

crobial resistance to the environment (Berendonk etal. 2015). This takes place since

the hospitals receive vast amounts of antimicrobial substances and human patho-

gens. A study got conducted in Singapore to assess antimicrobial resistance in hos-

pital wastewater by analyzing the presence of antibiotic resistance factors in hospital

efuents such as resistant bacteria, antibiotic residues, and genetic determinants.

Levels of trimethoprim, azithromycin, clarithromycin, sulfamethoxazole, and cip-

rooxacin were quite reduced (around tenfold) as compared to those reported in

M. Z. Hyder etal.

325

another research study (Rodríguez-Blanco etal. 2012). Bulk of antibiotics deployed

in hospitals gets discharged into wastes, and thereby a selection pressure on bacteria

is generated. As a result, bacteria depicting resistance become prevalent in hospital

wastewater at such concentrations which are capable enough to terminate suscepti-

ble bacterial growth (Beyene and Redaie 2011). Therefore, hospital wastewater may

enhance level of microbes depicting resistance in recipient sewers through selection

pressure as well as introductory channels (Stalder etal. 2014). The environmental

exposure with the resistant pathogens may cause crucial health concerns because of

the existence of transmittable genes. Resistant pathogens may also function as a

reservoir of resistance genes that lead to serious health concerns (Keen and Patrick

2013). Campylobacter, Clostridium, Salmonella, Pseudomonas aeruginosa,

Shigella, Vibrio, Staphylococcus aureus,Leptospira, Enterobacter, Klebsiella, and

E. coli are the most prevalent bacteria in hospital wastewater (Arshad Sid 2017).

Studies have shown that limiting the use of antibiotics could increase or decrease

the phenomenon of antibiotic resistance depending upon the antibiotic class.

Treatment of antibiotics may accelerate the dissemination of drug-resistant bacteria

in multiple ways. Firstly, commensal ora that protects against invading bacterial

colonization gets disrupted by antibiotics, making patients more vulnerable to

acquire new bacterial strains. Thus, patients exposed to antibiotic resistant bacteria

after or during antibiotic treatment are more likely to become colonized. Secondly,

antibiotics have the potential to remove competing commensal bacteria in patients

whom antibiotic resistant bacteria have already colonized which allows overgrowth

of the bacteria that are resistant. This enhanced load of antibiotic-resistant bacteria

may lead to greater shedding and hence greater contagiousness (Kraemer et al.

2019). Consequently, superbugs are becoming common and claiming lives.

The most prevalent among them are CRE, MRSA, ESBL-producing

Enterobacteriaceae, VRE, multidrug-resistant Acinetobacter, Pseudomonas aeru-

ginosa, and Klebsiella. Interventions to limit the use of antibiotics can potentially

reduce the spread of antibiotic resistance. CDC’s Antimicrobial Resistance Threat

Reports 2019 include the recent death as well as infection estimates that highlight

the urgent threat of antibiotic resistance in the United States. It has been stated that

around 2 million people in the United States acquire an antibiotic infection and

around 23,000 people die each year (Table13.1).

13.2.5 Disposal ofUnused andExpired Antibiotics

Antibiotic consumption has been reported to be increased in 76 countries(Klein

etal. 2018). The increased antibiotic consumption is greater among the low- as well

as middle-income nations as compared with the higher-income countries. The inap-

propriate disposal of unused and expired antibiotics is much often ignored driver of

AMR.The vast majority of the drug users do not know how to properly dispose

unused and expired antibiotics and simply throw away their unwanted medications.

This improper disposal of antibiotics leads to their piling up in the landlls, drains,

13 Antibiotics: Multipronged Threat toOur Environment

326

and water supplies that leads to both environmental contamination and toxicity to

human, animal, and aquatic life. The disposed of drugs when not properly removed

during wastewater treatment process thereby reach surface water and are ultimately

released into the aquatic environment (Anwar and Saleem,2020). The concentra-

tion of these antibiotics has sufcient capability to promote resistance by target

modication or by HGT.Host genomes get repositioned and thereby function as

vehicles for acquiring resistance and dissemination. Therefore, the indiscriminate

discharge into the environment compromises the antibiotics’ effectiveness as well

as augments resistance as less harmful microbes mutate to deadly pathogens (Anwar

etal. 2020). As a result, the same bacteria when spread to humans are already resis-

tant to those antibiotics causing increased mortality and morbidity.

13.2.6 Industrial Discharge ofAntibiotics fromDrug

Manufacturing Facilities

Industrial discharge of antibiotics from drug formulation facilities is considered a

crucial risk factor leading to antibiotic resistance dissemination. Detection of high

levels of antibiotics (mg/L) specically uoroquinolones, tetracycline, and penicil-

lin in efuents from antibiotics manufacturing bodies in India and China highlights

the signicance of analyzing and monitoring the results of the high selection pres-

sure on the microbial communities (González-Plaza etal. 2019). Enhanced level of

antibiotics in the environment can foster the development of ARGs because of natu-

ral selection and may help establish environment as a reservoir for further prolifera-

tion of antibiotic resistance genes to microbes through water and food webs. These

industrial discharges which pollute receiving aquatic bodies are recognized to lead

to an enrichment of ARGs, accelerating their dissemination. The practice of dis-

charging hazardous industrial waste from drug manufacturing facilities is not

Table 13.1 Bacteria listed in antibacterial resistance threat report in 2019 (Biggest Threats and

Data | Antibiotic/Antimicrobial Resistance | CDC, n.d.)

Serial

no. Name of bacteria

Estimated cases in

2017

Deaths in

2017

1. Carbapenem-resistant Acinetobacter 8500 700

2. Clostridioides difcile 223,900 12,800

3. Carbapenem-resistant Enterobacteriaceae 13,100 1100

4. Drug-resistant Neisseria gonorrhoeae 550,000 –

5. Drug-resistant Campylobacter 448,400 70

6. ESBL-producing Enterobacteriaceae 197,400 9100

7. Vancomycin-resistant Enterococcus 54,500 5400

8. Multidrug-resistant Pseudomonas

aeruginosa

32,600 2700

9. Nontyphoidal Salmonella 212,500 70

10. Drug-resistant Shigella 77,000 Less than 5

M. Z. Hyder etal.

327

limited to only Asian countries but can be observed around world. Industrial dis-

charge of antibiotics from drug formulation facilities is considered a substantial

point source with levels higher than other routes (Khan etal. 2013).

13.2.7 Municipal Sewage, Wastewater, andSewage

Treatment Plants

The traditional wastewater treatment plants have been designed to effectively

remove certain pollutants and pathogens but are not effective in eliminating antibi-

otics or antibiotic resistance genes. Wastewater treatment plants serve as hotspots

for the spread of antibiotic resistance genes. Antibiotics get discharged into WWTPs

from hospitals, pharmaceutical industries, and households. Antibiotic residues from

households enter together with sewage to wastewater treatment plants. Sewage

microbiota consists of human commensal microbiota which gets mixed with bacte-

ria that colonize the sewage system. The fraction of antibiotic-resistant bacteria in

sewage can reach more than 50% in a given group like Enterobacteria. Leachate

from municipal solid waste pollutes environment by antibiotics thrown into house-

hold rubbish bins.

Wastewater from wastewater treatment plants contains a signicant load of anti-

biotics. Tetracyclines, β-lactams, quinolones, sulfonamides, and macrolides have

frequently been detected from emissions of WWTPs. The biological treatment pro-

cesses create favorable conditions for the development of antibiotic resistance genes

and horizontal gene transfer under sub-inhibitory concentrations of antibiotics.

Variations in the concentrations of antibiotics in wastewater are due to several rea-

sons: the size of wastewater treatment plant, seasonal uctuations, and antibiotics

usage patterns. Activated sludge is an important wastewater treatment process for

controlling pollutants and it serves as an important route for the spread of antibiotic

resistant genes in the environment. Antibiotic resistant bacteria present in the acti-

vated sludge go down into the water of aeration tank and sedimentation tank and get

released with the efuent. These bacteria can potentially contaminate soil when the

activated sludge is used as a fertilizer. Moreover, the antibiotic resistance genes in

the treated water are released through efuent into the surrounding water (Gupta

and Singhal 2018).

13.2.8 Antibiotics fromSurface Treatment Compounds

intheEnvironment

Contaminating bacteria can sustain for long time periods on any surface exhibiting

resistance to the applied disinfectants. Nosocomial pathogens may survive on dry

surfaces for weeks, but some pathogens, including Acinetobacter baumannii and

13 Antibiotics: Multipronged Threat toOur Environment

328

P. aeruginosa, require humidity for their survival. These pathogens can easily trans-

mit if disinfection is not done properly. The multidrug-resistant bacteria Klebsiella

pneumoniae and E. coli survive for several weeks on steel surfaces according to a

study. Research has shown that horizontal gene transfer of β-lactamase genes occurs

when recipient and donor cells are mixed upon steel. The study shows the potential

of bacteria to retain on touch surfaces plays a vital role in horizontal gene transfer

of resistance genes. Recent reports demonstrate that biolm producing strains of

A. baumannii can persist on the inanimate surfaces longer than the non-biolm

producing ones (Cantón etal. 2013). Excessive and inappropriate use of antibiotics

in this situation may contribute to the persistence of antibiotic resistant bacteria.

Inappropriate control of infection can propagate the antibiotic resistant bacteria and

can further lead to endemics. The used antibiotics in hospitals get discharged into

aquatic environment through wastewater leading to an increase in the rate of antibi-

otic resistance in the environment (Kraemer etal. 2019).

13.2.9 Antibiotics fromtheAquatic Environment

Antibiotics are discharged into the aquatic environment through wastewater efu-

ents and improper disposal from livestock and humans. Antibiotic resistance genes

have been frequently detected in surface river water, municipal wastewater, water

supply reservoirs, and drinking water (Huerta etal. 2013). Runoff from agriculture

and damaged sewage pipes are responsible for the entry of antibiotic resistance

bacteria into groundwater. Antibiotic concentrations in untreated wastewater were

measured in the United States according to a report. The estimated concentrations

ranged from 4 ng/L to 27,000 ng/L.The basis of this estimation was the number of

administered antibiotic prescriptions. It was found that the major classes of antibiot-

ics present in the aquatic environment were quinolones, sulfonamides, and macro-

lides. Among quinolones and sulfonamides, ciprooxacin and sulfamethoxazole

were the most prevalent in municipal water efuents, and sulfamethazine was the

most prevalent in farm runoff (Huang etal. n.d.). Antibiotic concentrations were

much lower in the efuents of highly advanced treatment processes because of sig-

nicant eradication of antibiotics by these processes. Levels of antibiotics in drink-

ing water are mostly reported to be minute when compared to the high levels in

surface waters, agricultural runoff, and wastewaters.

13.2.10 Antibiotics fromSediments

Sediments often contain antibiotic-resistant bacteria because of the unmonitored

application of antibiotics in aquaculture. Substances used in aquaculture may

directly enter the sediments from water without any pre-treatment process. This

leads to high concentration of antibiotics in sediments. Sulfonamides, tetracyclines,

M. Z. Hyder etal.

329

and quinolones get readily adsorbed in sediments. Antibiotics have both quantita-

tive and qualitative effects on the microbial communities residing in sediments. The

excess use of antimicrobials for treatment of bacterial diseases in aquaculture has

led to antibiotic resistance development in Aeromonas salmonicida, Vibrio anguil-

larum, Pasteurella piscicida, and Aeromonas hydrophila. Therefore, the high anti-

biotic load in sediments is strong enough to inhibit bacterial growth for aquaculture

(Kümmerer etal. 2009a).

13.3 Airborne Antibiotic Resistance Genes

intheEnvironment

The airborne bacteria in healthcare environment are mostly multidrug resistant and

hence pose a threat to humans even outside medical settings through airborne trans-

mission. Antibiotic resistance genes have been reported from air samples collected

wastewater treatment plants (WWTPs), livestock, and hospitals. Airborne particles

in highly contaminated places provide greater number of adhesion sites which facil-

itates microorganisms to suspend with increased stability in air. Airborne transmis-

sion plays an important role in the environmental dissemination of antimicrobial

resistance. Distribution pattern of airborne drug-resistant bacteria depends on phys-

iochemical factors, bacterial communities, meteorological parameters, antibiotic

usage, and air quality (Jing Li etal. 2018). Detailed information on airborne patho-

gens and their impacts on human and environmental health is unfortunately not

enough, and further research is required in this domain.

13.4 Hazardous Consequences ofAntibiotics

intheEnvironment

There is a great concern about the deleterious effects of antibiotics on our environ-

ment over the last few years; therefore much is not known about the hazards of

antibiotics entering the water sources. Moreover, the concentration of the antibiotics

present in waters is generally very low due to which it cannot be reliably measured

by common analytical methods. Although individual concentrations of antibiotics in

waters are low, but a large number of antibiotics when combined can cause serious

environmental and health problems (Kümmerer etal. 2009a). Horizontal gene trans-

fer between bacterial species in wastewater may be fostered by rich nutrient content

and high density of bacteria in the biolms. Co-selection through substances like

heavy metals and biocides that are present in sewage sludge, wastewater, and fer-

mentation residues is another mechanism via which antibiotic-resistant bacteria

occur in the environment (Gupta and Singhal 2018). Efuents from veterinary clin-

ics and hospitals also contribute to antibiotic pollution. Hotspots for the occurrence

of antibiotic- resistant bacteria include livestock keeping and hospitals. From here,

13 Antibiotics: Multipronged Threat toOur Environment

330

antibiotic-resistant bacteria get introduced to the environment through wastewater or

via spread of sewage sludge or fermentation residues. Aquaculture is another path-

way where antibiotics are overused. When medicated foods are used by sheries,

antibiotics are released directly into surface water (Whitacre 2015). Antibiotics may

enter the environment by animal farming when manure is used as a fertilizer. Some

antibiotics get sprayed on crops; all the spray does not remain on the plant rather

major portion is washed into the soil and thereby reaches groundwater (Pareek etal.

2015). Leachate from municipal solid waste pollutes the environment by antibiotics

thrown into household rubbish bins. Antibiotic resistance genes (ARGs) have been

observed in the air samples from places that are around WWTPs. Mutual interac-

tions take place between all the entry routes that generate new threats of spread of

ARGs and ARB to humans and animals through airborne aerosols and dust. Some of

the major hazards regarding the antibiotic presence in the environment include elim-

ination of the entire trophic levels in ecosystems and entry of multidrug-resistant

bacteria into the food chain. Microbial communities are complex and have the major

task of nutrient cycling. Cycling of the nutrients is important for maintaining quality

of soil and for sustainable agricultural land use. Nitrogen is one such essential nutri-

ent, and two main genera of gram-negative bacteria drive its cycling that are

Nitrosomonas and Nitrobacter. Broad-spectrum antibiotics like tetracyclines and

sulphonamides at high concentrations disrupt the nitrication process and inhibit

nutrient cycling signicantly (Frade etal. 2014). Antibiotics primarily affect micro-

organisms like bacteria, fungi, and microalgae. Sensitivity of microalgae varies to

antibiotics. For example, cyanobacteria (blue-green algae) show sensitivity to sara-

oxacin. Antibiotics exposure to the environment inuences the early life stages of

various organisms and exhibits adverse effects on reproduction (Pareek etal. 2015).

Behavior of the aquatic organisms is also impacted by antibiotics exposure to the

environment (Fig.13.2). One such example is that the antibiotics impact locomotion

(phototaxis) of the aquatic organism Daphnia magna. Primary antibiotic resistance

is present naturally in microorganisms. Secondary resistance on the other hand

develops when microorganisms encounter antimicrobial drugs during therapy.

Through horizontal gene transfer or conjugation, the plasmid mediated resistance is

easily transferred between microorganisms. Resistance then reaches the environ-

ment with the ability to adversely affect terrestrial and aquatic organisms. Important

examples are methicillin-resistant Staphylococcus Aureus (MRSA) and vancomy-

cin-resistant Enterococci (VRE). The drug-resistant bacteria can get transferred to

humans when manure is used as a fertilizer or when plants get watered with surface

water (Küster and Adler 2018). The problem of antibiotic resistant bacteria is accel-

erating, and tools to combat this problem are decreasing in power.

13.5 Effect ofIrrational Use ofAntibiotics onHuman Health

Misuse of antibiotics in humans in therapeutic regimens ultimately develops antibi-

otic resistance (Animals et al. 1999). Two main human health consequences of

increased AMR due to misuse of antibiotics are rise in foodborne diseases and

M. Z. Hyder etal.

331

increased cases of treatment failures (de Kraker etal. 2016). Increased human infec-

tions by resistant bacteria from food take place as there is rise in the prevalence of

antibiotic resistance because of increased human exposure to antibiotics (Smith

etal. 2005). Consuming an antibiotic can reduce the infectious dose for Salmonella,

if the bacteria is resistant to that antibiotic, and the same goes for other foodborne

bacteria. Several analyses of outbreaks of antibiotic-resistant Salmonella have

shown that prior exposure to antibiotics may result in a huge number of cases as

compared to the cases that would have taken place if a sensitive strain had caused

the outbreak (Mølbak 2005). It has been observed in the case of Salmonella out-

breaks that unrelated previous treatment with an antibiotic can predispose humans

to infection with susceptible or resistant Salmonella. As bacteria become more and

more resistant, treatment of patients with antibiotics for whatever reason enhances

risk for patients to develop subsequent infections caused due to resistant bacteria.

Thereby the public health impacts are increased cases of infections and larger

outbreaks (Anderson etal. 2003). In addition, increasing AMR in bacteria can lead

to treatment failures if the bacteria are resistant to an antibiotic used for treatment.

Fig. 13.2 Environmental hazards of antibiotics

13 Antibiotics: Multipronged Threat toOur Environment

332

An example of treatment failure is a case in Denmark where an AMR S. typhimurium

DT104 outbreak due to contaminated pork got traced back to a swine herd (Mølbak

etal. 1999).

13.6 Management Strategies forControl ofAntibiotics

Release intheEnvironment

The deaths estimated per year because of antibiotic resistance are approximately

70,000 globally (Kraemer et al. 2019), which makes its management crucial.

Dissemination of antibiotic resistance can be effectively controlled by the applica-

tion of appropriate measures for improving wastewater treatment processes as well

as by restricting the antibiotic use in livestock as well as agriculture. “One Health

Model” which connects animal, human, and environmental health domains should

be applied to resolve this issue worldwide. Understanding antibiotic resistance and

antibiotic pollution as one health approach may help in creating more effective poli-

cies. Little has been known about the fate, occurrence, risks, and effects linked with

the discharge of antibiotics and antimicrobials into the environment. There must be

fundamental data on the fate, sources, and effects of antibiotics in the environment

for appropriate risk management. The discharge of antibiotics into the environment

should be greatly reduced, and for this purpose, the unused drugs should never be

ushed down the drains (Kraemer etal. 2019). The misuse of antibiotics by the

general public should be stopped by making people aware that the antibiotics only

help against the bacterial diseases and not against the viral diseases. There should

be procedures to regulate suppliers in the pharmaceutical industry to make sure that

antibiotics do not get released into surrounding waters during their production

(Fig.13.3). Future antibiotic interventions should be “targeted antimicrobials” with

a narrow spectrum of activity to facilitate early responses instead of broad-spectrum

agents. Furthermore, the usage of these antibiotics should be implemented with

antimicrobial susceptibility testing. Moreover, the usage of biomarkers should be

encouraged to pinpoint when any antibiotic is essentially required and also when

antibiotic treatment should be terminated. Resultantly, the selection impact would

be lower on the microbiota (Cantón etal. 2013). Societies should publish proper

guidelines for appropriate antibiotic use and to reduce the antibiotic resistance in

the environment. These guidelines must include coordination between clinicians,

infection control teams, pharmacists, microbiologists, and drug-use prescribers. A

collaboration between the disciplines of epidemiology, microbiology, nursing, phar-

macy, and infectious diseases could result in an efcient program to mitigate antibi-

otic pollution in the environment.

M. Z. Hyder etal.

333

13.7 Conclusion

Antibiotic pollution has not only contributed to antibiotic resistance but also directly

affected human and environmental health. However, little information is present on

the sources, occurrence, fate, effects, and risks associated with antibiotic consump-

tion globally.

There is a signicant gap in understanding the interactions between antibiotics

and their metabolites and development of antibiotic resistance after their discharge

in the environment. Multiple approaches should be considered to reduce release of

antibiotics in the ecosystem for appropriate risk management. Currently, no proper

regulations are present for antibiotics monitoring in surface water, drinking water,

or groundwater. The scientic community has started to realize the signicance of

designing plans to regulate antibiotic pollution in the environment in the past few

decades. New policies should be implemented locally to restrict the dissemination

of antibiotic resistant bacteria and antibiotic resistance genes through environmen-

tal routes.

Fig. 13.3 One health approach to combat antibacterial resistance

13 Antibiotics: Multipronged Threat toOur Environment

334

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Chapter 14

Remediation ofPlastic Waste Through

Cohesive Approaches

BibiSaimaZeb, QaisarMahmood, HaleemaZebAbbasi, andTahseenZeb

Abstract Growing volume of environmental plastic waste has generated global

concerns because of its persistence in the environment. Plastic is one of the main

environmental problems because of its slow degradation rate or organic matter’s

non-biodegradability in natural conditions. Plastic contamination and global warm-

ing are caused not only by increasing the issue of waste disposal and landlling but

also by burning CO2 and dioxins. Not only the environment is contaminated, but

plastic also poses health risks to wildlife. Plastic waste burning produces poisonous

gases that pose a health hazard after inhalation causing cancer and lung diseases.

Biodegradation of plastics by microbes is one possible solution to this problem.

Plastic waste has not been much treated so far by means of combination of biologi-

cal along with the physicochemical methods; this chapter explores the potential of

cohesive methods for remediation of plastic waste. Main benets of plastic are

lightweight, inertness, toughness, strength, and low cost, but it alsohas the disad-

vantagessuch as recalcitrant biodegradation and difcult to naturally degrade. This

chapter highlights the effect of cohesive methods on the plastic degradation by

potential microbes. PET type of plastic was treated biologically by various microbes

including microalgae, lichens, fungi, and bacteria subjected to either pretreatment

or not. It is concluded from the different review studies that pretreatment had marked

effect on the cracking and alteration of plastic polymer which helped to grow micro-

bial species on the cracked surface.

B. S. Zeb (*) · Q. Mahmood · H. Z. Abbasi

Department of Environmental Sciences, COMSATS University Islamabad, Abbottabad

Campus, Islamabad, Pakistan

e-mail: saimazeb@cuiatd.edu.pk; drqaisar@cuiatd.edu

T. Zeb

Agriculture Research Station Baffa– Mansehra, Agriculture Research System,

Khyber Pukhtunkhwa, Pakistan

338

14.1 Introduction

Plastic consumption is increasing day by day, and plastic pollution has amplied

manifold (Haward 2018). About 100 million tons of plastics are manufactured

around the world every year (Payne etal. 2015). The use of the synthetic polymers

is part of our daily life; polythene and plastics are widely used as packaging, food,

medicine, clothing, shelter, transport, industry, and agriculture in not only rural but

also urban areas since the last few decades (Cragg etal. 2015). This causes waste

disposal and contamination due to extensive use of polythene and plastics. The best

(Eichinger etal. 2005) way to degrade water treatment and remove pollutants from

the environment is through biodegradation (Sanchez etal. 2015). Biodegradation is

the degradation of the natural and articial polymers by different microorganisms

(fungi, bacteria) (Sanchez etal. 2015).

Plastic pollution is increasing at such an alarming rate that plastic disposal seems

very difcult due to limited dumping sites (Restrepo-Flórez etal. 2014). In all eco-

nomic sectors, plastic polymer has been widely used for manufacturing various use-

ful products. Because of being versatile, elastic, durable, and recalcitrant, it has

brought quality to life as it acts as an outstanding barrier to external stress (Singh

and Sharma 2008; Alimi etal. 2018). Moreover, it has unique mechanical and ther-

mal properties: cost-effective, low-weight indestructible, and highly moldable, and

is widely used at industrial and household levels. Plastic polymer like polyethylene

is a man-made polymer which has high molecular weight and greatly hydrophobic

in nature (Ahmed etal. 2014). It causes adverse impact to the environment because

of its recalcitrant nature and extensive use in the production of grocery bags, con-

veyance material, and beverage bottles and in making of electrical and medical

appliances (Krupp and Jewell 1992).

Polythene is sustainable and will require up to 1000 years for natural environ-

mental degradation (Sangale etal. 2012). Plastic is one of the main environmental

problems because of its slow degradation rate or organic matter’s non-

biodegradability in natural conditions. Ali etal. have claried in 2009 that improper

disposal of waste and landlling are not the only cause of plastic contamination and

global warming, but other activities like burning carbon dioxide as well as carcino-

genic hydrocarbons called dioxins are also contributing to it. Burning of plastic

waste produces poisonous gases that pose a health hazard after inhalation causing

cancer and lung diseases (Pramila and Ramesh 2011). The accumulation of syn-

thetic polymers in the environment is mostly because of the unavailability of effec-

tive methods of disposing these polymers and thus increasing the environmental

hazards to plants and animals (Barnes etal. 2009).

The main characteristics of plastic are lightweight, inertness, toughness, strength,

and low cost, but it also has some drawbacks, like it is intractable to degradation and

very hard to decay naturally (Leja and Lewandowicz 2010). The best (Eichinger

etal. 2005) way to degrade water treatment and remove pollutants from the environ-

ment is by biodegradation (Sanchez etal. 2015). Biodegradation is the method of

degrading natural polymers like cellulose, lignin, and articial polymers like

B. S. Zeb etal.

339

polystyrene and polyethylene by the enzymatic activity of microbes such as fungi

and bacteria into metabolites such as H2O, CO2, CH4, biomass, etc. (Sheel and

Pant 2018).

14.2 Plastic asSource ofPollution

The amount of plastic deposition in the environment is evident that environmental

contamination is caused by plastic. Around 10% of global waste disposal is reported

to be plastic (Lebreton and Andrady 2019). According to a general estimate, the

annual production of plastic has reached to approximately 52 million tons and is

increasing day by day and contributes to almost 60% of ocean debris, and it is esti-

mated that total accumulation of plastic will be reached to 250 million tons till 2025.

Plastic contamination has been described as a global concern in freshwater and

marine environment. Plastic waste is estimated to account for 60–80% of marine

debris, exceeding 90–95% in some areas (Kibria 2017). Eighty percent of the total

plastic waste is from sources that are land based, while the remaining 20% has

ocean origin, which includes different sources like ropes and nets used for shing

(Van Sebille et al. 2016). Plastic debris is an increasing pollutant which does not

degrade easily, but remains for long periods in the aquatic ecosystem. An estimated

5 trillion fragments of plastic oat in the oceans of the planet (Tunçer etal. 2019).

The plastics are manufactured at a large scale because it is used in textile indus-

try, food synthesis, construction activities, and for the synthesis of carrying and

conveyance material. The accumulation of plastic in the water bodies is considered

a major problem and may undergo mechanical and chemical breakdown, causing

water pollution and threat to aquatic life (Eriksen etal. 2014). Its direct contact to

the ultraviolet rays from sunlight and disintegration by the ocean waves breaks plas-

tic into micro and nano forms which more toxic and easily become the part of the

food chain. The studies suggest that the plastic present in the oceans is difcult to

degrade due to pertaining environmental conditions (i.e., exposure to UV radiations

and its conversion into micro and nano form) (Cole etal. 2011). The high-density

polyethylene usually sinks down into water, undergoing torpid degradation and

changing into microplastics, causing huge threat to marine biota (Andrady 2017),

while the low-density polyethylene and polypropylene oats on water surface

(Alimi etal. 2018). Dangerous waste has been exposed to the natural environment.

In many areas, the local environment has been destroyed by major disasters includ-

ing oil spills every year, and the unnecessary use of plastics has degraded soil and

water. Million tons of polythene are produced worldwide. It is used in the develop-

ment of plastic lms to make containers and other products like cups. Polythene

waste also causes damage to the health of sh, birds, goats, deer, and other animals

(Lora and Andrade 2009). Plastic pollution emerges as a threat to global ecology, as

it is resilience to degradation (Saxena etal. 2009). The continuous plastic pollutant

ow is sustained by two means: deliberately by unsafe domestic and industrial

waste disposal and by improperly contained static and transported waste directed by

14 Remediation ofPlastic Waste Through Cohesive Approaches

340

the weather; land-based plastic waste migrates to the oceans, where it is further

introduced by the dumping or destruction of underwater ships and offshore oil plat-

forms. Such pollution has a number of deleterious consequences. Plastic waste in

the marine environment is the cause of numerous dangerous and environmentally

harmful effects. Plastic remains pose a direct threat to wildlife, with many and var-

ied species recognized as having an undesirable impact on plastic objects (Mussgnug

etal. 2010).

The one main source of environmental pollution is LDPE (Romero Saez etal.

2017). High-density polyethylene generally sinks into water undergoing degrada-

tion and converting into microplastics (Andrady 2011), and the low-density poly-

ethylene and polypropylene oats on the surface of water (Alimi etal. 2018).

The key risks coupled with plastic objects to animals are the entanglement and

ingestion of such objects (McKendry 2002). Not only the environment is contami-

nated, but also plastic poses health risks to wildlife. The improperly disposed and

utilized plastic bags don’t allow air and water to enter the earth which leads to

exhaustion of fresh water and is also an ultimatum to a creature’s life. Direct contact

to ultraviolet rays from sunlight degrades plastic into small toxic parts, which can

be easily entered into the food chain by ingestion of especially aquatic animals

(Denuncio etal. 2011). A wide range of humans have been noted to have negative

impacts on plastic wreckage, ocean birds, sea turtles, cetaceans, lter feeders, fur

seals, and sharks (Srirangan etal. 2012). Marine birds are particularly prone to

plastic items through ingestion, which they mistake for food (Sims etal. 2006).

Furthermore, plastic contamination annually records higher amounts of marine

mammal death approximately 1 lakh and seabirds deaths up to 1 million (Kedzierski

etal. 2018).

Plastic eaten or taken up by these animals does not digest and contribute to

decrease stimulation of the diet and blocking of gastro intestine, reduce secretion of

gastric enzymes, and lower the steroid hormone level and raising reproductive prob-

lems (Horton etal. 2017). Plastic particulates in the ocean were shown to retain very

high concentrations of organic toxins. Harmful chemicals like polychlorinated

biphenyls (PCBs), nonylphenols (NPs), organic pesticides including dichlorodiphe-

nyltrichloroethane (DDT), polycyclic aromatic hydrocarbons (PAHs), polybromi-

nated diphenyl ethers (PBDEs), as well as bisphenol A (BPAs) have been consistently

found across oceanic plastic wreckage (Sharma etal. 2019).

The existence of these substances even further raises the risk involved with the

consumption of plastic debris by wild animals (Kurian etal. 2013).

14.3 Nature andKinds ofPlastics

Plastics are synthetic long-chain polymeric particles and are considered very resil-

ient toward environmental changes (Kumar etal. 2017). Plastics can be dened as

long-chain polymers, which can occur naturally or synthetically (Ghosh etal. 2013).

Natural plastics consist of polymers that include chitin, lignin, starch, etc., whereas

B. S. Zeb etal.

341

synthetic plastics are generally derived from petrochemicals such as polyethylene,

polystyrene, silicone, nylon, etc. (Narwal and Gupta 2017). Polymers are mainly

petrochemical in nature and have semisynthetic organic compounds and high

molecular weight which can be molded into different shapes like bags, household

items, wires, packaging and wrapping material (40% consumption), agriculture

mulch, pipes, and electronics (Accinelli etal. 2012). Monomers of ethylene form

the polyethylene, which is an organic polymer, nonpolar, porous, high molecular

weight hydrocarbons formed primarily by cracking ethane and propane, naphtha,

and gas oil (Khoddami etal. 2013). High-density polyethylene (HDPE) and low-

density polyethylene (LDPE) are the two most common types of polyethylene.

Polyethylene is completely linear and available from 0.91 to 0.97g/cm3 with elastic

thickness range. Furthermore, high-density polyethylene is additionally linear with

marginal splitting resulting in high packing density (Kigozi etal. 2013).

Basically, polyethylene is an organic polymer which is made up of long-chain

monomers known as ethylene (C2H4) molecules. Polythene is produced by ethane

degradation or cracking propane and gas oil (Sangale etal. 2012). The general for-

mula of polyethylene is CnH2n, and the n is the number of carbon. Polythene com-

pounds have two types that are most common which include HDPE and LDPE

(Romero Saez etal. 2017). Polyethylene having little density is completely linear

and accessible from 0.91 to 0.97g/cm3 with elastic thickness range. High-density

polyethylene is additionally linear with marginal splitting resulting in high packing

density (Kigozi etal. 2013). Polyethylene (HDPE, LDPE, LLDPE, and MDPE),

polystyrene (PS), polypropylene (PP), and polyvinyl chloride (PVC) have been

classied as commonly used plastics (Muhonja etal. 2018).

Plastic is composed of different elements like oxygen, nitrogen carbon, hydrogen

chloride, and silicon. Coal and hydrocarbons are used in extracting the fundamental

plastic material (Ali etal. 2016). Therefore plastics are classify into two various

types, that is, thermoset and thermoplastics. Thermoplastics are classied as non-

biodegradable, and these are generally allowed for their hardening and softening to

cool and heat repetitively. On the other hand, thermoset plastics have a strong cross-

linked structure, and they are considered linear solids (Bardají etal. 2020).

14.4 Uses ofDifferent Plastic Types

Food, cosmetics, pharmaceutical chemicals, and detergents are packed mostly by

using synthetic plastics. Thirty percent of plastics have their usage in packaging

worldwide. Plastic’s usage is increasing at a rapid level of 12% annually (Sabir

2004). The most commonly used plastics in packaging are polyethylene (HDPE,

LDPE, LLDPE, and MDPE), polyethylene terephthalate (PET), polystyrene (PS),

polypropylene (PP), polyvinyl chloride (PVC), polyurethane (PUR), polybutylene

terephthalate (PBT), and nylons which are shown in Table14.1 below. The major

use of plastics is not restricted to their mechanical and thermal characteristics but

depends on the durability and stability of plastics.

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342

14.5 Plastic Waste Disposal

Plastic disposal is a global issue.Around the world, the most widely plastic disposal

methods are recycling, landlling, and incineration (Silva etal., 2020).

14.5.1 Combustion ofPlastic

Combustion of plastic products also produces gases as by-product, and these

released gases are hazardous as their inhalation by living organisms especially

humans can lead to several respiratory disorders and in some cases can also cause

cancer (Pramila and Ramesh 2011). The plastic waste is mainlyburned in landlls,

thisthreatens Natural environment due to emission of toxics gases from itcausing

air pollution and ozone layer depletion, in addition to this dioxins release that have

potential of causing various anthropogenic problems like hormonal abnormalities

(Raziyafathima etal. 2016). The aromatic rings, chains, and bonds make the plastic

polymer resistant to microbial degradation, thus persisting for centuries and affect-

ing the natural environment, causing serious air, water, and soil pollution (Eriksen

etal. 2014).

Table 14.1 Table showing different uses of plastics (Shah etal. 2008)

Plastic Uses

Polyethylene Plastic shopping bags, food packaging lm, bottles of milk and

water, toys, pipes used for drainage and irrigation purposes, bottles

of motor oil

Polyethylene terephthalate

(PET)

Bottles of carbonated soft drink, packages of processed meat, jars

of peanut butter, lling of sleeping bags and pillows, textile bers

Polystyrene Disposable items, packaging, laboratory and electric products

Polyvinyl chloride Automobile seat covers, shower hangings, raincoats, bottles, visors,

soles of shoes, garden hoses, and electricity pipes

Polyurethane Tires of automobiles, gaskets, automobile bumpers, insulation of

refrigerators, cushioning of furniture, and life jackets

Polypropylene Bottle caps, drinking straws, medicine vials, seats, batteries and

bumpers of automobiles, disposable syringes, and carpet backings

Polycarbonate Making nozzles on papermaking machinery, streetlights, safety

wires, car’s rear lights, baby feeders, housewares, skylights, and

greenhouse roofs and sunrooms

Polytetraouroethylene

(PTFE)

Industrial applications, that is, chemical plant, electronics, and

bearings. Coatings on nonstick saucepans and frying pans

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343

14.5.2 Landlling

Around 60% of plastic waste is discarded in a landll, which is known to be one of

the best methods of disposing of solid waste material. It’s a widely used method for

disposal of plastic, but the main drawback of this approach is that on the open land,

the dumped plastic is not quickly degraded (Qasaimeh etal. 2016). Plastic litter,

which is dumped openly or in sanitary landlls, produces harmful leachate. In addi-

tion, disposing plastic in landlls results in land degradation and also increases the

chance of plastic ingestion by animals. Ultimately, the release of plastics into

aquatic environments leads to their intake by aquatic animals which causes death of

such organisms and creates a high risk of biomagnications and bioamplication of

harmful plastic substances (Denuncio etal. 2011).

14.5.3 Recycling

It is essential to have proper treatment as well as disposal options for plastic waste

treatment. Recycling plastic is a better disposal option, but this method has its draw-

backs since it can no longer be recycled at the end of the life of products. The pro-

duction and use of biodegradable plastics is another method (Al-Salem etal. 2009).

14.6 The Assessment ofBiodegradable Nature

The assessment of the biodegradable nature of plastic can be done by measuring the

structural changes under the microscope or by evaluating the growth of microorgan-

isms after the biological and enzymatic action along with the evolution of carbon

dioxide (Kissi etal. 2001; Ahmed etal., 2018). Plastics are of numerous kinds such

as polystyrene (PS), polyethylene (PE), polyurethane (PU), polypropylene (PP),

poly(vinyl chloride) (PVC), and poly(ethylene terephthalate) (PET). Plastic poly-

mers basically comprise of hydrocarbon monomers created by natural and synthetic

organic and inorganic raw material. Generally, there are two main kinds of plastic,

that is, thermoplastics and thermoset plastics. Thermoplastics are long linear carbon

chains, having different molecules which are joined end to end. Among different

kinds of plastics, the microplastic is more dangerous (Cole etal. 2011) as it is dif-

cult to identify and tracked (Kutten, 2019) and is accumulating inside the body of

different organisms causing severe anomalies resulting visible decline in abundance

and diversity of sh and coastal birds.

14 Remediation ofPlastic Waste Through Cohesive Approaches

344

14.6.1 Factors Affecting Biodegradation ofPlastics

The effects of the biodegradation process are also depending on some main factors

like characteristics of the polymers and the condition of the environment. The char-

acteristics of the polymer include functional group, morphology, molecular weight,

stability, crystalline nature, additives, cross-link, and copolymers. Low molecular

weight polymers are favorable for biodegradation (Varjani and Upasani 2017), and

environmental conditions like temperature, ultraviolet radiations, pH, hydrophobic-

ity, salinity, presence or absence of O2, etc. also affect the biodegradation of plastics

(Gu 2003). In the formation of polymers, stabilizers and antioxidant are used which

drop off biodegradation time, and also it can be harmful for microbes (Kale etal.

2015). In addition to all listed above, the structural factors (linearity and polymer

branching; bonding type, such as C-C, amide, and ester), the polymers’ molecular

composition, and physical structure such as powder, lms, pellets, and bers can

also affect the polymer’s biodegradability. The rate at which the polymer degrades

eventually depends upon the procedure of decaying and speeding of process.

14.6.2 Different Steps ofBiodegradation Mechanisms

Biodegradation is a process of degrading complex organic polymers into simpler

forms by using microbes (Restrepo-Flórez etal. 2014). Processes causing altera-

tions in polymer functions or properties due to chemical, physical, or biological

reactions ultimately result in bond breakage. Chemical alterations have been cate-

gorized as polymer degradation (Ghosh etal. 2013). Optical mechanical or electri-

cal properties of a substance or material change due to degradation through cracking,

crazing, erosion, discoloration, or phase separation. The changes comprise bond

breakage and chemical transformation, and new functional groups are also formed

(Nigam 2013).

Degraded particles are again scattered in the environment, and those particles are

generally nontoxic. For biodegradation, microbes form the catalytic enzymes in

nature (Hadad etal. 2005). Through various enzymatic activities and cleavage of

bonds, the degradation process is achieved by microbes (Pathak and Navneet 2017).

The degradation process occurs in sequential phase’s bio-deterioration (changing

the the physicochemical characteristics of the polymer), bio-fragmentation (break-

down of polymers into simpler form through enzymatic cleavage), assimilation

(microbes uptake the molecules), and mineralization (after the degradation, oxi-

dized metabolites such as CO2, H2O, and CH4 are produced, which are shown in

Fig.14.1).

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345

14.6.3 Aerobic andAnaerobic Degradation ofPolymers

Degradation of polymers depends on polymers’ physicochemical properties. The

weight and crystalline nature are the main properties of polymers which affect the

efciency of microbial degradation. The polymer degradation enzymes are divided

into two types, that is, extracellular depolymerase and intracellular depolymerase

(Gu 2003). In the degradation of complex polymers into simple units such as mono-

mers and dimers, exoenzymes are generally involved. They are also used as carbon

and energy sources by microbes. During or at the end of processes, polymer degra-

dation (mineralization) produces new products, for example, CO2, H2O, or CH4 (Gu

2003). On the availability of oxygen, this degradation process is dependent. In both

aerobic and anaerobic cases, mineralization of polymers takes place. Polymers are

converted into simple form by using microorganisms, and mineralization produces

CO2 and H2O in the presence of oxygen, while in anaerobic conditions, it produces

organic acids like CH4 and H2O which are shown in Fig.14.2. Biodegradation is an

efcient way to clean up the waste of plastic with the help of microbes (Kumar etal.

2011). Enzymes of microbial species are used for pollution control and contribute

to the creation of an environment that is friendly (Gu 2003). Various types of

microbes are known to be used through the process of mineralization.

Fig. 14.1 Different steps of microbial polymer degradation

Enzymes

POLYMERDimers

Anaerobic

Aerobic

Microbial Biomass

, CO

, H

Oligomers

Monomers

Microbial Biomass

, H

Fig. 14.2 Polymer degradation by aerobic and anaerobic condition

14 Remediation ofPlastic Waste Through Cohesive Approaches

346

14.7 Major Properties Affecting Plastic Biodegradation

14.7.1 Characteristics ofPlastics

Plastic products take hundreds of years to degrade naturally, and the material only

partially degrades after that. It is important to know the structure and characteristics

of polymers that change with external environmental factors according to the life

cycle of the material. Weight reduction is an important parameter that helps to mea-

sure the degradation rates. This section describes some of the important properties

that assist in indicating the rate of degradation (Artham and Doble 2008).

14.7.2 Weight ofPlastic Films

Plastic lm is preferred as it isLight weight, durable nature, and low cost. Therefore,

due to these properties of plastic it isused in the world for many applications and

mostly in packaging (Kumar etal. 2013). Plastic is not easily degraded because they

are durable and made up of such a strong C-H bond. One way for the degradation of

plastic is to degrade plastic biologically, which is commonly known as biodegrada-

tion (Moharir and Kumar 2019). Some researchers have placed the lms of plastic

in the soil to analyze the rate of biodegradation of plastics (Chiellini etal. 2003).

The loss of plastic lm rate before and after the study is used as a degradation rate

parameter with some other relevant parameters. Weight loss of plastic lm is the

indicating parameter of degradation. Therefore the essential parameter to be consid-

ered is the weight of plastic lms before and after the process of degradation (Hadad

etal. 2005).

14.7.3 Thickness ofPlastic Films

Any plasticmaterial strength is related to the thickness of material similarly thick-

ness of plastic shows its strength, thicker lm will be more strength and vice-versa.

In plastic lm degradation studies, it is one of the most signicant parameters that

must be taken into account. The degradation rate of thicker plastic lms is slow, and

a thinner plastic lm will degrade quickly. The thickness of plastic depends on the

application in which they are used (Moharir and Kumar 2019).

B. S. Zeb etal.

347

14.7.4 Density ofPlastic Films

Types of plastic are categorized by their densities. With the range of thickness,

every plastic has its density. It is an important parameter to count the viability of a

lm, and it plays an important role in which the transparency of the lm is a key

factor needed for certain applications (Gulmine etal. 2003).

14.7.5 Mechanical Properties ofPlastics

Plastic’s mechanical and elastic properties are useful in identifying the plastic

strength that would be useful for any further research to be carried out and used in

particular applications (Gerald 2000). Stress increases as these polymers distort

under pressure, and it relies on the polymers’ structure and mechanical characters,

and some of the main polymer mechanical properties are as follows.

14.7.6 Tensile Strength ofPlastic Films

TheTensile strength is a signicant mechanical character that shows the durability,

strength, and rigidity of the polymers (Ferreira etal. 2005). In many applications,

various thickness levels of polymers are tested in for tensile strength to know the

effectiveness in resisting external loading. The tensile test is performed to control

tension till the failure stage to understand the strength and capability of the polymer.

14.7.7 Plastic Film Elongation

Elongation is another important character. The breakpoint of polymers can be iden-

tied by performing this test that will help to understand the efciency of material

breakage at a particular length (Pedroso and Rosa 2005). Some external factors such

as temperature, sunlight, and UV radiation can affect the elongation of the polymer.

14.7.8 Young’s Modulus ofPlastics

Now the term Young’s modulus is replaced by the elastic modulus. For determining

any solid, material stiffness is measured by Young’s modulus. The linear elasticity

of materials basically denes the solid material stiffness. With different tempera-

tures, Young’s modulus varies. Young’s modulus of polymers is measured to

14 Remediation ofPlastic Waste Through Cohesive Approaches

348

analyze its elastic behavior. The stress-strain relationship is dened by this mechan-

ical property (Pedroso and Rosa 2005).

14.8 Potential Degradation Procedures

A process which causes the breakage or splitting of complex or larger fragments

into simple and small size particles is known as degradation; degradation of these

polymers into monomers can be done as a result of any physical and chemical

changes; in the degradation process, a lot of procedures are involved. The plastic

degradation includes all processes (either natural or synthetic) accounting for

changing plastic properties (Yousif and Haddad 2013). Depending upon composi-

tion and type, the degradation time of plastics varies like plastic bottles require

400–500 years and grocery bags require 10–1000 years to degrade (Eriksen etal.

2014). Plastics can be degraded by a number of physical, chemical, and biological

methods. Physical degradation includes polymer recrystallization or denaturation of

protein structures and exposure to ultraviolet rays which refer to the polymer break-

down by photooxidation, releasing different chemical compounds and radicals,

decreasing molecular weight leading to polymer destruction, and converting it into

a more hazardous form. Several procedures like photochemical and thermal degra-

dation can be used for the biodegradation of polythene (Lu etal. 2009). Plastic

accumulation in our environment is a very serious concern, and its accumulation in

the environment is causing long-term problem to living organisms and their habi-

tats. It is actually destroying the natural habitat of ora and fauna, especially those

in the aquatic environment (Restrepo-Flórez etal. 2014). Degradation of plastic

mainly occurs by three processes which are physical, chemical, and biological deg-

radation process (Yousif and Haddad 2013). The biodegradation of plastics occurs

actively, depending on their properties, under different conditions, and degrading

microorganism varies from one another and has its own optimum soil and water

growth conditions. Ecological factors such as humidity, pH, temperature, salinity,

aerobic and anaerobic conditions, solar light, water, pressure, as well as plant envi-

ronment not only affect the degradation of polymers but also have a critical impact

on the microbial community and enzymatic activity (Nigam 2013).

Plastic biodegradation requires adherence of the microbes to the polymer layer,

microorganism growth by using the polymer as the origin of carbon source, and

polythene degradation (Gunatillake etal., 2006). The biological decomposition of

plastic, extracellular depolymerization and intracellular metabolism, involves at

least two forms of enzymes (Tilman 1977). From the previous work, it is observed

that UV due to the synergistic effect of nitric acid and microbial action encouraged

an oxidation reaction that improves and increases the rate of LDPE biodegradation

(Egli 1995).

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349

14.9 Properties andApplications

PET is semicrystalline thermoplastic polyester (Harrison and Wren 1976). It is pro-

duced by different companies under separate trade names. PET is strong and dura-

ble, stable both chemically and thermally with low gas permeability, and easy to

handle and manage (Ingram etal. 1999). This combined effect of properties makes

PET a valuable product for a variety of applications and a considerable component

of global plastic usage (Chen etal. 2011). More than 50% of the synthetic fabrics

generated globally consist of PET, and global usage of PET has been reported to

exceed $17 billion per year (Chen etal. 2011). The Sheets, lms, fabrics, food and

beverage packaging (especially soft drinks and water bottles), appliances, auto

parts, home appliances, lighting products power tools, sports goods, photography

devices, X-ray sheets and textiles are products based on the actual use and the

desired properties of PET.By controlling the polymerization conditions, PET can

be manufactured to specications (Nigam 2013).

14.10 Pretreatments forPlastic Degradation

It was anticipated that physical treatment may enhance the biodegradation rate

(Arkatkar etal. 2009). Physicochemical treatments of the polymer by microbes like

fungus lead to oxidation and further breakdown. Thus physicochemical pretreat-

ment of polymers helps in easy assimilation by the microbes (Arkatkar etal. 2009).

The oxidized polymer helps in adhesion of microorganisms and easily adheres to

the oxidized polymers surface, which become less hydrophobic and it the prerequi-

site biodegradation.

14.10.1 Physical Methods

The physical treatment strategies involve decreasing the plastic waste through phys-

ical methods like crushing (Al-Salem etal. 2009), incineration, and pulverizing.

Some of the other treatments of physical mode include thermal treatment, treatment

with ultraviolet rays, photooxidative degradation, etc. In addition, these types are

responsible for altering the polymer’s nature, shape, and structure to some extent

(Mohan etal. 2016). Plastic modications are identied by surface splitting, crack-

ing, polymer disintegration, degradation, decreased polymer weight, discoloration,

and gaps on the polymer surface, also referred to as aging.

Mechanical stress is provided by giving high speed or stirring and powdering,

splitting, mixing, chopping, crushing, etc.; this mechanical strength breaks the poly-

mer and decreases its molecular bulk (Ahmed etal. 2018). Plastic polymers is com-

plex compounds and microorganisms cannot ability to utilized it directly. The

14 Remediation ofPlastic Waste Through Cohesive Approaches

350

oxidation process reduces the long chain of plastic polymers and make availability

to microorganism by reducing its hydrophilic level. It also included UV exposure

and provides temperature.

14.10.2 Photodegradation

In order to degrade the larger and complex molecules into simple, smaller particles,

high-intensity photon particles are used like ultraviolet radiations to react with the

photo reactive groups, so the chains of polymers cleave in a procient way.

Photodegradation is a polymer degradation process that includes placement of lms

under the sunlight or ultraviolet rays and photodegrade them with time (Moharir

and Kumar 2019). Strong bond of polymers is hard to disrupt, but this kind of pre-

treatment will increase the rate of biodegradation.

14.10.3 Thermal Degradation

Thermal degradation is similar to the photodegradation (Ray and Cooney 2018).

Photodegradation includes chemical reactions occurring on the outer surface, while

thermal degradation occurs on the greater surface of the polymer (Ray and Cooney

2018). Thermal degradation occurs with heat treatments such as incineration, pyrol-

ysis, and gasication, but treatments such as incineration emit toxic gases, like diox-

ins and furans which are known to be the main hazards to humans and to the

environment as well (Erceg etal. 2018).

14.10.4 Chemical Degradation

Chemical treatment methods depend on different chemicals usage that have capabil-

ity of splitting plastic polymer’s chain and converting it into forms which are non-

toxic in nature (Lin and Yang 2009). These methods cannot be used on large scale

due to the problem of disposing these chemicals that are used in these methods.

Treating plastic polymer with nitric acid enhances the rate of biodegradation (Leja

and Lewandowicz 2010). Many previous investigations also reported that providing

pretreatment enhanced the rate of biodegradation (Ahmed etal. 2018). Pretreatment

may enhance the breaking of polymer bond due to oxidation, and it also improved

the hydrophilic level and converted plastics into a more available form which can be

easily assimilated by microorganisms (Vimala and Mathew 2016). UV, nitric acid,

and temperature exposure are the best ways for physicochemical degradation as

reported by Ray and Cooney (2018).

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351

14.10.5 Biological Degradation

Biodegradation is another method for the disposal of plastic waste, it is an environ-

mental friendly technique, and it is more suitable than physical and chemical degra-

dation (Shah etal. 2008). Latest developments have advocated that many organisms

(bacterial and fungal species) have the ability to degrade plastics, and in this pro-

cess, by-products are produced that are nontoxic in nature (Restrepo-Flórez etal.

2014). As no secondary contaminants are produced like landlling and incineration,

this method of treatment is cheap, efcient, and protable that can be applied on

large scale in reactor operation for organic waste treatment (Michaud etal. 2007).

Ethanol and biofuels are useful end products of microbial degradation of pollutants

(Iranzo etal. 2001). But this technique is not practically applied at commercial scale

(Shah etal. 2008).

The natural process of organic and inorganic degradation by microbes into nutri-

ents is known as biodegradation. Degradation is conducted by different organisms

(bacteria, algae), insects, and those organisms which eat dead matter and recycle it

into new forms. All naturally produce plastic like cellulose, chitin, and PHAs which

can be completely broken down by microorganisms. Under natural conditions,

polyethylene degrades slowly, or it is nonbiodegradable, and this causes major envi-

ronmental problems. Nondegradable solid waste such as polyethylene is most com-

monly used, and increasing the amount of waste in the environment has been a

threat to the world (Arkatkar etal. 2009). Decaying of polymer or plastic means any

type of physicochemical changes in the plastic construction and nature results from

the ecological factors, like light, heat, humidity, biological activities, or any chemi-

cal condition (Nigam 2013). Polymeric substances are the potential carbon and

energy sources for heterotrophic microorganisms, including bacteria and fungi, in

many respects (Ghosh etal. 2013). Biodegradation is dened as the decaying or

dissolution of pollutant molecules by microbial actions and secretion of enzyme.

Microorganisms biodegrade the polymers which are natural or synthetic. The mak-

ing alterations mostlydeteriorate the sturucture/function of the polymers like bond

breakage having biological, physical and chemical reactions and arecategorized as

polymer degradation processes. (Ghosh etal. 2013). These degradation processes

bring changes in the optical mechanical or electrical characteristics, crazing, crack-

ing, discoloration, erosion, or phase separation. The changes comprise bond scis-

sion, chemical transformation, and the formation of new functional groups

(Nigam 2013).

Biodegradation refers to the degradation or deterioration of complex organic

polymer into simpler components by the help of microbes (Restrepo-Flórez etal.

2014). Biochemical or microbial degradation is a novel concept which involves liv-

ing microbes in the degradation process by expending the enzyme produced by

these organisms. In the complete process, these microbes utilize these polymers as

their carbon and energy source (Nigam 2013).

Biodegradation happens by enzyme activity and chemical degradation by living

organisms. Initially, the breakdown of polymers into smaller molecules, that is,

14 Remediation ofPlastic Waste Through Cohesive Approaches

352

monomers, is through abiotic reactions such as oxidation (Patel and Bhaskaran

2016). Photo degradation also known as hydrolysis, or biotic reactions such as

microorganism degradation during thismany microbes are active in the presence of

oxygen or in the absence of oxygen (Zheng etal. 2005). Environmental factors such

as light, temperature, humidity, and chemical conditions also help in plastic degra-

dation. Breakdown of polymers by means of microbes, that is, algae, fungi, and

bacteria, is actually chemical degradation material, that is, polymer degradation, so

it is a type of degradation involving biological activity (Patel and Bhaskaran 2016).

It generally denotes the degradation and accommodation of polymers by living

microorganisms to produce degradation products. Biodegradable polymer is then

degraded, and carbon dioxide, methane, and biomass are the end products (Zheng

etal. 2005).

This is comparatively more suitable method than physical and chemical degrada-

tion as it has less or no hazardous impacts and has relatively fast and efcient deg-

radation potential and is an environmentally friendly technique, but yet not

practically applied at commercial scale (Shah etal. 2008). Polymer conversion is

done by microbes by mineralization, and under aerobic conditions mineralization

produces carbon dioxide and water, while in the absence of oxygen, it forms meth-

ane and carbon dioxide (Singh and Sharma 2008). In our natural environment, the

biodegradation process is performed by different microbes, but their polymer con-

sumption rate is slow (Shah etal. 2008). It is evident that some microbial strains

have the potential to degrade the plastic; thus such strains can be employed in the

degradation of polymer by providing appropriate controlled environment (Zheng

etal. 2005). Both natural and articial plastic can be utilized effectively by different

microbial strains. Degradation is a very complex and slow process. It doesn’t start

by direct action of microorganisms but is highly inuenced by ecological factors,

that is, pH, temperature, and UV. The biological degradation is accompanied by

solubilization, dissolution, charge formation, enzyme-catalyzed degradation, and

hydrolysis (Singh and Sharma 2008).

Microbes are present in all kind of environments where life exists. Different

organisms mainly fungi bacteria produce variety of enzymes they also differs

between the similar species, and these enzymes also help in degradation of polymer

(Zheng etal. 2005). Microbes have special plan for the utilization of plastic as it acts

as a carbon and energy source for them. Degradation of plastic waste by means of

microbes is the most expedient method of degradation. It is generallybased on 2

steps, in the rst step adhering of enzyme substrate(polyethylene) occurs and causes

hydrolytic cleavage, fungus and bacteria that produces intra and extracellular

enzymes and further cause the degradation of polymer (Singh and Sharma 2008).

The most prominent microbes that have the capability of polymer degradation

are fungi and bacteria, but both have quite different mechanisms of degradation, and

both require different conditions for their growth (Anthony 2016). The assessment

of biodegradable nature of plastic can be done by performing the measurement of

structural changes by microscope observation or by evaluating the growth of micro-

organisms after the biological and enzymatic action along with the evolution of

carbon dioxide (Anthony 2016). Many microorganisms (bacteria, fungus, and

B. S. Zeb etal.

353

algae) have been isolated with the ability to grow on polyethylene. The effects of

these microbes have been described on the physiochemical properties of these poly-

mers, including changes in crystalline, molecular weight, sample topography, and

functional groups found on the polythene layer. While several scientists have dem-

onstrated the biodegradation of polyethylene, the enzymes involved and the mecha-

nisms associated with these phenomena remain unclear (Restrepo-Flórez etal. 2014).

Biodegradation is inuenced by various factors, including the features of plastic,

the type of pretreatment, and the type of organisms. The characteristics of polymers

like mobility, tacticity, crystalline nature, molecular weight, the form of functional

groups and substituents present in their structure, and the added plasticizers or addi-

tives to the polymer all play an important role in their degradation (Hu etal. 2019).

Microbes are present in every environment where life exists; different organisms

mainly fungi and bacteria produce a variety of enzymes, and they also differ between

similar species, and these ten enzymes also help in the degradation of polymer

(Zheng et al. 2005). The most prominent microbes that have the capability to

degrade polymers are fungi and bacteria, but both have quite different mechanisms

of degradation, and both require different conditions for their growth.

14.11 Enzymatic Degradation by Microbial Agents

Different microbial species excrete different enzymes for LDP degradation, such as

bacterial enzymes which include laccases, peroxidases, lipases, hydrolases, and

glycosidase and fungal enzymes which include catalases, proteases, ureases, hydro-

lases, laccases, peroxidases, and lipases (Bhardwaj etal. 2013). Different enzyme

like Lignin that is a degrading enzyme produced by fungi and manganese peroxi-

dase, that ispartially puried from the strain of Phanerochaete chrysosporium also

aids in the degradation of high molecular weight polyethylene under carbon limited

and nitrogen-limited conditions (Restrepo-Flórez etal. 2014).

14.12 Mechanism ofEnzymatic Degradation

14.12.1 Lignin-Degrading Enzymes

A number of enzymes are involved in hydrolysis of polymers. These enzymes are

laccase, manganese peroxidase, glycol oxidase, lignin peroxidase, sugar oxidase,

alcohol oxidase, and quinone oxidoreductase (Martínez et al. 2005). Lignin-

degrading fungi release more than 100 laccases to date and can range in size from

60 to 70kDa (kilo Dalton) (Baldrian 2006). Laccases are copper-containing oxi-

dases that catalyze the electron oxidation of primarily phenolic and lower-redox

potential compounds, although they can oxidize non-phenolic compounds in the

14 Remediation ofPlastic Waste Through Cohesive Approaches

354

presence of mediators, such as 2,2’-azino-bis (3-ethylbenzothiazoline-6-sulphonic

acid) (Martínez etal. 2005). Glycol oxidase, sugar oxidase, and alcohol oxidase are

a diverse group of enzymes that also take part in lignin degradation. These enzymes

produce H2O2, a vital product in ligninase activity through the oxidation of ligninase

enzymes (Martínez etal. 2005). Lignin is a plant woody biomass organic aromatic

polymer and intransigent to nature degradation. White rot fungi have been widely

studied for plastic degradation as the most effective lignin degrading microbes.

Polyethylene membrane degradation by lignin-degrading fungus. Under various

nutrient conditions, Phanerochaetechrysosporium, Trametesversicolor, showed that

manganese peroxidase (MnP) is the primary enzyme in polymer degradation.

In the presence of Tween 80, Mn (II) and Mn (III) chelators, partially distilled

MnP used for polyethylene surface treatment led to major degradation (Iiyoshi etal.

1998). Four groups, CHO, NHCHO, CH3, and CONH2 were formed through nuclear

magnetic resonance (NMR) examination of bio-degraded nylon-66 with fungus

IZU-154 that decay lignin also showed that the nylon66 was decayed oxidatively

(Deguchi etal. 1997).

Lignin-degrading fungi primarily secrete laccases, where the oxidation of vari-

ous polyaromatic compounds is catalyzed. Laccase is also known for nonaromatic

substrate degradation (Mayer and Staple 2002). Laccase can also perform oxidation

of polyethylene’s hydrocarbon backbone. There will be reduction of 20% and 15%,

respectively, of the average molecular weight and molecular number of polyethyl-

ene when we incubate cell-free lacquers with polyethylene (Bhardwaj etal. 2013).

The degradable polymer (comprising pro Oxidant and 6% starch) was allowed to

treat with Phanerochaete chrysosporium, Streptomyces viridosporus T7A, S. badius

252, S.Setonii75 Vi2 among them Streptomyces viridosporus T7A treated plastic

showed a 50% decline in tensile strength.

The ability of Pleurotus ostreatus to break down oxo-biodegradable plastics

without prior physical intervention, such as UV or thermal heating, racks, and small

holes was formed on the surface of plastic from the formation of OH groups and

C-O bonds after the incubation period of 45 days. In fact, the dye deterioration in

such bags has been noted. La and MnP enzymes secreted by polyethylene can be

degraded through Chaetomium globosum fungus (Sowmya etal. 2015). Various

biological mechanisms such as chemical, thermal, photo, and biodegradation play

their role in polyethylene deterioration (Shah etal. 2008). Microbes as part of sec-

ondary metabolism have a natural capability to convert or absorb mass of sub-

stances, including hydrocarbons (PAHs), pharmaceutical products, and metals.

Plastic polymer build functional groups by solubilizing through enzymes to enhance

hydrophilicity, and the main polymer chains are weakened, which results in bad

mechanical properties and in low molecular weight polymers which makes them

more available for further microbial incorporation (Shah etal. 2009).

Biodegradation of plastics often contributes to the breakdown of polymers by

certain enzyme systems into oligomers and monomers or further transformation

into organic intermediates (such as acids, alcohols, and ketones) (Arkatkar etal.

2009). Microbial cells absorb these water-soluble cleaved products where they are

metabolized. After aerobic metabolism, CO2 and water formed, while anaerobic

B. S. Zeb etal.

355

metabolism produced carbon dioxide, water, and methane as end products. The

polymers mechanically breakdown through dome physical variables like pressure,

temperature, and humidity by which the process is stimulated by biological agents

such as enzymes as well as other metabolites.

Plastic biodegradation due to difculties in penetrating extracellular enzymes

into the plastic polymer is usually called surface degradation, therefore acting only

on the surface of the plastic polymer. Plastic degradation is when the pro-oxidants

catalyze the formation of free radicals in polyethylene that react to the polyethylene

matrix with molecular oxygen. The enzymatic hydrolysis degradation of plastic

polymers is a two-step process: Initially, the enzyme attaches to the substratum of

the polymer and then catalyzes a hydrolytic cleavage. Intracellular deterioration is

the hydrolysis of an endogenous carbon supply by the growing microbe itself,

whereas extracellular degradation does not necessarily require the use of an exoge-

nous carbon source. La and MnP enzymes secreted by Chaetomium globosum fun-

gus were responsible for the degradation of plastic polymer (Sowmya etal. 2014).

14.12.2 Laccases

Laccase enzyme is a benzene diol, a multi-copper enzyme and one of the three main

ligninases. Laccase catalyze the oxidation of wide range of phenolic substrates

including diphenols, polyphenols, substituted phenols, diamines, and aromatic

amines, with the reduction of molecular oxygen to water. Laccase is widely present

in the number of bacterial fungal and plant species as well. Laccase is involved in

the degradation of lignocellulose substances, plant pathogenesis, and pigment pro-

duction; they also act as oxidizing agent for variety of inorganic and organic com-

pounds like aromatic amines, substituted phenols, diphenols, polyphenols, and

diamines with associated reduction of molecular oxygen to water; in recent studies

laccases are also being used in industrial applications like biopolymer modication,

bioremediation, bleaching agent in textile industry, detoxication of efuent, and

pulp lignication. For industrial application discovery of novel laccases with variety

of substrate specications is very important that makes them highly useful biocata-

lysts for various biotechnological applications.

14.13 Plastic Biodegradation Analysis Techniques

Biodegradability of polyethylene can be described through tracking the modica-

tion of CO2, the intake of O2, improvements in the attribution of polymers (physico-

chemical), and the maturing of species. Several experiments could be carried out to

assess plastic degradation for the mentioned purposes (Mohan and Shrivastava

2010). Loss of weight may be caused by chemical leaching, including plasticizers.

The degradation of polymers having low molecular weight fraction without

14 Remediation ofPlastic Waste Through Cohesive Approaches

356

degrading long chains can result in the development of carbon dioxide. Very minor

changes in the chemical composition or skipping any additives of plastics affect the

quality of plastic. To check the level as well as nature of decaying, there are a num-

ber of techniques that are available.

14.13.1 Mechanical Properties

The Tensile strength-Elongation at fail and modulus of the plastic polymer is

mostlyexamined by dynamic mechanical Analysis (DMR).

14.13.2 Physical Properties

Morphology, that is, micro cracks, are analyzed by scanning electron micro-

scope (SEM).

14.13.3 Chemical Properties

Chemical properties are determined by Fourier transform infrared spectros-

copy (FTIR).

14.13.4 Molecular Weight

Thethin layer Chromatography (TLC), Chemilluminesence, Gas Chromatography-

Mass Spectrometry (GC-MS), Gas Chromatography (GC), Nuclear Magnetic

Resonance (NMR), Matrix Assisted Laser Desorption Ionization-Time of Flight.

14.14 Mechanism ofPlastic Biodegradation

Different microorganisms like algae, fungi, and bacteria produce different chemi-

cals like mucilaginous substances by algae, while bacteria and fungi produce lac-

cases, hydrolases, PETases, peroxidases, and lipases which help in cleaving the

polymer structure into simpler and available form for microbes as reported by

Bhardwaj et al. (2013). Lignin-degrading fungi secrete laccase enzyme having

capability to break the complex structures like aromatic and polyaromatic

B. S. Zeb etal.

357

compounds. Meanwhile, laccases are also involved in degradation of nonaromatic

compounds (Restrepo-Flórez etal. 2014).

Different microorganisms produce a variety of enzymes, and they also differ

between the similar species, and these enzymes also help in the degradation of poly-

mers like plastics (Zheng etal. 2005). Microbes have a special plan for the utiliza-

tion of plastic as it acts as a carbon and energy source for them. Degradation of

plastic waste by means of microbe is the most expedient method of degradation. It

is based generally on two steps; in the rst step adhering of enzyme to substrate

(polyethylene) occurs, and the second involves the hydrolytic cleavage as fungus

and bacteria produce intra- and extracellular enzymes that further cause the degra-

dation of polymer (Singh and Sharma 2008). Recently, it has been reported (Kumar

etal. 2017) that the most dominant microalgae were Scenedesmus dimorphus (green

microalga), Anabaena spiroides (blue-green alga), and Navicula pupula (diatom). It

was shown that polyethylene sheet showed the proliferation of microalgae in both

outer and inner sides, and the erosion cum degradation was obvious.

14.14.1 Microbial Growth andPlastic Degradation

It was evident that the microbial species produced biolms on the surface of PET

plastic during the current study and the growth of microbes on plastic lms was

efcient when provided with pretreatment. The growth of various microbial species

like bacteria, fungi, microalgae, and lichens on plastic was regarded as a milestone

in plastic biodegradation. It was evident from compound microscopy and scanning

electron microscope (SEM) analyses that microbes were able to grow on cracks and

shers created during pretreatment. Very few literature is published on the PET

biological degradation or its utilization to support microbial growth. Rare examples

are members of the lamentous fungi Fusarium oxysporum and F. solani, which

have been shown to grow on a mineral medium with PET yarn (although growth

rates have not been given). Once identied, microorganisms with the enzymatic

machinery needed to break down PET could serve as an environmental remediation

strategy as well as a breakdown and/or fermentation platform for the biological

recycling of PET waste products. The use of PCL as a selective isolation substrate

deserves a comment. Cutinase, a serine esterase secreted by many phytopathogenic

fungi, including F. solani f. sp. pisi (Murphy etal. 1996), may have a low substrate

specicity. Certain cutinases hydrolyze cutin and can also degrade PET (Lin and

Kolattukudy 1978). Cutinase is induced by cutin or suberin (Murphy etal. 1996)

and can be repressed by glucose (Lin and Kolattukudy 1978). On this general basis,

PCL hydrolysis has been used as an initial screen to study fungal isolates that pro-

duce enzymes that may be active on aromatic synthetic polyesters such as

PET.Esterases and cutinases from various fungi and bacteria can hydrolyze ester

bonds in PET (Muller etal. 2001; Nimchua etal. 2007).

14 Remediation ofPlastic Waste Through Cohesive Approaches

358

Regarding PET degradation by microalgae, a recent report showed that diatoms

(a group of microalgae) have the ability to degrade PET through the production of

the enzyme PETase under eosinophilic marine conditions (Moog et al. 2019).

Another aspect of the biodegradation of plastic is the development of efcient

closed or open loop recycling strategies for TPA (and EG) in order to synthesize

new PET from its own degradation products through to further metabolism.

Engineering microalgae metabolism to create cells that can fully metabolize PET

and use it as a carbon source (Moog etal. 2019). The same authors suggested that

physically treated PET can be efciently biodegraded by enzymes such as PETase,

which are produced by microalgae such as diatoms. Once an enzyme such as PETase

or laccase has started to break down PET, it is speculated that its by-products may

be further affected by some other enzymes produced by other microbial consortia in

the same environment. down PET, it is speculated that its by-products may be fur-

ther affected by some other enzymes produced by other microbial consortia in the

same environment.

14.14.2 Products ofMicrobial Degraded or Treated Plastics

Previous research has demonstrated that carbon dioxide is the prime product

released through polythene biodegradation. The production of aldehydes, ketones,

and carboxylic acids was reported in LDPE lm extrusion smoke in the extrusion

coating. Rhodococcus rubber (C208) generated polysaccharides and proteins using

polythene as a carbon source in another study. Rhodococcus rhodochrous

ATCC29672 (bacterium) and Clados produced polysaccharides and proteins.

Rhodococcus rubber (C208) formed polysaccharides and proteins using polythene

as a carbon source (Sivan etal. 2006). In one more study, Rhodococcus rhodochrous

ATCC29672 (Bacterium) and Cladosporium cladosporioides ATCC 20251 (fun-

gus) utilized polythene to generate polysaccharides and proteins, while Nocardia

asteroides GK911 (bacterium) generated proteins only.

14.15 Conclusion

Different pretreatment and cohesive methods with the most effective species are

very helpful in the degradation of plastic. The use of different efcient species on

different types of plastic and examine which plastic type can be more easily

degraded. In order to understand the complete process of biodegradable plastics

over a longer period of time, prolonged biodegradation studies on plastics using

selected microorganisms should be carried out.

B. S. Zeb etal.

359

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14 Remediation ofPlastic Waste Through Cohesive Approaches

T. Ahmed, M. Z. Hashmi (eds.), Hazardous Environmental Micro-pollutants,

Health Impacts and Allied Treatment Technologies, Emerging Contaminants and

Associated Treatment Technologies, https://doi.org/10.1007/978-3-030-96523-5_15

Chapter 15

Treatment Technologies

fortheEnvironmental Micro-pollutant

AyeshaAyub andSheikhSaeedAhmad

Abstract Advance studiesrelated to MPs contaminationalong with their metabo-

lites are detected in the aqueous environment throughout the world. Their biological

nature and continuous emission render them as “prospective pollutant” or “emerg-

ing pollutants.” The major categories of MPs are divided into eight groups. For the

absolute removal of MPs and their metabolites, there is no specic technique and is

quite difcult and somewhat impossible because of their distinctive properties. The

emission of MPs in large amounts in different aqueous bodies in different parts of

the world renders a serious threat to the aquatic as well as human ecosystem. So, the

most applicable methods used for MPs are activated carbon absorption, coagulation-

occulation, advanced oxidation process, and ozonation membrane bioreactor and

membrane process. The typical WWTPs cannot provide the expected results for the

elimination of signicant MPs. However, with little efforts, upgrading and optimiz-

ing the current protocols in the WWTPs is all set to crucially decrease the loading

rates of MPs. Besides all the conventional techniques and processes, advanced oxi-

dation processes (AOPs), activated carbon adsorption (granular activated carbon

and powdered carbon), coagulation-occulation, membrane bioreactor, and mem-

brane process are also applied for the removal of MPs. Amongall these persistent

treatment methods, advanced oxidation processes and membrane systems are the

most efcient techniques and come to the forefront. For both removal of micro-

pollutant and inhibiting the production byproducts and metabolites and other pollut-

ants, a combined treatment should be preferred to achieve the desired results.

A. Ayub · S. S. Ahmad (*)

Department of Environmental Sciences, Fatima Jinnah Women University,

Rawalpindi, Pakistan

e-mail: drsaeed@fjwu.edu.pk

366

15.1 Introduction

Among different pollutants micro-pollutants (MPs) are dened as anthropogenic

chemical compounds that mainly occur in the aquatic environment quite above the

natural substantial background level mainly because of urbanization and human

activities in modern as well as developing worlds but with concentrations so minute

that is found to be in trace levels (i.e., up to μg/L range). Therefore, MPs are speci-

cally dened by their occurrence in low concentration level and anthropogenic ori-

gin. Billions of natural as well as anthropogenic chemicals fall into this group of

pollutant. Few decades back, the occurrence and concentration level of MPs in the

aquatic environment have become an alarming global issue of increasing ecological

concern. MPs are also termed as emerging contaminants, engulng a vast and

expanding category of natural as well anthropogenic substances (Stamm et al.

2016). As of today, majority of the countries in the First World have successfully

been able to reduce the overall level of MPs in the aquatic environment by legalizing

and adopting appropriate effective measures. Consequently, the focus has been

shifted to this emerging class of contaminants because of their hazardous nature to

the elements of the biotic sphere. Ample of research found that it is not only the

pollutants that have been introduced into the environment most recently but also the

advancement in the development of analytical techniques and protocols that made it

possible to detect such substances despite their minute concentration in the aquatic

environment (Brack etal. 2015; Gavrilescu etal. 2015; Guibal etal. 2015).

The signicance of MPs in the environment is not essentially due to persistency

but because of their biological nature and continuous emission render them as “pro-

spective pollutant” or “emerging pollutants.” Advance research found that billions

of MPs along with their metabolites have been detected in aqueous bodies all around

the world (Escher etal. 2014). Meanwhile the existence of these MPs is very low in

the aqueous environment and unlikely results into acute toxicity, but it is concluded

that their long-term presence may cause chronic health conditions (Schriks etal.

2010). One study conducted in Germany detected the concentration up to several

μg/L of about 55 active pharmaceuticals with nine metabolites in the wastewater of

about 49 sewage treatment plants. Similarly, wastewater of several European treat-

ment plants was analyzed, and the result detected about 27 pharmaceutical com-

pounds and four metabolites, with the highest average concentration of about 1.0

μg/L (Larsen etal. 2004). Many of the detected MPs were active pharmaceutical

components, additives, excipients, and EDCs. These concluded results are alarm-

ing, but the situation is even worse in the developing countries, where the concentra-

tion and the number of many MPs have been detected exceedingly high. This can be

mainly attributed to the fact that in the developing countries, the majority of these

MPs are being sold as off-exchange products, consequently resulting in increasing

levels in the aqueous environment (Garcia-Galan etal. 2016). At the end, the wide-

spread scientic viewpoint concluded that a more advanced management approach

should be developed and implemented all around the globe (Brack etal. 2015). Yet

A. Ayub and S. S. Ahmad

367

precise management approach and legislation regulation for the safe permissible

level of MPs in the environment needs a further understanding of their fate anddis-

tribution, and concerning theirharmful effects should also be characterized. This

may include the transformation mechanism of several MPs in the environment, the

level of toxicity they cause in living organisms, and signicant effect on the ecosys-

tem along with the remediation strategies.

15.2 Transport andSources ofMPs inEnvironment

Micro-pollutants accumulated in the waterbody have a diverse origin, among which

the domestic waste efuents are the main source from surface water. In the aquatic

environment, pharmaceuticals which are detected frequently mainly originated

from convenience stores, drug stores, and hospitals. The main drawback of such

chemicals is that they are available without a prescription (i.e., ibuprofen, aspirin,

naproxen, acetaminophen). However, these medicines are mainly produced for

healthcare purposes for humans and animals, but they are not completely metabo-

lized in the body (Thomas and Foster 2005). Both the residual medicine and their

metabolites are excreted by animals and humans into the wastewater. Moreover, the

source of waste can be from the manufacturing industries and also expired medi-

cines. Pathways and sources of PMs in the urban water cycle are shown in Fig.15.1.

Fig. 15.1 Pathways and sources of PMs in the urban water cycle. (Ellis 2006)

15 Treatment Technologies fortheEnvironmental Micro-pollutant

368

EDCs consist of natural hormones, nonylphenol, insecticides, and bisphenol A,

considered as signicant MPs. Release of such compounds is from raw materials

like ame retardants and plastics. But these compounds can also directly be gener-

ated by humans (Poulsen etal. 2005; Prevedouros etal. 2006). These compounds

have hormone-like properties, and these EDCs have adversely affected the human

health (Sonnenschein and Soto 1998; Ellis 2006). Excretion of these compounds

from the human body into the sewage is directly discharged into the water system

nearby like lakes and rivers. Therefore, waste from sewage is commonly considered

a major source of MPs.

The physical and chemical properties and the bioavailability can inuence the

existence of MPs in the aquatic environment. A study conducted by Caliman and

Gavrilescu evaluated and categorized the elimination and generation of MPs based

on some signicant factors, that is, environmental factors, physicochemical proper-

ties, accumulation and transformation, retention, and transport (Caliman and

Gavrilescu 2009).

Moreover, it has been observed that the physical properties of MPs can inuence

the mobility of pollutants from one phase to another (e.g., soil-water movement).

Precipitation, sorption, colloid formation, and complexation all contribute to the

retention of MPs. The signicant mechanisms of transport consist of dispersion,

diffusion, active transport, and advection. The transformation processes, also called

the decomposition of the parental compounds as a byproduct, are ineffective to

prevent the complete reaching of MPs into the natural environment. In the applica-

tion of adequate conversion processes to treat the wastewater, it is very difcult to

control the concentration of MPs in the marine environment to be accumulated and

emitted (Moon-Kyung and Kyung-Duk 2016).

15.3 Categories ofMPs inAquatic Environment

The major categories micro-pollutants in the aquatic environment are divided into

eight groups, that is, personal care products (PCPs), agriculture, detergents, and

peruorinated compounds (PFCs), additives, ame retardants, new class, human

pharmaceuticals and veterinary drugs, and endocrine disruptive chemicals (EDCs).

A. Ayub and S. S. Ahmad

369

15.3.1 Personal Care Products (PCPs) (Table15.1)

15.3.2 Agriculture (Table15.2)

15.3.3 Detergents andPeruorinated Compounds (PFCs)

(Table15.3)

Table 15.1 Class, mode, and fate of PCPs

Micro

pollutant Class

Mode of

entry Fate Examples Author

Personal

care

products

(PCPs)

Fragrances and

synthetic musks

Direct

disposal of

industrial

efuents

and shower

waste

Terrestrial

runoff

freshwater,

wastewater

treatment

plants,

estuaries,

and

sediments

Musk ketone,

galaxolide, polycyclic

and macrocyclic musks,

tonalide

Ellis (2006)

and

Verlicchi

etal. (2010)

Antiseptics Chlorophene

Triclosan

Stimulants Caffeine

UV lters Methylbenzylidene

camphor, Benzophenone

Antihypertensive Diltiazem

Insect repellents N,N- diethyltoluamide

Table 15.2 Class, mode, and fate of agriculture

Micro

pollutant Class Mode of entry Fate Examples Author

Agriculture Pesticides Agricultural

waste

Water

and soil

DDT, chlordane,

aldrin

Ellis (2006) and

Verlicchi etal.

(2010)

Herbicides Terbuthylazine,

diuron, mecoprop

Table 15.3 Class, mode, and fate of PFCs

Micro pollutant Class Mode of entry Fate Examples Author

Detergents and

peruorinated

compounds

(PFCs)

Peruorooctanoic

acid

Households,

pesticides,

industries,

laundries,

agricultural

applications in

dispersants and

pesticides

Sewage

treatment

plants

Alkylphenol

carboxylates,

alkylphenols

(octylphenol

and

nonylphenol)

Ellis (2006)

and

Verlicchi

etal. (2010)

Peruorooctane

sulfonate

15 Treatment Technologies fortheEnvironmental Micro-pollutant

370

15.3.4 Additives (Table15.4)

15.3.5 Flame Retardants (Table15.5)

15.3.6 New Class (Table15.6)

15.3.7 Human Pharmaceuticals andVeterinary Drugs

(Table15.7)

Table 15.4 Class, mode, and fate of additives

Micro

pollutant Class Mode of entry Fate Examples Author

Additives Gasoline Disposal of

exhausted engine oil

and mobile exhaust

Water,

soil, and

air

Methyl t-butyl

ether, dialkyl

ethers

Ellis (2006) and

Verlicchi etal.

(2010)

Industrial Municipal waste and

food resources

Aromatic

sulfonates,

chelating agents

(EDTA)

Table 15.5 Class, mode and fate of ame retardants

Micro

pollutant Class

Mode of

entry Fate Examples Author

Flame

retardants

Industries

and

household

stuff

(electronics,

baby

products,

furniture,

appliances)

Dry and wet

disposition on

sediment and soil

that leads to

bioaccumulation

in the food chain

Hexabromocyclododecane,

diphenyl ethers,

tetrabromobisphenol A

tris(2-chloroethhyl)

phosphate, C10–C13

chloroalkanes,

polybrominated

Ellis (2006)

and

Verlicchi

etal.

(2010)

Table 15.6 Class, mode, and fate of new class pollutants

Micro

pollutant Class Mode of entry Fate Examples Author

New

class

Antibiotic

resistance genes

Genetic

adaptation

and mutations

Transfer of

horizontal gene in

microorganisms

tet (O), tet

(W), sul (I),

sul (II)

Ellis (2006)

and

Verlicchi

etal. (2010)

Nanomaterials Research

institutes

Water

A. Ayub and S. S. Ahmad

371

Table 15.7 Class, mode, and fate of pharmaceuticals and veterinary drugs

Micro pollutant Class Mode of entry Fate Examples Author

Human

pharmaceuticals and

veterinary drugs

Antibiotics Hospital disposal/

discharges, farmland

waste, accidental

spills

Groundwater, streams,

river and wastewater

treatment plants

Cefazolin, ciprooxacin, erythromycin,

lincomycin, amoxicillin, chlortetracycline,

noroxacin, doxycycline, penicillin

Ellis (2006) and

Verlicchi etal.

(2010)

Antidiabetics Glibenclamide

Analgesics Acetylsalicylic acid, diclofenac, ibuprofen,

indomethacin, acetaminophen, codeine,

dipyrone, ketoprofen, paracetamol,

mefenamic acid naproxen

Blood lipid

regulators

Bezabrate, etobrate, fenobric acid,

atorvastatin, clobric acid, pravastatin,

gembrozil

Cardiovascular

drugs (β-blocker)

Metoprolol, sotalol, atenolol, propranolol,

timolol

Psychiatric drugs Gabapentin, salbutamol, phenytoin,

primidone, carbamazepine, diazepam

Veterinary drugs Flunixin

X-ray contrast

agent

Diatrizoate, iopromide, iopamidol

Drugs of abuse Cocaine, tetrahydrocannabinol, amphetamine

15 Treatment Technologies fortheEnvironmental Micro-pollutant

372

15.3.8 Endocrine Disruptive Chemicals (EDCs) (Table15.8)

MPs are commonly found in water bodies at very low concentrations, ranging from

a few mg/L to more than a few μg/L.The “minimum concentration” and the vast

variety of MPs are not only difcult to detect by the associated analysis procedure

but also generate challenges for wastewater and drinking water treatment processes.

Wastewater treatment plants (WWTPs) nowadays are not designed specically to

eliminate MPs. Consequently, the majority of these MPs are able to pass through the

treatment methods used for wastewater because of their continuous introduction

and signicance of persistency. Furthermore, monitoring actions and precautions

for MPs have been fully implemented in majority of the wastewater treatment plants

(WWTPs) (Bolong etal. 2009). So, as a result, the fate of most of these MPs lies

within the aquatic environment, where they pose great threats to the biological eco-

system and also create mass trouble for the drinking water plants. The occurrence of

MPs in the marine environment has been most commonly associated with a large

number of harmful effects which consist of long-term and short-term toxicity and

microorganisms resistant to antibiotic and disrupting effects of endocrine (Fent

etal. 2006; Pruden etal. 2006).

Currently, for most of the micro-pollutants, standard protocols and discharge

guidelines do not exist. In order to set proper guidelines and standard permissible

limits for signicant MPs, further advanced research on the biotic responses to these

pollutants (including long-term and short-term toxic effects) is of utmost impor-

tance. Furthermore, the regulatory and scientic communities should provide

insight into the impact of each of the MP and also their antagonistic and synergistic

effects. Throughout the globe many research articles have been published regarding

the occurrence of emerging MPs in different aquatic environments and water bodies

such as groundwater (Deblonde etal. 2011) and wastewater (Lapworth etal. 2012)

as well as effective treatment methods for the removal of MPs (Bolong etal. 2009).

Additionally, researchers reviewed the removal of pharmaceutical and its efciency

by the conventional activated sludge systems by analyzing the municipal wastewa-

ter (Verlicchi et al. 2010). Similarly, Ze-Hua etal. (2009) studied the signicant

biological, chemical, and physical removal of endocrine-disrupting compounds.

Moreover, no data have been recorded yet concerning the comprehensive summary

of the occurrence of such miscellaneous MPs in the aquatic environment and also

the removal of signicant MPs in advanced treatment processes.

Table 15.8 Class, mode, and fate of EDCs

Micro

pollutant Class

Mode

entry Fate Examples Author

Endocrine

disruptive

chemicals

(EDCs)

Steroids

and

hormones

Groundwater

and soil

Estriol, diethylstilbestrol,

estradiol, androstenedione,

ethinylestradiol, estrone,

testosterone, progesterone

Ellis (2006)

and Verlicchi

etal. (2010)

A. Ayub and S. S. Ahmad

373

15.4 Environmental Effects

Environmental risks and effects posed by MPs mainly depend on their chemical and

physical speciation and afnity for water and solid matter, which can cause a sig-

nicant change and impact on their bioavailability. Moreover, the danger of such

MPs for the biotic entities is also dependent on the mobility and their ability to

accumulate and end up in the food chain. In recent studies, it has been revealed that

contaminants get accumulated in the tissues of marine organisms mainly by sus-

pended matter or ingesting water. Results however concluded that the concentration

level of MPs in the tissue of marine organisms may be recorded at a level compa-

rable with the concentration level found in the marine environment or even more.

The vast variation in the ecological conditions in different aqueous regions can also

inuence the bioavailability. Conditions such as temperature, pH changes, salinity,

and turbidity can be illustrated. Additionally, the physicochemical parameters along

with the species sensitivity can change the ability to bioaccumulate the malicious

pollutant. The majority of different MPs have different potential levels to bioaccu-

mulate, even when they are being exposed to the same concentration level of a

specic pollutant. Similarly, individuals of one species belonging to a specic group

when exposed to an equal concentration of contaminants during the same period of

time cannot possibly accumulate the contaminant at the same rate. It is associated

with many factors such as individual size, age, sex, and other physiological condi-

tion of the organism (Garnaga 2012).

The current data recorded for the concentration of MPs in the treated efuents

are quite low in order to assess the risk posed to the marine ecosystem. Target and

nontarget compounds after being chemically analyzed provided only a little infor-

mation about the signicant danger associated with MPs to the human life and the

surrounding environment. Furthermore, the analysis and detection of nontarget ele-

ments posed difculties for a research analyst. Despite the fact that in treated sew-

age efuents a complex mixture of MPs is present along with transformation and

degradation of MPs is also occurring, therefore it is difcult to foresee the hazard

associated with this type of approach, which is entirely based on the criteria for each

of the chemical substance (Fang etal. 2017). Most of the MPs in the treated waste-

water that are present exhibit toxic properties. Therefore, the major detrimental con-

sequence of MPs is basically attributed to the potential sublethal and acute toxicity

effects on the marine biota. Several studies on ecotoxological provided the desirable

results and seem to be an effective and suitable tool for assessing the negative

impacts arising from the treated wastewater ooded with MPs. In certain marine

ecosystems, the occurring results reecting from the ecotest are posing the actual

threat to the organisms. They are performed in less time, and the need of specialized

analytical tools and analyst is excluded. Ecotoxicity experiments are carried out on

a biological sample, that is, a population of a specic species of organism, exposed

to certain modications, that is, a particular contaminant for a period of time.

Advance studies associated with the ecotoxicological studies are based on marine

organisms, that is, bacteria, macrophytes, mollusks, crustacean, algae, and sh.

15 Treatment Technologies fortheEnvironmental Micro-pollutant

374

Furthermore, it is highly recommended to perform experiments incorporating dif-

ferent species that represent several trophic levels (Tran etal. 2018).

Research studies made in decade back revealed that many of the MPs identied

have a great potential to interrupt the endocrine processes in many organisms. These

chemicals are termed as endocrine-disrupting chemicals (EDCs). Basically, EDCs

are occurring naturally as well as anthropogenically in the environment. The deni-

tion adopted by the World Health Organization (WHO) is that EDCs are exogenous

and a mixture of EDCs compounds have the ability to disrupt the function of

theentire endocrine system which will consequently shownegative responsesin

anindividualorganism or affecttheir offsprings or intheentire subpopulation. The

EDCs belong to different families and are being able to disturb the natural hormonal

system by counteracting or mimicking as a natural hormone in the organisms that

are exposed to such chemicals (Huerta etal. 2016). At present estimation, there are

about a hundred thousand of emerging compounds among which thousand are

EDCs (Gore etal. 2014). Those chemicals may include bisphenol, phthalates, bro-

minated ame retardants, polychlorinated biphenyls (PCBs), organic tin com-

pounds, and some pesticides (Kima etal. 2015). Standard protocols for the biological

treatment of waste efuents incorporated in a typical WWTPs result only to remove

a certain fraction of compounds from the entire group of EDCs, comprising mainly

of polar nature (Välitalo etal. 2016). The presence of EDCs is detected in samples

taken from the surface water as well as in the groundwater. This observable fact is

alarming due to EDCs, when released into the water bodies are more likely to affect

the biotic entities, even when they are present at very low concentration (Kima etal.

2015). Ample of literature reported that even at very low concentrations EDCs can

cause a very adverse effect on the marine environment. One study reported that

zebrash were susceptible to estradiol at a concentration very low, that is, 0.2 ng/L

(Westerlund etal. 2000).

15.5 Treatment Technologies forMicro-pollutant Removal

For the complete elimination of MP groups, there is no specic technique and is

quite difcult and somewhat impossible because of their distinctive characteristics.

The treatment methods cannot remove both MPs and bulk compounds with a maxi-

mum efciency rate. The most applicable treatment technique used for MPs is acti-

vated carbon absorption (GAC and PAC), coagulation-occulation, advance

oxidation process (AOPs) and ozonation, membrane bioreactor (MBR), and mem-

brane processes.

A. Ayub and S. S. Ahmad

375

15.5.1 Coagulation-Flocculation

Coagulation-occulation treatment process is generally used to eliminate most of

the dissolved particulate matter and colloids. Table15.9 represents the removal ef-

ciencies of some of the signicant MPs processed by the coagulation- occulation

process.

Commonly, the coagulation-occulation treatment procedures are ineffective for

the removal of most of the MPs. A study is conducted by Matamoros and Salvadó

(2013) to evaluate the elimination efciency of MPs in a coagulation-occulation.

Similarly, a maximum elimination efciency recorded was 50% in treated hospital

wastewater by the process of coagulation-occulation, and a signicant reduction

was recorded up to 80% of compounds such as musk, that is, tonalide and galax-

olide. Similarly, other elimination efciencies were 23%, 42%, and 46% for ibupro-

fen, naproxen, and diclofenac, respectively. Another similar study was done by

Asakura and Matsuto (2009) which concluded that by the treatment technique of

coagulation, the removal of bisphenol A was not very effective for the treated land-

ll efuents, but comparatively results for MPs such as nonylphenol (90%) and

DEHP (70%) were quite impressive.

Taking into account, all the techniques and process of coagulation-occulation

provided a minimum elimination efciency for majority of MPs except for some

signicant pharmaceuticals and musk, that is, nonylphenol and diclofenac. This

procedure also showed poor results for the pesticides. Moreover, neither the tem-

perature factor nor the dose of coagulant effect of the removal of pesticide substan-

tially was recorded in various studies (Thuy etal. 2008). The chemical composition

of wastewater, when treated by the coagulation-occulation processes, inuences

the elimination rates of MPs either positively or negatively. However, the waste

efuents have a huge content of fats that enable to remove large amounts of

Table 15.9 Eliminations of some MPs during coagulation-occulation progression

Coagulant pH and dosage Compounds

Removal efciency

(%) Author

Al2(SO4)3/

FeCl3

7 and 25, 50

ppm

Diclofenac 21.6 ± 19.4 Surez etal.

(2009)

Al2(SO4)3/

FeCl3

7 and 25, 50

ppm

Carbamazepine 6.3 ± 15.9

Al2(SO4)3/

FeCl3

7 and 25, 50

ppm

Tonalide 83.4 ± 14.3

Al2(SO4)3/

FeCl3

7 and 25, 50

ppm

Ibuprofen 12.0 ± 4.8

Al2(SO4)3/

FeCl3

7 and 25, 50

ppm

Naproxen 31.8 ± 10.2

Al2(SO4)3/

FeCl3

7 and 25, 50

ppm

Sulfamethoxazole 6.0 ± 9.5

Al2(SO4)3/

FeCl3

7 and 25, 50

ppm

Galaxolide 79.2 ± 9.9

15 Treatment Technologies fortheEnvironmental Micro-pollutant

376

hydrophobic compounds (Surez etal. 2009). However, due to the fact that the dis-

solved humic acid maximizes the elimination rates of common pharmaceutical

compounds such as ibuprofen, diclofenac and bezabrate (Vieno etal. 2006). On

the other hand, the suspended organic matter in the waste efuents may block the

elimination of MPs (Choi etal. 2008). Factors like pH, temperature, alkalinity, and

mixing conditions also affect the efciency of coagulation-occulation (Alexander

etal. 2012).

15.5.2 Activated Carbon Adsorption

Basically, the treatment technique of activated carbon adsorption (ACA) is used to

control odor and taste in treated water, especially in drinking water. ACA techniques

provide better removal of more specically the secondary waste efuents for treat-

ment. ACA procedure when compared to coagulation-occulation is more efcient

in the elimination of MPs from the treated wastewater (Choi et al. 2008).

Furthermore, granular activated carbon (GAC) and powdered activated carbon

(PAC) have been widely applied for the adsorption purposes. The efcient elimina-

tion of MPs is dependent on the properties and type of adsorbate and also the adsor-

bent used (Kovalova etal. 2013).

15.5.3 Powdered Activated Carbon (PAC)

Removal of biodegradable organic compounds and resistant compounds when

treated with powdered activated carbon (PAC) is considered an exclusive and effec-

tive adsorbent. One of the main advantages of using PAC is that they supply con-

tinuously fresh carbon, and that in turn can be utilized in certain prevailing

circumstances, that is, when the level of contaminant rise in water (Snyder etal.

2007). One research was conducted by Kovalova etal. (2013) in which PAC proce-

dure was applied to evaluate the elimination efciency of MPs in the treated efu-

ents taken from the MBR hospital wastewater. In the conducted study, PAC dosages

were chosen as 8 mg/L, 23 mg/L, and 43 mg/L, and the time selected for retention

was about 2 days. Results for the study revealed that PAC adsorbent provided sub-

stantial elimination efciency, especially for metabolites, industrial chemicals, and

pharmaceuticals. The removal rate of total load was recorded as 86%. In another

study batch tests were conducted and concluded that the high removal rate was >94

% for bisphenol, personal care products, and nonylphenol (Hernandez-Leal

etal. 2011).

The removal efciency of PAC reactors for many MPs also depends on many

factors like contact time, physical properties of targeted contaminants, PAC concen-

tration/dosage, and water composition (Snyder etal. 2006; Boehler etal. 2012).

Similarly, a research study is conducted by Westerhoff et al. (2005), and they

A. Ayub and S. S. Ahmad

377

observed in their experiments that at the higher dosage of PAC (i.e., 20 mg/L), the

elimination efciencies of MPs were quite impressive regardless of their initial MP

concentration. So it was concluded from the study that the addition of PAC in the

wastewater treatment plants seems to be an efcient way for the elimination of

majority of micro-pollutants in unit time (Bolong etal. 2009).

15.5.4 Granular Activated Carbon (GAC)

Rossner etal. (2009) assessed that the dose of about <10 mg/L of granular active

carbon (GAC) was used in order to control the taste and odor of drinking water. The

dose used was sufcient enough for the treatment of lake water and the majority of

compounds were removed, providing an elimination efciency of about 99%.

Elimination efciencies of pharmaceuticals and steroidal estrogen were evaluated

and found to be in a full-scale GAC plant for the treatment of wastewater. Maximum

removal rates were recorded for steroidal estrogens, but the removal rates recorded

for pharmaceuticals were found to be very low. More specically, the elimination

efciencies of indomethacin, diclofenac, and mebeverine ranged from 84% to 99%.

However, the elimination efciencies of propranolol and carbamazepine ranged

from 17% to 23% (Grover etal. 2011). Evaluating PAC the contact time of GAC

also inuenced the efciency rates. The minimum contact time of GAC reactor

decreased its adsorption performance. More specically, the removal of contami-

nants depends upon the association between contaminant and particle and pore

blocking (Bolong etal. 2009). So treating high contaminated waste efuent with

GAC provides very poor results. Overall study results showed that PAC and GAC

processes can be considered as efcient techniques for the removal of MPs from the

treated wastewater. Moreover, maximum elimination rates of MPs can be achieved

by some signicant factors such as shape of contaminant, its high compliance of

pore size, and its nonpolar characteristics (Rossner etal. 2009; Verlicchi etal. 2010).

However, the blocking of pores is basically due to the existing organic matter (OM)

that minimizes the efciency of active carbon (Table15.10).

15.5.5 Ozonation andAdvanced Oxidation Processes

Conventional biochemical and physicochemical actions are not effective for the

elimination of major MPs due to their determined structure. In such type of cases,

advanced oxidation process and ozonation are the solution considered. Having more

degradation rates, the stated technology is not selective to remove contaminants.

Besides this, these procedures have an effect of disinfection for water to reuse

(Hernandez-Leal etal. 2011). Ozone destroys the pollutants directly or indirectly,

but most of the time by producing the hydroxyl (OH), which is strong enough and

less choosy for the emerging compounds. The nature of mostof theMPs are very

15 Treatment Technologies fortheEnvironmental Micro-pollutant

378

sensitive towards advanced oxidation processes (AOPs) and ozone such as

naproxenbut some of theMPsare only sensitive to (OH) radicals like atrazine.

However, some MPs like TCEP and TCPP have resistance to both forms of oxida-

tion and ozonation (Gerrity etal. 2011). The presence of ultraviolet, Fenton reagent,

and H2O2 are responsible for the production of hydroxyl radicals (OH).

Ozonation is an effective method of removing tiny pollutants in a full-scale

WWTPs (Hollender etal. 2009). Hernandez-Leal etal. (2011) examined the rate of

elimination of MPs in the biological way of treatment gray water by ozonation by

ozone dose of 5 mg/L.In a wide range, all MPs are selected and treated under sub-

stantial levels. Under the same environment with the only change in ozone dose of

5 mg/L, it showed higher removal percentage for most of MPs (Sui etal. 2010). The

elimination rates of most signicant MPs such asdiclofenac, carbamazepine, sul-

piride, trimethoprim, and indomethacin exceeds more than 95%. However, therate

for bezabrateremoval was evaluated, which resulted in 14% onlybecause ofthe

stable molecular structure of bezabrate (Kim etal. 2009) compared the elimination

efciencies of compounds like pharmaceutical compound using UV. The results

show us that the UV process alone acquires high rates of removal (>90%) for diclof-

enac, antipyrine, and ketoprofen, but the rate of elimination for macrolides ranged

from 24% to 34%. Another study conrmed that H2O2 and UV together achieved

much higher rate of efciencies for most micro-pollutants. However, under the

same situation when UV is applied to the Fenton process, the total rate of removal

is increased. In addition, the presence of such dissolved organic material in waste-

water enhances the removal rate of MPs. The oxidation process is not able to pro-

vide the complete mineralization of such emerging compounds and produce

byproducts. Also, metabolite arises from such reactions (Hollender etal. 2009;

Reungoat etal. 2011). Sand ltration or activated carbon ltration may be applied

to eliminate these unwanted compounds (Table15.11).

Table 15.10 Elimination of MPs during the process of adsorption

Adsorbent

Dosage

mg/L Contaminants

Removal

efciency (%) Author

PAC 8, 23,

and 43

Sulfamethoxazole 2, 33, 62 Grover etal. (2011) and

Kovalova etal. (2013)

PAC 8, 23,

and 43

Diclofenac 96, 98, 99

PAC 8, 23,

and 43

Carbamazepine 98, 99, 100

PAC 8, 23,

and 43

Propranolol >91, >94

GAC Full scale Carbamazepine 23

GAC Full scale Diclofenac >98

GAC Full scale Estrone 64

GAC Full scale Proponolol 17

GAC Full scale 17α-Ethinylestradiol >43

GAC Full scale 17β-Estradiol >43

A. Ayub and S. S. Ahmad

379

15.5.6 Membrane Processes

Usually,the removal of micro-pollutants by the process of membrane isacquired by

adsorption process onto charge repulsion, membrane and size of pores. The removal

percentage of membrane processes mostly depends upon the membrane process

type, blocking of membrane pores, operating condition, properties of selected tiny

pollutants, and characteristics of membrane (Schäfer et al. 2011). Ultraltration

(UF) and microltration (MF) are more effective in eliminating process for turbidity,

and such type of processes are inadequate for eliminating micro-pollutants because

of the molecular sizes of signicant MPs. Contaminants, however, can be eliminated

via contact with the natural organic matter (NOM), or it can be eliminated through

adsorption onto the polymers of membrane. Jermann et al. (2009) examined the

efciency removal of estradiol and ibuprofen by ultraltration without the existing

natural organic matter. In hydrophilic ultraltration membrane, removal rates of

estradiol and ibuprofen were found nearly 8% and negligible, respectively. In hydro-

phobic membrane, eliminating efciencies of estradiol and ibuprofen are generally

increased to 80% and 25%, respectively. However, UF and MF processes worked

alone in removing of MPs due to their poor performance. So these processes have to

combine with other methods of treatment, like reverse osmosis (RO) or nanoltra-

tion (NF). Garcia etal. (2013) combined the RO and MF processes for the reuse of

domestic wastewater and for the removal of micro- pollutants. For example, up 50%

DEHP was removed with the microltration treatment technique only. However, the

combined system of RO and MF improved the rate of elimination of micro-pollut-

ants. Removal efciencies of such MPs lied between 65% and 90% excluding non-

ylphenol and ibuprofen. A study presented that the combined system of RO and MF

has signicant removal efciencies greater than 95% for most MPs, except caffeine

and mefenamic acid (Sui etal. 2010) (Table15.12).

Reverse osmosis (RO) has such a great effect for the complete removal of almost

all the persistent micro-pollutants (Yangali-Quintanilla et al. 2011).

Comparatively, the performance rate of reverse osmosis treatment is more effec-

tivethan nanoltration for pesticides, endocrine disruptorsand pharmaceuticals.

The removal rate of micro-pollutants obtained by RO was very similar to NF’s

result. Removal efciencies for ionic contaminants and neutral contaminants treated

by the NF were estimated as 97% and 82%, respectively. Removal efciencies of

same pollutants treated by reverse osmosis were found as 99% and 85%, respectively.

Table 15.11 Removals of some MPs during ozonation and AOPs

Treatment (Dose) Compounds Removal efciency (%) Author

O3 (5 mg/L) Metoprolol 80–90 Luo etal. (2014)

O3 (5 mg/L) Trimethoprim >90

O3 (5 mg/L) Bezabrate 0–50

O3 (5 mg/L) Carbamazepine >90

O3 (5 mg/L) Ibuprofen 83

O3 (5 mg/L) DEET 50–80

O3 (5 mg/L) Diclofenac >90

15 Treatment Technologies fortheEnvironmental Micro-pollutant

380

15.5.7 Membrane Bioreactor (MBR)

Membrane bioreactor is a process that combines the treatment of membrane ltra-

tion and stimulated sludge biological treatment. There are so many benets of this

technology (MBR) associated with conventional WWTPs. Such benets involve the

higher efuent quality, precise control of the SRTs, higher biomass concentration,

less requirement of space, minimum increasing of the sludge problem, and convert-

ing the exibility of current WWTPs to MBR system. Membrane bioreactor has a

great ability to eliminate a very wide range of MPs that include the emerging com-

pounds resistant to stimulated sludge process (Radjenovic etal. 2009). The removal

of MPs through the MBR process most of the time depends upon the SRT, content

of water, concentration, conductivity, operating temperature, and pH (Kovalova

etal. 2012).

Trinh et al. (2012) investigated that the MBR process eliminates the micro-

pollutants on a full scale. Higher rates of elimination were found for most of the

micro-pollutants. However, the removal efciencies of carbamazepine, diclofenac,

amitriptyline, diazepam, sulfamethoxazole, uoxetine, omeprazole, trimethoprim,

and gembrozil ranged in between 24a% and 68%, and such compounds are said to

be the indicators due to their less rate of removal in MBR treatment. The main

source of drugs is waste efuents that arise from hospitals (Verlicchi etal. 2010).

Kovalova etal. (2012) examined the fate of such MPs in the membrane bioreactor

process treating hospital waste. Hence, the wastewater is mainly composed of iodin-

ated contrast mean, and total eliminating rates of metabolites and pharmaceuticals

were found at only 22%. Total reduction would be around 90% in case if such con-

tent were ignored. Beier etal. (2011) suggested that the waste of hospitals could be

Table 15.12 Elimination of some MPs by membrane processes

Membrane Water type

Membrane

type Compounds

Removal

efciency (%) Author

UF Synthetic

water

RC4

at-sheet

Estradiol Up to 80 Yangali-Quintanilla

etal. (2011)

UF Synthetic

water

PES

at-sheet

Ibuprofen Negligible

UF Synthetic

water

PES

at-sheet

Ibuprofen 7

UF Synthetic

water

RC4

at-sheet

Estradiol Up to 25

RO Secondary

efuent

Filmtec

TW30

Sulfonamides >93

RO Secondary

efuent

Filmtec

TW30

Ibuprofen >99

RO Secondary

efuent

Filmtec

TW30

Bisphenol A >99

RO Secondary

efuent

Filmtec

TW30

Macrolides >99

A. Ayub and S. S. Ahmad

381

efciently treated if we maintain the age of sludge very high (>100 days) in a mem-

brane bioreactor system designed especially for treating the hospital efuent.

MBR technology and conventional activated sludge process usually linked with

each other in the sense of removing the MPs. Radjenovic etal. (2007) compared the

performance of treatment of laboratory-scale conventional activated sludge and

MBR process in terms of removing the pharmaceuticals. Both systems are treated

with ibuprofen, naproxen, hydrochlorothiazide, paroxetine, and acetaminophen in

high level. However, results showed that membrane bioreactor system was com-

paratively stable for removing several contaminants, and some MPs were treated

somewhat more than the process of conventional activated sludge.

Like other technologies of treatment, MBR processes were also inuenced by

numerous factors such as HRT, operating temperature, and SRT. MBR systems

functioned at greater sludge age offer greater eliminating efciency for such pollut-

ants due to diverse MPs present in wastewater (Roh etal. 2009) (Table15.13).

15.6 Conclusion

In the present time, MPs are frequently detected in signicant drinking water reser-

voirs and sources like rivers, lakes, and groundwater. Presences of the MPs in high

amount in different aqueous bodies in various parts of the world pose a threat to the

aquatic as well as human ecosystem severely. However, the typical WWTPs cannot

provide the expected results for the elimination of the majority of MPs. In order to

achieve the desired results, it is important to apply appropriate treatment technolo-

gies to minimize the ecotoxicological effects of MPs in the surrounding environ-

ment. Many of the existing conventional WWTP elimination performances of MPs

are futile because of the presence of low amount of MPs in the waste efuents and

also because of the vast MP physicochemical properties. MPs especially having the

biodegradable nature and polar molecular structure pass during the WWTPs to the

water bodies receiving such treated water without being sufciently treated.

However, with little effort, upgrading and optimizing the current process in the

WWTPs is all set to crucially decrease the loading rates of MPs. Besides all the

conventional procedures and processes, coagulation-occulation, advance oxida-

tion processes (AOPs), activated carbon adsorption (granular activated carbon and

powdered activated carbon), membrane bioreactor, and membrane processes are

also applied for the removal of MPs. Within the persistent treatment procedures,

membrane system and advanced oxidation processes come to forefront. However,

these treatment techniques are very effective in eliminating the MPs, but they also

have some disadvantages such as causing to produce new byproducts and metabo-

lites at a very high operating cost. In the removal of micro-pollutant and inhibiting

the production byproducts and metabolites and other pollutants, a combined treat-

ment should be preferred to achieve the better results.

15 Treatment Technologies fortheEnvironmental Micro-pollutant

382

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Table 15.13 Elimination of some MPs by MBR

Water type Membrane type Contaminants

Removal

efciency (%) Author

Raw

wastewater

Full-scale hollow

ber

Carbamazepine 24 Radjenovic etal.

(2007)

Raw

wastewater

Full-scale hollow

ber

Estriol ~100

Raw

wastewater

Full-scale hollow

ber

Ibuprofen ~100

Raw

wastewater

Full-scale hollow

ber

Estrone ~100

Raw

wastewater

Full-scale hollow

ber

Bisphenol A ~100

Raw

wastewater

Full-scale hollow

ber

Diclofenac 43

Raw

wastewater

Full-scale hollow

ber

Trimethoprim 30

Raw

wastewater

Full-scale hollow

ber

Sulfamethoxazole 60

Hospital

efuent

Full-scale at

sheet

Ibuprofen >80

Hospital

efuent

Full-scale at

sheet

Diclofenac <20

Hospital

efuent

Full-scale at

sheet

Carbamazepine <20

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Health Impacts and Allied Treatment Technologies, Emerging Contaminants and

Associated Treatment Technologies, https://doi.org/10.1007/978-3-030-96523-5

Accelerated population rate, 242

Acclimatization, 256

Acetylcholinesterase activity (AChE), 184

Acid rain, 13

Actinobacteria, 188

Activated carbon adsorption (ACA), 376

Acute poisoning, 259, 260

Acute renal dysfunction, 45

Acute silicosis, 43

Acute toxicity, 259–260

Administration of drugs, 247

Adsorption, 8, 272–276

Adsorption-membrane ltration, 277

Advanced oxidation processes (AOPs), 92

Adverse effects, 266

Aeroallergens, 223

Aeromycoora

environmental protection, 220

fungi, 220

humans, 220

Aerosolization chamber, 221

Aatoxin B1 (AFB1), 298

Aatoxins, 292, 293

African trypanosomiasis, 23–24

Agency for Toxic Substances and Disease

Registry (ATSDR), 269

Agent blue, 252

Agricultural sector, 56

Agriculture crops, 293

Agriculture soil, 249

Airborne fungal spore

fungal kingdom, 220

sensitization, 220

taxonomic groups, 220

Air contaminated with arsenic, 258

Air contamination, 206

Air pollution, 15, 54

Air toxins, 206

Alimentary toxic aleukia (ATA), 291

Alkaloids, 291

Alkylphenol ethoxylates (APEs), 114

Allergic response, 232

Alloys, 253

Alpha-proteobacteria, 188

Alternaria alternata, 310

Alternaria species, 298

American Association of Poison Control

Centers, 259

Analgesics and anti-inammatories, 121

Anemia, 266

Anthropogenic activities, 248, 251

Anthropogenic contaminants, 56

Anthroponosis, 23, 25

Anthropophilic fungal dermatophytes, 231

Antibiotic resistance genes (ARGs), 330

Antibiotic-resistant bacteria, 323

Antibiotics, 9

airborne antibiotic resistance genes, 329

antibiotic-resistant bacteria, 320

aquatic environment, 328

disposal of unused and expired, 325, 326

ecosystem, 320, 333

environment, 320, 321

hazardous consequences, 329–331

hospital wastewater, 324–326

Index

388

Antibiotics (cont.)

human and animal therapy, 320

human health, 330, 331

humans, 323

industrial discharge, 326, 327

infectious diseases, 320

management strategies, 332, 333

medical settings, 324

medical waste, 324–326

municipal sewage, 327

poultry, veterinary and

aquaculture, 321–323

resistance, 324–326

sediments, 328, 329

sewage treatment plants, 327

surface treatment compounds, 327, 328

wastewater, 327

wastewater treatment plant, 320

water and soil, 320

Antifungal compounds, 253

Antimicrobial growth promoter, 250

Antimicrobials, 322

Applications of As

biotic weapon, 252, 253

oral administration, 253

Roxarsone, 253

wood preservative, 253

Aquatic pathogens, 26

Arable land, 244

Aromatic and methylated arsenicals, 257

Aromatic arsenicals, 257

Arsenate toxicity

mechanism, 270–272

Arsenate (V), 245, 248, 254, 255, 258,

268, 271

Arsenic (As)

agricultural soil, 249

anthropogenic activities, 248

applications, 252–253

arsenic-rich soils, 244

biogenic/biological sources, 248

chronic respiratory, 245

concentration, 248

environment, 252

environmental and human health, 244

environmental toxic substance, 244

formation, 245

gaseous, 249

genotoxicity effects, 267–270

groundwater, 249–251

history, 246

human-induced ventures, 244

inorganic, 245

ionic characteristics, 245

microorganisms, 249

multicellular living organism, 244

noncorrosive minerals, 248

old remedy, 246, 247

origin, 246

pesticide- and herbicide-containing

arsenic, 249

phosphatic fertilizers, 248

physical characteristics, 245

preservation of wood, 248

properties, 244

qualitative and quantitative effects, 249

removal technologies, 272–279

toxicity, 244, 245 (see also Toxicity of As)

trace element in earth’s crust, 244

transfer of (see Transfer of As)

valence states, 245

volcanic eruptions, 248

Arsenic (As) exposure

biogeochemical cycles, 256

food and water, 257

rocks, 257, 258

Arsenic-based compounds, 250

Arsenic-based organic compound, 247

Arsenic-contaminated groundwater, 261

Arsenicosis, 264

Arsenite (AsIII), 245, 248, 251, 254–256, 258,

261, 264, 266–268, 270, 271

generation, 254

Arsenolite (As2O3), 250

Arsenolysis, 271

Arsenopyrite, 247

Arsphenamine, 247

Arteriosclerosis, 260

Articial Neural Networks (ANNs), 31

Articial sweeteners, 5

Aspergillus, 227

Aspergillus avus, 290

Aspergillus ochraceus, 294

Aspergillus parasiticus, 290

Asthma, 261

Atherosclerosis, 263

Atmospheric residence, 256

Azithromycin, 324

Bacillus natto, 309

Bacillus subtilis, 309

Bacitracin, 322

Bacteria, 187, 193

Bacteria and iron electrocoagulation (bio-

FeEC), 277

Bacterial infections, 323

Index

389

Bacterial strains, 309

Bambermycin, 322

Basal cell carcinoma, 269

Beta-proteobacteria, 188

Bioaccumulation, 243

Biochemical effects, 267, 268

Biochemical/microbial degradation, 351

Biocides, 79

Bioconcentration, 256

Biodegradable plastic assessment

factors, 344

microplastic, 343

plastic polymers, 343

polymer degradation

aerobic, 345

anaerobic, 345

steps, 344, 345

thermoplastics, 343

types, 343

Biodegradable plastics, 343

Biodegradation, 256, 338, 345, 346,

351, 353

Biodegradation of organophosphates, soil

organisms

bioremediation, 188

chlorpyrifos, 189–190

glyphosate, 191

mechanisms, bioremediation, 190–192

monocrotophos, 190

profenofos, 191

Biolms, 329

Biogenic manganese oxide (BMO),

93–94

Biogeochemical cycles, 9, 256

Biological degradation, 351–353

Biological mechanisms, 354

Biological methods, 301

Biological methylation, 255

Bioremediation, 16, 164, 187, 188,

190–193, 257

Biosorption, 243

Biosphere, 180

Biotic weapon, 252, 253

Bio-volatilization, 257

Birth defects, 268

Blackfoot disease (BFD), 262, 269

Blastomyces dermatitidis, 226

Bloody rice watery diarrhea, 259

Body enzymatic system, 270

Bone marrow, 266

Bowen’s disease, 269

British anti-lewisite, 259

Bronchiectasis, 268

Busulfan, 247

Cacodylic acid, 253

Caffeine, 122

Campylobacter jejuni, 26

Carbamazepine, 122

Carcinogenic effect

body enzymatic system, 270

epidemiological data act, 269

lung cancer, 270

skin cancer, 269

Carcinogens, 41, 44

Carcinoma in situ, 269

Carcinomas, 44

Cardiac arrhythmias, 262

Cardiovascular disease, 260

Cardiovascular effects

atherosclerosis, 263

blood vessels, 261

cardiac arrhythmias, 261–262

CVD, 262

epidemiological analysis, 261

epidemiological studies, 261

hypertension, 263

IHD, 262

myocardial depolarization, 261

PVD, 262

voluntary consumption, 261

Cellular biochemical functioning, 256

Cerebrovascular disease (CVD), 260, 262

Chemical agents, 186

Chemical alterations, 344

Chemical constituents, 206

Chemical degradation, 350, 352

Chemical methods, 186

Chemisorption, 155, 272

Chernobyl atomic reactor, 4

Chernobyl incident, 60

Chikungunya, 24

Chinese Nei Jing Treaty, 247

Chlorination, 186

Chloroacetamide, 10

Chlorouorocarbon, 12

Chlorpyrifos, 181–183, 186, 188–190,

192, 193

Chlortetracycline, 322

Cholera, 26, 27

Chromated copper arsenate (CCA), 248, 253

Chromatographic techniques, 299

Chromosomal aberration, 267

Chronic asthmatic bronchitis, 261

Chronic lung disease, 260

Chronic myelogenous leukemia (CML), 247

Chronic obstructive pulmonary disease

(COPD), 39, 43

Index

390

Chronic poisoning, 260

Chronic renal insufciency, 46

Chronic respiratory, 245

Chronic silicosis, 43

Chronic toxicity

chronic poisoning, 260

respiratory effects, 260, 261

Ciprooxacin, 323, 324

Cirrhinus mrigala, 183

Clarias garipenus, 183

Clarithromycin, 324

Class 1 carcinogen agent, 245

Classication and regression tree (CART), 31

Claviceps purpurea, 298

Climate change (CC), 22, 23

anthroponosis, 25

cholera, 26

COVID-19, 24, 25

ID, 28–30

geographical impact, 27, 30

modelling, 31

respiratory disease, 25

VBD, 24

waterborne disease, 26

zoonotic disease, 25

Climate changes, 60, 61, 63, 64

CLIMEX model, 31

Clinical abnormalities, 266

Clinical complications, 260

Clostridium perfringens, 322

CO2 emissions, 54, 55

Coccidioidomycosis infection, 225

Coccidioidomycotic infection, 225

Cohesive methods, 358

Combustion of plastic products, 342

Comparative analysis, 267

Conidia, 222

Container-inhabiting mosquito simulation

model (CIMSiM), 31

Contamination

arable land, 244

As (see Arsenic (As))

and distribution, 248

environmental, 252

groundwater, 244, 245

and pollution, 242, 243

soil and water, 249

Conventional activated sludge process

(CAS), 89, 92

Copper (Cu), 146

Coprecipitation-hydrothermal method, 273

Cosmetics, 106, 114

COVID 19, 23–25

Cryptococcosis infection, 228

Culture techniques, 233

Cupriavidus nantongensis, 193

Cutinase, 357

Cypermethrin, 185

Cysteine, 271

Czapek dox agar, 233

Dangerous waste, 339

Daphnia magna, 330

Degradation, 208, 243, 256, 257, 348,

351, 352

Degraded particles, 344

Derivatives of phenylalanine, 291

Dermal exposure, 212

Dermatitis, 48

Dermatophytes, 229

Detoxication, 187, 188, 193

Deuteromycetes, 222

Developmental disorders, 266

Diabetes mellitus, 263

Diarrhea, 259

Diazinon, 183

Diet acts, 258

Dimethoate, 181

Dimethylarsinate (DMA), 257

Dinitroanilines, 12

Dioxins, 207, 209

Direct genetic mutation, 267

Diseases, 269

Disinfectants, 327

Disodium methanearsonate (DSMA), 249, 253

DMA (V), 252, 255, 257–259, 279

DNA repair system, 267

Dose-response relationship, 261

Dracunculus medinensis, 25

Drug-resistant bacteria, 325

Dry-wet phase inversion technique, 278

Dyeing industry, 3

Dynamic mechanical Analysis (DMR), 356

Earth Summit, 60

Earthworm species, 186

Eco-epidemiological methods, 27

Ecological factors, 348

Electrical cataracts, 45

Electrocardiogram, 261

Electrochemical process mechanism, 155

Electrocoagulation (EC), 155, 273, 274, 277

Electrocoagulation-electrootation (EC-EF)

process, 160

Index

391

Electrocoagulation using iron electrodes

(ECFe), 277

Electromyography, 265

Electronic industries, 253

Electrooxidation (EO), 155

Elongation, 347

Emerging contaminants (ECs), 3, 106, 111

Emerging groundwater contaminants (EGC)

physical and chemical characteristics, 107

types, 108

Emerging organic contaminants (EOC)

adsorption/migration, 127, 128

analgesics and anti-inammatories, 121

antibiotics, 120

caffeine, 122

DEET, 123

degardation, 128

degradates, 106

distinct array, 105

ECs, 106

hormones/sterols, 114

industrial compounds, 111

landlls, 125

lifestyle compound, 110

lipid regulators, 121

micro-contaminants, 106

micro-pollutant, 106

nonvolatile compounds, 131

PPCPs, 106, 123

soil surface contaminants, 129

surfactants, 114

underground environment, PPCPs, 127

underground water contamination, 106

Encephalopathy, 265

Endocrine, 263, 264

Endocrine disruptive chemicals (EDCs), 3,

6, 78, 372

Endophytic bacteria, 188

Engineering measures, 47, 48

Engineering microalgae metabolism, 358

Environment

micro-pollutants, 56–58

pollution, 54–55

Environmental degradation

chernobyl incident, 60

Pakistan (see Pakistan)

Environmental development, 60

Environmental issues, 59

Environmental laws, 58–61

Pakistan (see Pakistan)

pollution remediation, 58–61

Environmental legislations

European countries, 59

national government's role, 59

Environmental micro-pollutants (MPs)

additives, 370

agriculture, 369

analytical techniques, 366

anthropogenic chemical compounds, 366

chemical substance, 373

chronic health conditions, 366

detergents, 369

emerging pollutants, 366

endocrine disruptive chemicals

(EDCs), 372

ame retardants, 370

food chain, 373

groundwater, 374

human pharmaceuticals, 370–372

marine ecosystem, 373

marine organisms, 373

new class pollutants, 370

peruorinated compounds (PFCs), 369

personal care products (PCPs), 369

prospective pollutant, 366

protocols, 366

sources, 367, 368

transformation mechanism, 367

transport, 367, 368

treatment technologies

activated carbon adsorption (ACA), 376

advanced oxidation processes

(AOPs), 377–379

coagulation-occulation, 375, 376

granular active carbon (GAC), 377

membrane bioreactor (MBR), 380, 381

membrane processes, 379

ozonation, 377–379

powdered activated carbon (PAC),

376, 377

veterinary drugs, 370–372

wastewater, 366

Environmental Policy, 63, 64

Environmental pollutants, 242, 243

Environmental pollution, 39, 58, 340

Environmental Protection Act of 1997, 67

Environmental Protection Agency (EPA),

42, 59, 65

Environmental renement, see Micro

pollutants

Enzymatic degradation mechanism

laccases, 354, 355

lignin-degrading enzymes, 353–355

Enzymatic hydrolysis degradation, plastic

polymers, 355

Enzymes, 184

Eosinophilic aggregation, 224

Epichlorohydrin (ECH), 155

Index

392

Equine leucoencephalomalacia (ELEM), 295

Ergotism, 291

Escherichia coli, 322

Esterases, 191

Ethylenediaminetetra-acetic acid

(CS-EDTA), 155

European Community (EC), 308

European Drinking Water Directive

(EDWD), 107

European Food Safety Authority, 310

European Union (EU), 61

European water frame directive (WFD), 61

Fabric-like nonwoven polypropylene bags, 66

Fatal injury, 38

Fertilizer, 56

Fibrotic lung disease, 42

Filamentous fungi, 291

First aid services, 47

Fluoralkylsilane agent, 279

Fluorescence, 299

Fluorescence polarization immunoassay, 300

Food and Drug Administration (FDA), 295

Fourier Transform Infrared (FTIR), 153

Fowler’s solution, 247

Fragmentation, 222

Fragments of aerosols, 221

Fumonisin B1 (FB1), 294

Fumonisins (Fm), 294, 295

Fundamental Social Rights of the Workers, 48

Fungal aeroallergens

cause, 223

pollens, 223

spores, 223

stomach, 224

Fungal infections, 236

Fungal metabolic compounds, 291

Fungal mycelium, 227

Fungal sensitization, 233

Fungi, 187

Fungicides, 236

Furans, 207, 209

Fusarium proliferatum, 294

Fusarium verticillioides, 294

Gallium arsenide, 254

Gamma-proteobacteria, 188

Gas chromatography–mass spectrometry, 299

Gaseous arsenic, 249

Gastrointestinal (GIT) effect, 261

Gastrointestinal tract, 258, 259

Genotoxicity effects

biochemical effects, 267, 268

carcinogenic effect, 269–270

chromosomal aberrations, 267

human health effects, 268

mutagenesis, 267

renal effects, 268

Geogenic hazardous chemicals, 57

Geographical distribution, 27

German water protection policy, 61

Giemsa, 225

Global Beauty Market, 79

Global biogeochemical cycles, 243

Global warming, 30

Glucose transport, 267

Glycine/Glyphosate, 9

Glyphosate, 9, 181, 182, 184, 185, 191

Granular activated carbon (GAC), 376, 377

Granulomatous lesions, 225

Ground-level air pollution, 54

Groundwater, 249, 251

Group V contain semimetallic element, 253

Growth retardation, 268

Guillain-Barré syndrome, 260

Gut-associated lymphoid tissue (GALT), 305

Haloacetic acids, 111

Halogen Immunoassay (HIA), 232

Harmful chemicals, 340

Hazard Analysis and Critical Control Point

(HACCP) system, 307

Hazardous materials, 254

Healthy environment, 242, 243

Heavy metals, 2, 80, 243, 256

chromium, 145, 146

chromium and copper, 146

anthropogenic, 147, 148

environmental effects, 148–150

health effects, 151, 152

natural, 147

chronic exposure, 144

Cu, 146

denition, 144

essential, 144

hexavalent chromium/cooper removal

physico-chemical methods, 153

Hematological disorders, 266, 267

Hematopoietic system, 266

Hemodialysis, 259, 260

Hemolysis, 267

Hepatic, 264

Index

393

Hepatic effects, 303

Hepatocellular carcinoma, 303

Hepatocytes, 303

Hereditary disorder, 267

Heterogeneous photocatalysis, 186

High Efciency Particulate Air (HEPA), 235

High-density polyethylene (HDPE), 339, 341

High-ux ultraltration membrane, 278

Histoplasmosis, 225

Homogeneous photocatalysis, 186

Horizontal gene transfer (HGT), 7

Human activities, 60

Human epithelial cells, 212

Human health, 184

Human health effects, 268

Human-induced activities, 244

Hydrochars, 15

Hydrogel beads, 278

Hydrolases, 191

Hydroxyl (OH), 377

Hyperpigmentation, 265

Hypertension, 263

Imidazolinone, 10

Indoor environment, 221

Industrialization, 59

Infectious disease (IDs), 22, 23

Inhalable marble dust, 42

Inhalation exposure, 211, 212

Inorganic arsenic, 245, 252

Inorganic arsenite (As III), 255

Insecticides, 180, 181

Intergovernmental Panel on Climate Change

(IPCC), 22, 60

International Agency for Research on Cancer

(IARC), 41, 48, 148, 208

International Labor Organization (ILO), 39

Intracellular deterioration, 355

Ion exchange, 275, 277, 278

Ionic liquids, 120

Irrigation, 56

Ischemic heart disease (IHD), 260, 262

Kingdom fungi, 222

Kyoto protocol, 60

Laccases, 353–355, 357

Landlling, 343

Landlls, 125

Landry-Guillain-Barre syndrome, 265

Lateral gene transfer, 7

Lead-acid batteries, 253

Leaky sewers, 126

Legionella pneumophila, 26

Legislations, 61

Leukopenia, 266

Life-sized model, 211

Light-releasing/light-emitting diodes, 253

Lignin-degrading enzymes, 353–355

Lignin-degrading fungi, 354, 356

Liver function tests, 264

Livestock breeding, 126

Living cells, 255, 256

Low-density polyethylene (LDPE), 339–341

Lung cancer, 270

Lung carcinoma, 44

Macrocyclic acid lactones, 291

Malaria-Potential-Occurrence-Zone model, 31

Malathion, 181

Malformation, 266

Managed aquifer recharge (MAR), 124

Man-made activities, 243

Marble

environmental and health hazards, 38

natural metamorphic rock, 38

Marble dust as occupational health hazard

dust clouds, 39

dust particulates, 39

economic impact, 48

epidemiological studies, 48

exposure calculation, 41, 42

exposure to dust concentration and intake

rate, 40

exposure to marble dust concentration, 41

health hazards at workplace

COPD, 43

lung carcinoma, 44

occupational lung diseases, 42

ophthalmic disorders, 45

pneumoconiosis, 44

renal disorders, 45, 46

silicosis, 42, 43

skin disorders, 44, 45

IARC, 48

ILO, 39

inappropriate management, 46

inhalable dust, 42

marble quarrying to waste, 40, 41

mechanical breakdown, 39

Index

394

Marble dust as occupational health

hazard (cont.)

particulate matter (PM2,5), 39

preventive measures

engineering measures, 47, 48

legislations, 48

medical measures, 47

multidisciplinary approach, 46

risk management, 46

respirable dust, 42

worker’s safety, 40

workers exposure, 39

Marble industry, 39

Marble quarrying, 40, 41

Marine birds, 340

Mechanical stress, 349

Medical measures, 47

Mees’ lines, 266

Melarsoprol, 247

Membrane biological reactor (MBR), 89, 92,

380, 381

Membrane ltration technologies, 161

Membrane technologies, 275, 278, 279

Metabolism, 272

Metal toxicity, 243

Metallic gray, 254

Meteorological parameters, 22

Methicillin-resistant Staphylococcus Aureus

(MRSA), 330

Methylated arsenic, 250, 252

Methylation, 254, 257, 258

Micro contaminants, 56

Micro pollutants

advanced anaerobic digestion systems, 94

agriculture purposes, 76

anthropogenic activities, 82

aquatic environment, 80, 81

biocides, 79

biological treatments, 89

chemicals, 84

coagulation/sedimentation, 96

constructed wetlands, 91

consumer products, 76

ecosystem, 76, 82

endocrine-disrupting chemicals, 78

enzymatic bioremediation, 94

ground water, 81

heavy metals, 80, 83

human activities, 76

human health

arsenic, 87

cadmium, 84

chromium, 84

chronic respiratory disorders, 84

endocrine-disrupting chemicals, 87

estrogenic chemicals, 88

heavy metals, 84

impacts, 85–87

lead, 84

mercury, 84

metals, 87

neurotransmitter activity, 87

organic and inorganic pollutants, 84

oxides, 87

pesticides, 87, 88

synaptic disorders, 87

industrial efuents, 76

KMnO4, 93, 94

mechanism of disinfection, 91

membrane bioreactors (MBRs) techniques, 92

microbial genes, 95

multiple anthropogenic activities, 76

nano ltration method, 90

nanoparticles, 80, 81

nitrifying activated sludge (NAS), 93

nonpoint source, 83

oxidation, 93, 94

ozonation oxidation processes, 90, 91

ozone (O3), 92

personal care products, 79

pesticides, 77

pharmaceuticals, 77, 78

pharmaceuticals and personal care

products, 83

physicochemical application, 89

reverse osmosis (RO), 90

soil, 81

soil and aquatic ecosystem, 82

transportation, 81, 82

wastewater, 76, 83

Microalgae, 358

Microbead-Free Water Act, 65

Microbes, 352–354, 357

Microbial community, 243

Microbial degradation, 187, 190

Microbial diversity, 256

Microbial fuel cell (MFC), 164

Microbial interaction-based strategy, 187

Microbial polymer degradation, 345

Microclimate, 234

Microltration (MF), 379

Microorganisms, 7, 95, 191, 193, 243, 249,

257, 301, 351, 352

Microparticles, 212

Microplastics, 64–66, 208

Micropollutants, 2, 56–58, 211

economy of Pakistan, 62, 63

environment, 56–58

Index

395

environmental laws, 58–61

government, 64–66

mitigation methods, 58

atmosphere, 14

characteristics, 10

human health, 14

impacts, 6, 7

inorganic, 5

management, 15

origin, 6

pharmaceutical residues on soil, 8

soil, 14

chemical substances, 11

herbicides, 9

microorganisms, 13

sustainable agriculture, 12

sources, 3, 4

sustainable agriculture, 12

types, 2

wastewater, 4

water, 14

xenobiotic, 7

Micro-stratication, 30

Miner lung, 44

Mineralization, 187, 345

Mining, 252

Ministry of Climate Change took the initiative

(MoCC), 66

Mitosis, 244

MMA (I), 255

MMA (III), 255

MMA (III) (monomethylarsonic acid), 255

MMA (V), 255

Modelling, 31

Molecular detection, 228

Molecular techniques, 234

Monocrotophos, 184, 185, 190

Monomethylarsonate (MMA), 257

Monosodium methanearsonate (MSMA), 249

Monosodium methyl arsenate (MSMA),

250, 253

Mortality, 232

Motor visual perception test (MVPT), 268

Mucorales causes disease, 227

Municipal solid waste, 55

Municipal waste management strategies, 66

Mutagenesis, 267

Mycotoxins

aatoxins, 292, 293

biological methods, 309

chemical methods, 308

climate change, 309, 310

detection

detoxication, 301

dietary modications, 301, 302

food, 300

food processing, 301

management, 300

methods, 300

production, 300

quantication, 300

traditional techniques, 299

discovery, 290, 291

ergot toxin, 297, 298

factors, 307

feed, 307

lamentous fungi, 291

food, 307

fumonisins (Fm), 294, 295

heterogeneous mixtures, 310

nitropropionic acid (NPA), 298

ochratoxins, 294

origin and chemical nature, 291

patulin, 297

physical methods, 307, 308

sterigmatocystin (STE), 298

toxicity and clinical manifestations, 292

trichothecenes (TCTCS), 295, 296

Turkey X disease, 290, 291

types, 292

zearalenone (ZE), 296, 297

Myocardial depolarization, 261

Myocardial infarction, 261

Myopathic disorders, 184

N-4-acetylated sulfamethazine, 322

Nano ltration method, 90

Nanoltration (NF), 379

Nanoparticle-based methods, 300

Nanoparticles, 212

National Environment Policy, 63

National Environmental Action Plan

(NEAP), 67

National Research Council (NRC), 269

National Water-Quality Assessment

(NAWQA), 113

Natural environment, 342

Natural organic matter (NOM), 379

Natural plastics, 340

Neurodegenerative diseases, 184

Neurodevelopmental dysfunctions, 6

Neurological disorders, 265

Neurological effects, 260

Neurotoxic effect, 304

Nitrifying activated sludge (NAS), 93

Nitrobacter, 330

Index

396

Nitrogenous gases, 12

Nitropropionic acid (NPA), 298

Nitrosomonas, 330

N-nitrosodimethylamine (NDMA), 111

Nonaromatic substrate degradation, 354

Nonchemical method, 236

Noncorrosive minerals, 248

Nondegradable solid waste, 351

Nonessential heavy metals, 144

Non-insulin-dependent diabetes mellitus, 260

Nordstrom, 258

Nuclear prevention, 60

Occupational eye illness

chemicals, 45

electrical injuries, 45

heat, 45

radiations, 45

Occupational health, 47

Occupational health legislations, 48

Occupational lung diseases, 42, 44

Occupational ophthalmic diseases, 45

Occupational renal disorders, 45, 46

Occupational Safety and Health (OSH)

programs, 48

Occupational skin disorders, 44

Ochratoxin A (OTA), 294, 305

Ooxacin, 323

OP acid anhydrase (OPA), 191

OP hydrolase (OPH), 191

Oral administration, 253

Oral exposure, 213

Organic acids, 308

Organic and inorganic As, 250

absorptive ability, 254

metallic gray, 254

methylation, 254

mobility of coprecipitation, 254

in periodic table, 253, 254

physical characteristics, 254–255

Organic arsenic, 253

Organic As (V), 257

Organic chemical degradation processes, 8

Organic materials, 67

Organic matter (OM), 377

Organic micropollutants (OMPs), 2

Organic pollutants, 67

Organoarsenical herbicides, 249

Organochlorines pesticides (OCPs), 2–3

Organophosphates (OPs)

application, agricultural practices, 193

compounds, 178

detoxication, 187, 188, 193

diazinon, 183

fosthiazate, 182

general structure, 179

herbicides, 185

hydrolyzing enzymes, 188

insecticides, 178, 182

malathion, 183

mechanism, microbial degradation, 193

mitigation

chemical-based strategy, 186, 187

microbial interaction-based

strategy, 187

strategies, 193

monocrotophos, 183 (see also

Organophosphorus

pesticides (OPPs))

pesticides, 178

tetraethyl pyrophosphate, 178

toxicity

aquatic fauna, 185

humans, 185

soil microbes, 185

Organophosphorus pesticides (OPPs)

applications, 180, 181

biodegraded products, 192

bioremediation, 187, 188, 193

cardiac problems, 184

case study, 192, 193

characteristics, 179, 180

gastrointestinal problems, 184

general formula, 192

sources and distribution,

biosphere, 180

toxicokinetics (see Toxicokinetics

of OPPs)

Orpiment (As2S3), 250

Oxidizing agents, 308

Oxidizing agents or endocrine disrupters, 111

Oxo-biodegradable technologies, 66

Ozonation oxidation processes, 90, 91

Pakistan

economic relation, 63, 64

environmental challenges, 63

environmental issues, 67

environmental laws, 55

environmental policy, 63, 64

Environmental Protection Act of 1997, 67

market-oriented policy reform, 64

microplastic contamination, 65

micro-pollutants

Index

397

annual risk, drinking contaminated

water, 62

contaminated water, 62

drinking water supplies, 62

economic costs, 62

environmental problems to Pakistan's

economy, 63

gross economic burden, health, 62

ground aquifers, 62

waterborne diseases, 62

mismanaged plastic, 65

non-distortionary economic policies, 64

oxo-biodegradable technologies, 66

Pakistan’s National Environmental Policy

(2005-15), 67

plastic bags, 65

solid waste, 66

vulture population, 57

Pakistan Environmental Protection Act, 63

Pakistan's Environmental Policy, 63

Pakistan's National Environmental Policy

(2005-15), 67

Paris green pesticide [Cu(CH3COO)2⋅3Cu(

AsO2)2], 249

Pathogenic mechanism, 224

Pathophysiological risk, 17

Patulin, 297

Penicillin, 9, 322

Penicillium, 298

Penicillium cyclopium, 294

Peruorinated compounds (PFCs), 369

Peruoro octane sulfonate (PFOS), 107

Peripheral vascular disease (PVD), 260, 262

Peroxidation, 256

Persistent organic pollutants (POPs), 2, 6, 206

Personal care products (PCPs), 84, 89,

106, 369

Pesticide-and herbicide-containing

arsenic, 249

Pesticides, 77, 109, 187, 192

classication, 178, 179

enzymatic activities, pests, 178

Petro-chemical industries, 250

Pharmaceutical and personal care products

(PPCPs), 93

Pharmaceuticals, 77, 78, 109

Phase inversion/sintering technique, 279

pH-associated reactions, 129

Phenoxycarboxylic acids, 11

Phenylarsine oxide (PAO), 267

Phosphate-based retardants, 114

Phosphatic fertilizers, 248

Photocatalytic degradation, 186

Photodegradation, 350

Photosystem ll, 11

Phylogenetic relationships, 222

Physical characteristics of As, 254–255

Physical degradation, 348, 352

Physical treatment, 349, 350

Physico-chemical methods

adsorption, 153

bioremediation, 164, 165

copper removal, technologies, 155–159

EC, 155, 160

FTIR, 153

ion exchange, 163

membrane ltration, 161, 162

technologies, 154

Physicochemical treatments, 349

Physisorption, 272

Phytoestrogen, 297

Phytoremediation, 188, 279

Plant community, 181, 182

Plastic bags, 65

Plastic biodegradation, 355

analysis techniques

chemical properties, 356

low molecular weight fraction, 355

mechanical properties, 356

molecular weight, 356

physical properties, 356

weight loss, 355

applications, 349

conditions, 348

microbes, 348

microorganisms

enzymes, 357

hydrolytic cleavage, 357

lignin-degrading fungi, 356

microalgae, 357

microbial degraded/treated plastic

products, 358

microbial growth and plastic

degradation, 357, 358

properties

characteristics, 346

characteristics of plastics, 346

density, 347

elongation, 347

mechanical and elastic, 347

tensile strength, 347

thickness, 346

weight, 346

Young’s modulus, 347

Plastic contamination, 66, 339

Plastic debris, 339, 340

Index

398

Plastic degradation, 348, 355

cohesive methods, 358

enzymatic degradation, microbial agents

laccases, 354, 355

lignin-degrading enzymes, 353–355

extracellular and intracellular, 348

physical, 348

pretreatments

biological degradation, 351–353

chemical degradation, 350

photodegradation, 350

physical methods, 349

thermal degradation, 350

procedures, 348

processes, 348

Plastic litter, 343

Plastic pollution, 64, 66, 338, 339

Plastic polymers, 338, 343, 354

Plastics, 65, 207, 212

accumulation, 348

characteristics, 338

consumption, 338

denition, 340

elements, 341

environmental problems, 338

nature, 340, 341

source of pollution, 339–340

types, 341

uses, 341, 342

Plastic waste, 64, 207

land-based, 340

marine debris, 339

marine environment, 340

Plastic waste accumulation, 66

Plastic waste disposal

combustion, plastic products, 342

landlling, 343

recycling, 343

Pleurotus ostreatus, 354

Pneumoconiosis, 44

Pneumocystis pneumonia (PCP), 228

Poison of kings, 246

Pollutants, 13, 57

Pollution, 54–55

and contamination, 242, 243

Pollution remediation, 58–61

Polyaromatic hydrocarbons (PAHs), 2

Polybrominated diphenyl ethers (PBDEs),

206, 207, 209

Polychlorinated biphenyls (PCBs), 2, 206–208

Polycyclic aromatic hydrocarbons (PAHs), 7,

207, 208

Polyethersulfone (PES), 162

Polyethylene membrane degradation, 354

Polyethylene terephthalate (PET)

biological degradation, 357

degradation, microalgae, 358

enzymes, 358

global usage, 349

plastic, 357

semicrystalline thermoplastic

polyester, 349

waste products, 357

Polyethylenimine (PEI), 155

Polyketides, 291

Polymer conversion, 352

Polymer degradation

aerobic, 345

anaerobic, 345

enzymes, 345

Polymeric substances, 351

Polymers, 341, 345, 353

Polyphenylsulfone ultraltration

membrane, 279

Polypropylene bags, 66

Polystyrene nanospheres, 211

Polythene, 338, 341

Polyvinyl alcohol (PFSP), 164

Polyvinyl chloride (PVC) particles, 212

Poultry slaughterhouse, 273

Powdered activated carbon (PAC), 376, 377

Primary airborne dust, 41

Principal component analysis (PCA), 31

Profenofos, 191

Protoplastic poison, 244

Pseudomonas aeruginosa, 26

Pseudomonas peli, 187

Pseudomonas putida, 188

Public awareness, 236

Pyruvate dehydrogenase (PDH), 271

Quinolones, 329

Ramsar Convention, 59

Rapid intensication, 3

Reactive oxygen species (ROS), 182, 256

Realgar (As4S4), 250

Recycling plastic, 343

Regression model, 32

As removal technologies

adsorption, 272–276

electrocoagulation (EC), 273, 274, 277

ion exchange, 275, 277, 278

membrane technologies, 275, 278, 279

Index

399

phytoremediation, 279

Renal disease, 260

Renal disorder, 266

Renal effects, 268

Reproductive effects, 260

Respirable marble dust, 42

Respiratory ailments, 231

Respiratory disease

aspergillosis, 227

blastomycosis, 226

coccidioidomycosis infection, 225

endospore, 225

fungal ora, 224

histoplasmosis, 225

laboratory diagnosis, 227

mucormycosis, 227

symptoms, 225

Respiratory disorders, 23, 25

Respiratory effects, 260, 261

Respiratory metabolite, 244

Respiratory symptoms, 212

Respiratory system, 260, 268

Reverse osmosis (RO), 90, 162, 379

Risk management, 46

Rocks, 251, 257, 258

Roxarsone, 253

Roxarsone [4-hydroxy-3-nitrophenylarsonic

acid, Rox (V)], 250

Saccharomyces cerevisiae, 309

Salmonella, 23, 331

Salty water inltration, 57

Scanning electron microscope (SEM), 356

Semiconductor, 253

Septic systems or on-site wastewater treatment

systems, 125

Serratia marcescens, 187

Sesquiterpenes, 291

Sewage treatment plants (STPs), 124

Sex hormones, 114

Short-chain fatty acid (SCFA), 305

Silicosis, 43

acute, 43

chronic, 43

brotic lung disease, 42

types, 43

Skin, 44, 265, 266

Skin ailments, 260

Skin cancer, 269

Skin disorders, 44, 45

Smelters, 249

Socio-economic factors, 22

Sodium arsenite, 248

Soil, 7, 185

Soil biota, 185

Soil fertility, 190

Soil microbes, 250

Soil microorganisms, 185, 250

Solid pollutants, 16

Squamous cell carcinoma, 269

Sterigmatocystin (STE), 298

Sterilization methods, 234

Strong base anion exchange, 163

Submicron fungal fragments, 221

Submucosal hemorrhages, 260

Sulfamethoxazole, 324

Sulfonamides, 322, 328

Sulfonylurea, 10

Sulfuric acid, 265

Surface and groundwaters, 56

Surface water-groundwater (SW-GW), 129

Synthetic organic composites, 105

Synthetic plastics, 341

Synthetic polymers, 338

Taiwan's Waste Disposal Act, 65

TCA cycle (tricarboxylic acid cycle), 270

Tetracyclines, 328

Tetraethyl pyrophosphate, 178

Thermal degradation, 350

Thermoplastics, 341

Thermoset plastics, 341

Thin-layer chromatography (TLC), 299

Threats, 321, 330

Thyroid-related disorders, 6

Timber treatment, 248

Tinea barbae, 230

Tinea capitis, 230

Tinea corporis, 230

Tinea pedis and tinea manuum, 231

Tissue biopsy specimens, 227

Toxic organic micropollutants (OMPs)

atmosphere, 214

carcinogenic risk, 206

classes, 206

exposure

dermal, 212

human body, 210

inhalation, 211, 212

oral, 213

health impacts, 208–210

pollution in groundwater, China, 206

recommendations, 214

sources, 207–208

Index

400

Toxic organic micropollutants (OMPs) (cont.)

sources of pollution, 206

types, 207–208

Toxicity, 84, 87, 91, 95

Toxicity of As

biological methylation, 255

biotransformations, 255

exposure, 256–258

inorganic arsenite (As III), 255

on living cells, 255, 256

Toxicity of OPs

aquatic fauna, 185

humans, 185

soil microbes, 185

Toxicokinetics of OPPs

animals, 182, 183

animal species, 181

human health, 184

living organisms, 181

non-target plant species, 181

plant community, 181, 182

soil biota, 185

Toxicology

acute and chronic illnesses, 302

agricultural products, 302

biomolecules, 306

cancer and immune deciency, 302

categories, 302

gastrointestinal tract, 305

H9c2 cardiac cells, 306

hepatic effects, 303

humoral immunity, 307

immune system, 306

immunosuppression, 306

infectious agents, 302

mutagenic effects, 305, 306

neurotoxic effect, 304

pulmonary and cardiovascular toxicity, 306

renal toxicity, 304, 305

Tracheobronchial mucosal, 260

Transfer of AS

acute poisoning, 259, 260

acute toxicity, 259–260

cardiovascular effects, 261–263

cellular processes, 258

chronic toxicity, 260, 261

developmental disorders, 266

endocrine, 263, 264

gastrointestinal tract, 258

GIT effect, 261

hematological disorders, 266, 267

hepatic, 264

neurological disorders, 265

reduction process, 258

skin, 265, 266

Transfer procedures, 8

Trichothecenes (TCTCS), 295, 296

Triclopyr, 9

Trihalomethanes, 111

Trimethoprim, 324

Trivalent arsenic toxicity, 271, 272

Tubular necrosis, 268

Type 2 diabetes, 263

Types of OP insecticides, 185

Ultrafast liquid chromatography connected

with tandem mass spectrometry

(UFLC-MS/MS), 300

Ultraltration (UF), 379

Ultraviolet coupled with high-performance

liquid chromatography, 299

Ultraviolet radiations (UV), 92

United Nations Environment Program

(UNEP), 59

United Nations Organization for Food and

Agriculture (FAO), 178

Urban water cycle, 5

Urinary and histopathological disorders, 184

US Geological Survey’s (USGS), 113

Vancomycin-resistant Enterococci

(VRE), 330

Vascular disease, 260

Vector-borne diseases (VBD), 24

Vibrio cholera, 26

Vigna radiata, 181

Virginiamycin, 322

Visual motor integration test (VMIT), 268

Volatile organic chemicals (VOCs), 304

Volcanic activity, 252

Volcanic and industrial activities, 251

Volcanic eruptions, 248

Vomiting, 259

Wasps (Trichogramma evanescens), 77

Waste generation, 54

Wastewater, 2, 4, 124

Wastewater treatment plant (WWTP), 6, 56,

329, 372

Wastewaters, 56, 273

Index

401

Water, 56, 57

Waterborne disease, 26

Waterborne diseases, 62

Waterborne pathogens, 56

Water chlorination, 186

Water contamination

chemical process, 16

physical process, 16

Water pollution, 15, 57, 339

Windblown dust, 247

Wood preservative, 253

World Health Organization (WHO), 54, 192,

242, 258, 269, 270, 374

Xenobiotic micropollutants, 7, 8

Young’s modulus, 347

Zar, 246

Zearalenone (ZE), 296, 297

Zirconium metal-organic frameworks, 273

Zoonotic diseases, 23, 25

Index

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Full-text available

Dec 2016

We examined the cytotoxicity evaluation of the plastic marine debris collected in the coasts of Southwest Japan using in vitro tests, primarily the colony-forming assay (CFA) with V79 cells; the test system was based on Annex B of ISO10993-5. In approximately 30% of samples(9 of 29 samples) , the cytotoxicities were detected by the CFA, with IC50 values in the range of 18-74%. In 5 samples in which cytotoxicities were detected by the CFA, cell viability assays with TK6 cells also showed cytotoxicities. Among the samples tested, "moderate" level of cytotoxicity is the level indicating the mucosal tissue inflammation potential, which might negatively influence the physiological condition of marine based organisms via uptake into the body. In addition, we showed that floating micro-plastics can be evaluated using the CFA. This is the first study to determine the in vitro cytotoxicities of plastic marine debris using an international standard test method and quantitatively determine the cytotoxicities of plastic marine debris.

Biological Transformation of Zearalenone by Some Bacterial Isolates Associated with Ruminant and Food Samples

Article

Full-text available

Oct 2021

Zearalenone (ZEA) is a secondary metabolite produced by Fusarium spp., the filamentous fungi. Food and feed contamination with zearalenone has adverse effects on health and economy. ZEA degradation through microorganisms is providing a promising preventive measure. The current study includes isolation of 47 bacterial strains from 100 different food and rumen samples. Seventeen isolates showed maximum activity of ZEA reduction. A bacterial isolate, RS-5, reduced ZEA concentration up to 78.3% through ELISA analysis and 74.3% as determined through HPLC. Ten of the most efficient strains were further selected for comparison of their biodegradation activity in different conditions such as incubation period, and different growth media. The samples were analyzed after 24 hrs, 48 hrs, and 72 hrs of incubation. De Man Rogosa Sharp (MRS) broth, Tryptic soy broth, and nutrient broth were used as different carbon sources for comparison of activity through ELISA. The mean degradation % ± SD through ELISA and HPLC were 70.77% ± 3.935 and 69.11% ± 2.768, respectively. Optimum reducing activity was detected at 72 hrs of incubation, and MRS broth is a suitable medium. Phylogenetic analysis based on 16S rRNA gene nucleotide sequences confirmed that one of the bacterial isolate RS-5 bacterial isolates with higher mycotoxin degradation is identified as Bacillus subtilis isolated from rumen sample. B05 (FSL-8) bacterial isolate of yogurt belongs to the genus Lactobacillus with 99.66% similarity with Lactobacillus delbrukii. Similarly, three other bacterial isolates, D05, H05 and F04 (FS-17, FSL-2 and FS-20), were found to be the sub-species/strains Pseudomonas gessardii of genus Pseudomonas based on their similarity level of (99.2%, 96% and 96.88%) and positioning in the phylogenetic tree. Promising detoxification results were revealed through GC-MS analysis of RS-5 and FSL-8 activity.

Journal of Pollution Effects & Control Plastic Pollution in Pakistan: Environmental and Health Implications

Article

Full-text available

May 2021

Plastic pollution is one of the prime and alarming issues in developing countries that have vast environmental and human health impacts which need to be addressed as a priority. Unfortunately, limited work has been done on the topic, especially on air and water pollution due to plastics in Pakistan. Informal solid waste management is being done by municipalities, which is not adequate, and the problem will increase with the upsurge in population and industrialization. There is a need to address the knowledge gap and improvements in the existing conditions to manage the issue of plastic pollution separately. In this chapter, causes; impacts of plastic pollution both on human and environmental health, plastic industries, and legislative context; and best practices to manage plastic pollution along with some important recommendations are discussed. It is expected the data presented may help the managers, environmental scientists, and policymakers to manage the problem of plastic pollution. Most plastic is Made from fossil fuels like oil and natural gas, which release toxic emissions when extracted from the earth. Plastic contribution has penetrated into all branches of human activity: everyday utensils to decorations, packing industry, construction and most importantly medical industry. Excessive use of plastics everywhere, on one hand has brought easy comforts while on the other hand its safe disposal has become a major issue that is leading to dangerous levels of environmental pollution. Soil, land, air and marine pollution has worsened due to unlimited use of plastic items. Pakistan is also facing health and other hazards being created due to extensive and widespread use of plastics in the country. Irrigations system of Pakistan is one of the largest gravity flow irrigations systems in the world comprising of dams, barrages, head-works, secondary and tertiary canals and water courses, bridges, syphons and other hydraulic structures. Plastic pollution starts from the catchment areas in the mountain ranges due to tourism, local population, agricultural, industrial and other activities which cause transportation of disposed plastic bags/ bottles etc. into streams/rivers due to wind or water flow actions. In this paper a review of issues/problems caused by plastic pollution to our irrigation system has been outlined with some remedial steps.

Groundwater investigations in the Hattar industrial estate and its vicinity, Haripur district, Pakistan: An integrated approach

Article

Full-text available

Dec 2020

The Hattar industrial estate in the Haripur district, Khyber Pakhtunkhwa (KPK), Pakistan, is investigated for the groundwater potential and aquifer vulnerability using vertical electrical sounding (VES) data, borehole logs, and hydrochemical analysis. A total of eight VES points were acquired in the Haripur region using Schlumberger configuration. The interpreted VES models are further constrained by four borehole logs to delineate comprehensive information of the thin lithological layers, subsurface layers configuration, and spatial extent in the area. A quantitative interpretation based on the VES and the borehole data suggests six main subsurface layers: (i) soil cover, (ii) gravel, (iii) clay, (iv) clay with gravel, (v) silty-clay, and (vi) sand with boulder in the study area. A fence diagram is also generated to provide a detailed paleo-depositional model of the subsurface layers. The interpreted VES data is utilized to compute aquifer thickness, longitudinal conductance, and transverse resistance within the study area. The lateral extent and protective capacity for the aquifer were inferred from these measurements. The aquifer thickness is relatively low in the central and eastern parts ranging from 10 m to 11 m. The longitudinal conductance map shows values greater than 2 mhos from the central region to northern one. This is indicative of moderate to good protective capacity for the aquifer and is less vulnerable to infiltration of Hattar industrial polluted fluid. However, the values less than 0.19 mhos in the southwest and east are indicative of weak protective capacity with risk of contamination. The hydrochemical analysis of the surface and subsurface water is carried out at eleven locations to identify the water quality within the study area. The chemical analysis of the water shows the presence of the high concentration of magnesium, bicarbonate, and chlorine away from the World Health Organization (WHO) standard.

Integrating biological As(III) oxidation with Fe(0) electrocoagulation for arsenic removal from groundwater

Article

Full-text available

Jan 2021
WATER RES

Arsenic (As) is a toxic element present in many (ground)water sources in the world. Most conventional As removal techniques require pre-oxidation of the neutral arsenite (As(III)) species to the negatively charged arsenate (As(V)) oxyanion to optimize As removal and minimize chemical use. In this work, a novel, continuous-flow As removal system was developed that combines biological As(III) oxidation by bacteria with Fe electrocoagulation (EC), an Fe(0)-based electrochemical technology that generates reactive Fe(III) precipitates to bind As. The bio-integrated FeEC system (bio-FeEC) showed effective oxidation and removal of 150 µg/L As(III), without the need of chemicals. To remove As to below the WHO guideline of 10 µg/L, 10 times lower charge dosage was required for the bio-FeEC system compared to conventional FeEC. This lower Fe dosage requirement reduced sludge production and energy consumption. The As(III) oxidizing biomass was found to consist of bacteria belonging to Comamonadaceae, Rhodobacteraceae and Acidovorax, which are capable of oxidizing As(III) and are common in drinking water biofilms. Characterization of the As-laden Fe solids by X-ray absorption spectroscopy indicated that both bio-FeEC and conventional FeEC produced solids consistent with a mixture of lepidocrocite and 2-line ferrihydrite. Arsenic bound to the solids was dominantly As(V), but a slightly higher fraction of As(V) was detected in the bio-FeEC solids compared to the conventional FeEC.

Bioremediation of Hexavalent Chromium by Chromium Resistant Bacteria Reduces Phytotoxicity

Article

Full-text available

Aug 2020
Int J Environ Res Publ Health

Chromium (Cr) (VI) has long been known as an environmental hazard that can be reduced from aqueous solutions through bioremediation by living cells. In this study, we investigated the efficiency of reduction and biosorption of Cr(VI) by chromate resistant bacteria isolated from tannery effluent. From 28 screened Cr(VI) resistant isolates, selected bacterial strain SH-1 was identified as Klebsiella sp. via 16S rRNA sequencing. In Luria–Bertani broth, the relative reduction level of Cr(VI) was 95%, but in tannery effluent, it was 63.08% after 72 h of incubation. The cell-free extract of SH-1 showed a 72.2% reduction of Cr(VI), which indicated a higher activity of Cr(VI) reducing enzyme than the control. Live and dead biomass of SH-1 adsorbed 51.25 mg and 29.03 mg Cr(VI) per gram of dry weight, respectively. Two adsorption isotherm models—Langmuir and Freundlich—were used for the illustration of Cr(VI) biosorption using SH-1 live biomass. Scanning electron microscopy (SEM) analysis showed an increased cell size of the treated biomass when compared to the controlled biomass, which supports the adsorption of reduced Cr on the biomass cell surface. Fourier-transform infrared analysis indicated that Cr(VI) had an effect on bacterial biomass, including quantitative and structural modifications. Moreover, the chickpea seed germination study showed beneficial environmental effects that suggest possible application of the isolate for the bioremediation of toxic Cr(VI).

Health toxicity effects of brominated flame retardants: From environmental to human exposure

Article

May 2021
ENVIRON POLLUT

Hexabromocyclododecane (HBCD) and Tetrabromobisphenol A (TBBP-A) are brominated flame retardants widely used in variety of industrial and consumer products (e.g., automobiles, electronics, furniture, textiles and plastics) to reduce flammability. HBCD and TBBPA can also contaminate the environment, mainly water, dust, air and soil, from which human exposure occurs. This constant exposure has raised some concerns against human health. These compounds can act as endocrine disruptors, a property that gives them the ability to interfere with hormonal function and quantity, when HBCD and TBBPA bind target tissues in the body. Studies in human and animals suggest a correlation between HBCD and TBBPA exposure and adverse health outcomes, namely thyroid disorders, neurobehavior and development disorders, reproductive health, immunological, oncological and cardiovascular diseases. However, in humans these effects are still poorly understood, once only a few data evaluated the human health effects. Thus, the purpose of this review is to present the toxicity effects of HBCD and TBBPA and how these compounds affect the environment and health, resorting to data and knowledge of 255 published papers from 1979 to 2020.

WATER IN A CHANGING WORLD

Article

Aug 2001

Global Environmental Policy: Concepts, Principles, and Practice

Book

Nov 2010

Activated carbon from a specific plant precursor biomass for hazardous Cr(VI) adsorption and recovery studies in batch and column reactors: Isotherm and kinetic modeling

Article

Aug 2020

The main aim of this work was the development of the chemical activated carbon (AC) method from specific wood biomass, i.e., Eucalyptus camaldulensis sawdust (ECS), and this AC is proposed as a promising alternative treatment for hazardous Cr(VI) from aqueous solution. ECS waste sawdust was carbonized in two stages, i.e. 170 °C for 60 min, followed by 500 °C for 120 min under the continuous steam of nitrogen gas, and rated as an efficient method with H3PO4 activation (>80% Cr(VI) removal). Finally, activated carbon-Eucalyptus camaldulensis sawdust (AC-ECS) was selected for batch and column reactor studies and different influencing parameters, such as contact time, pH, temperature, initial Cr(VI) metal concentration, particle size, and bed height were optimized. AC-ECS was characterized through analysis by SEM, EDX, FTIR, and BET. Cr(VI) adsorption was found to be highly pH-dependent, i.e., 87% at pH 3.0. AC-ECS adsorption mechanism for Cr(VI) with experimental and maximum predicted adsorption capacities of 104 and 125 mg g−1, respectively, was best described by the Langmuir isotherm (R2 = 0.999) and pseudo-second-order kinetics (R2 = 0.999). The column study showed an improvement in the breakthrough curve time from 5595 to 12,270 min, with the respective increase of bed height from 5 to 15 cm, respectively. Column breakthrough data was found to be well fitted to the bed depth service time model. Current batch and column studies indicate that freshwater contamination with Cr(VI) can be managed by upscaling the AC-ECS as an efficient treatment solution.

Environmental Degradation and Micro-pollutants in Light of Environmental Laws

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