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Metal(Loid) Levels in Biological Matrices from Human Populations Exposed to Mining Contamination—Panasqueira Mine (Portugal)
Abstract and Figures
Mining activities may affect the health of miners and communities living near mining sites, and these health effects may persist even when the mine is abandoned. During mining processes various toxic wastes are produced and released into the surrounding environment, resulting in contamination of air, drinking water, rivers, plants, and soils. In a geochemical sampling campaign undertaken in the Panasqueira Mine area of central Portugal, an anomalous distribution of several metals and arsenic (As) was identified in various environmental media. Several potentially harmful elements, including As, cadmium (Cd), chromium (Cr), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se), were quantified in blood, urine, hair, and nails (toe and finger) from a group of individuals living near the Panasqueira Mine who were environmentally and occupationally exposed. A group with similar demographic characteristics without known exposure to mining activities was also compared. Genotoxicity was evaluated by means of T-cell receptor (TCR) mutation assay, and percentages of different lymphocyte subsets were selected as immunotoxicity biomarkers. Inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) analysis showed elevated levels of As, Cd, Cr, Mn, and Pb in all biological samples taken from populations living close to the mine compared to controls. Genotoxic and immunotoxic differences were also observed. The results provide evidence of an elevated potential risk to the health of populations, with environmental and occupational exposures resulting from mining activities. Further, the results emphasize the need to implement preventive measures, remediation, and rehabilitation plans for the region.
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... After reading the full text of each study, a total of 18 studies were included in the review (Beaumont et al. 2008;Tubek et al. 2008;Kerger et al. 2009;Linos et al. 2011;Unisa et al. 2011;Sharma et al. 2012;Coelho et al. 2013;Sazakli et al. 2014;Karagiannis et al. 2015;Cárdenas-González et al. 2016;Arcega-Cabrera et al. 2017, 2018Filler et al. 2017;Marouf et al. 2017;Herath et al. 2018;Sánchez-Díaz et al. 2018;Whitaker et al. 2020;Vogel et al. 2021). Tables 6-11 give the main characteristics of the studies included in the final review. ...
... All the articles studied concern the period 2008 to 2021. The studies studied took place in regions of Greece (n ¼ 3) (Linos et al. 2011;Sazakli et al. 2014;Karagiannis et al. 2015), Mexico (n ¼ 3) (Cárdenas-González et al. 2016;Arcega-Cabrera et al. 2017, 2018, China (n ¼ 2) (Beaumont et al. 2008;Kerger et al. 2014), India (n ¼ 3) (Unisa et al. 2011;Sharma et al. 2012;Herath et al. 2018), the USA (n ¼ 1) (Whitaker et al. 2020), Germany (n ¼ 1) (Vogel et al. 2021), Finland (n ¼ 1) (Filler et al. 2017), Poland (n ¼ 1) (Tubek et al. 2008), Spain (n ¼ 1) (Sánchez-Díaz et al. 2018), Portugal (n ¼ 1) (Coelho et al. 2013), and Iraq (n ¼ 1) (Marouf et al. 2017). (Coelho et al. 2013;Marouf et al. 2017) and one cohort study (Karagiannis et al. 2015). ...
... The studies studied took place in regions of Greece (n ¼ 3) (Linos et al. 2011;Sazakli et al. 2014;Karagiannis et al. 2015), Mexico (n ¼ 3) (Cárdenas-González et al. 2016;Arcega-Cabrera et al. 2017, 2018, China (n ¼ 2) (Beaumont et al. 2008;Kerger et al. 2014), India (n ¼ 3) (Unisa et al. 2011;Sharma et al. 2012;Herath et al. 2018), the USA (n ¼ 1) (Whitaker et al. 2020), Germany (n ¼ 1) (Vogel et al. 2021), Finland (n ¼ 1) (Filler et al. 2017), Poland (n ¼ 1) (Tubek et al. 2008), Spain (n ¼ 1) (Sánchez-Díaz et al. 2018), Portugal (n ¼ 1) (Coelho et al. 2013), and Iraq (n ¼ 1) (Marouf et al. 2017). (Coelho et al. 2013;Marouf et al. 2017) and one cohort study (Karagiannis et al. 2015). ...
Both in developed and developing countries, there is a growing concern about the dangerous hexavalent chromium, in the consumption of drinking water. Hexavalent chromium is recognized to have a negative impact on the human body, both in the short and long term. The purpose of this study is to evaluate the relationship between hexavalent chromium in water and its impact on human health. A systematic review of the international literature is applied, according to the instructions of PRISMA protocol, in the databases PubMed and Scopus, for the years 2005–2022. The systematic literature review was conducted using inclusion and exclusion criteria, and appropriate keywords for exposure and outcome. A total of 18 studies met all inclusion criteria. Most research concludes that hexavalent chromium is a risk factor for humans, as opposed to trivalent chromium who is a protective factor. A study indicates the consumption of drinking water with high concentrations of hexavalent chromium, as a protective factor for human life, while eight of the total studies suggest hexavalent chromium as a potential risk factor. It is necessary to clarify the origin, the mode of action, and the negative impact has on human health, to create appropriate preventive and intervention measures.
HIGHLIGHTS
Assessment of the relationship between harmful hexavalent chromium in water and human health effects (systematic review – PRISMA protocol).;
Data on hexavalent chromium from an epidemiological point of view.;
A study indicates the consumption of drinking water with high concentrations of hexavalent chromium is a protective factor for human life.;
Eight of the studies suggest hexavalent chromium as a possible risk factor.;
... Previous studies on occupational exposure to Pb reported higher B-Pb levels compared to our results: 3.6 μg/dL among those exposed to mining contaminations (Coelho et al. 2012), 10.6 μg/dL among electrical solderers (Mohammadyan et al. 2019), and 6.5 μg/dL among workers in a manufacturing plant (Nakhaee et al. 2019). In addition, our study's average T-Pb concentration among the traffic enforcers is 1.0 μg/g. ...
... In addition, our study's average T-Pb concentration among the traffic enforcers is 1.0 μg/g. On average, the T-Pb contents showed in our study are lower than the ones reported for populations exposed to mining conditions (21.4 μg/g (Ndilila et al. 2014) and 1.11 μg/g (Coelho et al. 2012)), but slightly higher than a population exposed to welding fumes (0.39 μg/g (Grashow et al. 2014)). Future studies are warranted to measure the actual Pb content in the air of Metro Manila, Philippines, and the average cumulative Pb exposure in the air by traffic enforcers. ...
Purpose
Several epidemiological studies have linked lead (Pb) exposure to induced oxidative stress and the promotion of inflammatory response. We performed a within-subjects study (repeated measures study) to evaluate the relationship between the concentration of blood lead (B-Pb) and toenail lead (T-Pb) and circulating markers of inflammation.
Methods
We evaluated the associations between B-Pb concentrations and T-Pb concentrations and circulating markers of inflammation, soluble intracellular adhesion molecule-1 (s-ICAM-1), soluble vascular adhesion molecule-1 (s-VCAM-1), and high-sensitivity C-reactive protein (hs-CRP) on 158 traffic enforcers from the Metropolitan Manila Development Authority (MMDA) traffic enforcer’s health study. Linear mixed-effects models with random subject-specific intercepts were fitted to estimate the association between B-Pb and T-Pb exposure and circulating markers of inflammation, adjusting for confounding factors.
Results
Traffic enforcers were middle-aged men (89.4%) with a mean age (± SD) of 37.1 years ± 8.9 years and had a total of 293 valid markers of inflammation measurements. B-Pb concentration was related to increased hs-CRP levels. A 10% increase in B-Pb was associated with a 5.7% increase in hs-CRP level [95% confidence interval (95% CI): 1.3–10.1]. However, B-Pb was not associated with s-ICAM-1 and s-VCAM-1. Furthermore, no associations were observed between T-Pb and all the circulating markers of inflammation.
Conclusions
Low-level B-Pb may increase hs-CRP among traffic enforcers. Moreover, the study suggests that Pb via the oxidative and inflammation pathways may have an essential role in the development of cardiovascular disease. Furthermore, MMDA and the Department of Labor and Employment can use our study’s findings as evidence to conduct routine screening of blood heavy metals, especially Pb, among MMDA and other traffic enforcers as part of their yearly medical examination.
... A recent review was conducted evaluating available human biomonitoring data for the Portuguese population where metals and metalloids were included [48]. From these studies, only one reported urinary data for the populations living near and working in the Panasqueira mine [49], and results showed levels of As similar to the ones determined for our population. The authors believe these values were related to mine contamination and that this environmental contamination probably persists after mines are closed [48,49]. ...
... From these studies, only one reported urinary data for the populations living near and working in the Panasqueira mine [49], and results showed levels of As similar to the ones determined for our population. The authors believe these values were related to mine contamination and that this environmental contamination probably persists after mines are closed [48,49]. ...
Exposure to environmental chemicals during developmental stages can result in several adverse outcomes. In this study, the exposure of Portuguese children to Cu, Co, I, Mo, Mn, Ni, As, Sb, Cd, Pb, Sn and Tl was evaluated through the analysis of first morning urine through ICP-MS. Furthermore, we attempted to determine possible exposure predictors. The study sample consisted of 54% girls and 46% boys, with a median age of 10 years; 61% were overweight/obese and were put on a nutritionally oriented diet. For I, half of the population was probably in deficiency status. The median urinary concentrations (μg/L) were Cu 21.9, Mo 54.6, Co 0.76, Mn 2.1, Ni 4.74, As 37.9, Sb 0.09, Cd 0.29, Pb 0.94, Sn 0.45, Tl 0.39 and I 125.5. The region was a significant predictor for Cu, Co, Ni, As and Tl. Children living in an urban area had higher urinary levels, except for Co and Ni. Age was a significant predictor for Cu, I, Mo, Mn, Ni, Sb, Cd and Sn with urinary levels of these elements decreasing with age. No sex-related differences were observed. Diet and weight group were predictors for urinary Cu, Mn, Ni, Sb and As. Significant differences were observed between the diet/weight groups for Cu, Ni, Sb and As, with the healthy diet group presenting higher values.
... Cheyns et al. (2014) [9] in turn, investigated the level of human and environmental exposure to Co in Africa by analyzing dust, contaminated soils, and urine. Coelho (20112) [10] evaluated the adverse health effects of metal contamination by biomonitoring biological specimens and the MN in Portugal. Joca (2009) [50] evaluated the genotoxicity in workers exposed to silica in Brazil. ...
Environmental and occupational exposure to toxic metals has led many people around the world to have serious health problems. Mining activities contribute to an increased risk of exposure to these elements. In this work, a study of environmental biomonitoring and routes of exposure to toxic metals in a region of artisanal mining was performed. This study was carried out in the district of Taquaral de Minas, located in the Jequitinhonha Valley in the state of Minas Gerais. The valley is one of the wealthiest and highest gem-producing areas in Brazil. Five artisanal mines were sampled (Bode, Pirineu, Pinheira, Lajedo, and Marmita). Several potentially toxic metals (Be, Zn, Mn, Ba Cd, Hg, and U) were investigated in the soils and dust over the rocks and the soils. Samples from 22 individuals occupationally exposed and 17 unexposed persons, who formed the reference group, were analyzed for trace elements by an inductively coupled plasma mass spectrometer. The genotoxicity was evaluated by the micronucleus test in buccal mucosa epithelial cells, where the following changes were scored: micronuclei (MN) binucleate (BN) cells and kariolytic (KL) cells. The MN test showed significantly increased frequencies in all alterations of exposed individuals compared to the controls (p < 0.05, Student’s t-test). The urine analysis showed levels of Cr, Ni Ba, Pb, and As in the blood, which were higher than the ATSDR recommended levels. The association between the MN test and the trace element concentrations found in the blood and urine was significant (p < 0.05). The higher the number of years of working, the higher the concentrations in the blood were, due to chronic exposure. The results of the present study indicate environmental contamination and a potential risk to the health of miners, suggesting an intervention.
... These values are lower than the mean Se concentrations among women inthe same age group, 33 (0.064-103 µg/L) and among children aged 10-14 years, 45 (0.36-168.5 µg/L) in our study. While there is no commonly accepted concentration range established for Se, some studies suggest a range of 750-1250 µg/kg for both finger and toenails [3], while others [65] suggest a larger range of 620-1530 µg/kg. As far as we know, there are T.R. Godebo et al. no previous studies indicating nail and urine Se status within the MER region or other regions in Ethiopia. ...
Background:
Selenium (Se) plays an important role in human health, yet Se overexposure or deficiency can lead to deleterious health effects. This study aims to determine the concentration of Se in drinking water and staple cereal grain (maize, wheat, and teff) samples from the Main Ethiopian Rift (MER) Valley, and correspondingly, assesses Se biomarkers and their status as measured in the urine and fingernails of 230 individuals living in 25 MER communities.
Method:
The concentration of Se in drinking water and cereal grain (maize, wheat, and teff) samples, and urine and fingernail samples were measured using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Demographic, anthropometric, and elemental concentrations were described by their quartiles and mean ± standard deviations. The 5th and 95th percentiles were used to describe the concentrations Se biomarkers ranges. The Se biomarker distributions in different study communities were further characterized according to Se levels found in drinking water, sex, and age using ANOVA, and multivariate regression. We conducted a correlation analysis (with Pearson correlation coefficient) and fitted a regression to evaluate the associations between these variables.
Results:
The mean concentration of Se in the drinking water samples was 0.66 (range: 0.015-2.64 µg/L; n = 25), and all samples were below the threshold value of 10 μg/L for Se in drinking water set by the World Health Organiation (WHO). In Ethiopia, most rural communities rely on locally produced cereal grains. We found mean Se concentrations (µg/kg) of 357 ± 190 (n = 14), 289 ± 123 (n = 14), and 145 ± 100 (n = 14) in wheat, teff, and maize, respectively. Furthermore, Se concentrations in drinking water showed no significant correlation with biomarker measures, indicating that the primary source of dietary Se is likely from local foods including staple grains. The mean±SD (5th-95th percentiles) of Se concentrations in fingernails and urine among study subjects were 1022 ± 320 (624-1551 µg/kg), and 38 ± 30 (1.9-100 µg/L), respectively.
Conclusion:
A sizeable share of study participants (31%) fell below the lower limits of what is considered the currently accepted Se range of 20-90 µg/L in urine, though relatively few (only 4%) had similarly low fingernail levels. On the other hand, none of the samples reached Se toxicity levels, and the biomarker levels in this study are comparable to results from other studies that find adequate Se. Our results show that Se toxicity or deficiency is unlikely in the study population.
... Principio: Este sistema está basado en la capacidad de determinar metales y algunos no metales en solución, nos ayuda atomizar, ionizar y excitar todas las especiaciones del arsénico que son enviadas hacia el plasma para su detección (Martinez & Gasquez, 2005). (Coelho et al., 2012).. ...
Las actividades antropogénicas producen diversos desechos tóxicos que se liberan en el medio ambiente, y la principal exposición ocurre en la metalurgia del arsénico, que pueden provocar en el trabajador arsenicismo ocupacional con múltiples daños en el organismo y riesgos de contaminación en ríos, plantas y suelos. En Portovelo en el sector el Pache son principales sectores de explotación minera, donde evidencia altas concentraciones de arsénico, cianuro y mercurio. En la presente investigación se determinó la presencia de arsénico urinario en los trabajadores mineros, mediante espectrometría de emisión atómica con plasma de acoplamiento inductivo (ICP-AES), para estimar posibles riesgos de salud, se seleccionó una muestra de 30 trabajadores mineros en cinco plantas de beneficio cumpliendo con los criterios de inclusión e exclusión. Los resultados se obtuvieron utilizando modelos estadísticos, determinando que los trabajadores presentaron elevadas concentraciones de arsénico urinario mayor al Índice Biológico de Exposición (0,035 mg/l), en un porcentaje de 27% con una media de 0.23 mg/l, y un valor máximo de 0,4 mg/l y el 73 % se encontraron debajo de este índice. En relación al consumo de agua y los valores de arsénico elevados se encontró una correlación significativa con un R de 0.34 y una p de 0.000041. En la evaluación de transaminasas (TGO-TGP) urea y creatinina se encontraron valores normales y no hay diferencia significativa con relación arsénico. El estudio de biomarcadores es una herramienta que ayuda analizar efectos tempranos en poblaciones expuestas con el fin de prevenir enfermedades relacionadas con la ingesta de arsénico.
Due to the public health concern of arsenic, environmental management measures in mining areas had been implemented. To assess the effect of environmental management measures in the mining area comprehensively, arsenic accumulation in the urine, hair, nails, and urinary metabolites of residents in a realgar mining area in Hunan province, China were investigated in 2019, and the changes in arsenic levels in the biomarkers during 2012–2019 were tracked. The importance of confounding factors (age, sex, occupation, residence, clinical history, vegetable source, cooking fuel, smoking, alcohol consumption, BMI) was analyzed using the Boruta algorithm. After the implementation of environmental management measures (including ceasing mining and smelting activities, building landfills, adjusting the planting structure, and soil restoration), urine, hair, and nail arsenic concentration decreased drastically but were still excessive. Arsenic accumulation was highest in older male miners who were long settled in the mining area and consumed homegrown vegetables. The only factor for changes in urinary arsenic levels was the cooking fuel type; residents using wood as cooking fuel experienced sustained arsenic exposure. Occupation and sex were important for determining arsenic changes in the hair and nails. Short-term arsenic accumulation in urine was affected by arsenic exposure, while long-term accumulation in hair and nails by arsenic metabolic capacity. The percentage of urinary arsenic metabolism and arsenic methylation indices of the participants in the mining area were within the normal range (%iAs: 10–30 %, %MMA: 10–20 %, % DMA: 60–80 %); samples indicated worse metabolic capacity than the reference population. The arsenic metabolic capacity of male miners was relatively weak, probably aggravated by alcohol drinking and smoking. Without soil remediation, arsenic exposure will continue. Homegrown vegetables and biomass fuels should be abandoned; reduced cigarette and alcohol consumption is recommended. Urinary arsenic would be more proper for assessing environmental remediation in mining areas.
Republication or reproduction of this report or its storage and/or dissemination by electronic means is permitted without the need for formal IUPAC permission on condition that an acknowledgment, with full reference to the source, along with use of the copyright symbol ©, the name IUPAC, and the year of publication, are prominently visible. Publication of a translation into another language is subject to the additional condition of prior approval from the relevant IUPAC National Adhering Organization. Abstract: Numerous species of metal ions cause immunosensitization in humans. Possible approaches to determine those occupational and environmental exposures to metals that result in immunological changes include lymphocyte transformation assay, cytokine profiling, and measurement of lymphocyte subpopulations. In two previous papers, we considered lymphocyte transformation assay [1] and cytokine profiling [2]. Here we review the effects of exposures to metals on lymphocyte subpopulations. Specific consideration is given to beryllium, chromium, cobalt, nickel, palladium and platinum, cadmium, gold, mercury, and lead. Analysis of the scientific literature shows that immunosensitizing metals may have influences on the lymphocyte subset composition, but only in a few instances does exposure to metals cause reproducible shifts of lymphocyte subpopulations. If lymphocyte subpopulations are analyzed, each diagnostic step, including indication, sample handling, analytic procedure, and data interpretation, should adhere to good qual-ity assurance and quality control.
The age-related changes in absolute and percentage values of lymphocyte subsets in the peripheral blood of healthy children of different ages (1 month to 13 years) were studied by flow cytometry. The absolute and percentage values for most lymphocyte subpopulations differed substantially with age. Comparisons among age groups from infants through adults revealed progressive declines in the absolute numbers of leukocytes, total lymphocytes, and T, B, and natural killer (NK) cells. The percentages of T cells increased with age. Within the T-lymphocyte population, the CD8 ⁺ subset increased but the CD4 ⁺ subset decreased, resulting in a declining CD4 ⁺ /CD8 ⁺ ratio. The percentage of B cells declined, but that of NK cells remained unchanged. The percentage of HLA-DR ⁺ T cells increased over time, but their number changed inconsistently. Our findings confirm and extend earlier reports on age-related changes in lymphocyte subpopulations. These data should be useful in the interpretation of disease-related changes, as well as therapy-dependent alterations, in lymphocyte subsets in children of different age groups.
Amid the traditional development and applications work reported during the period covered by this review, the most obvious identifiable trend is that of downsizing. This is seen with techniques requiring smaller sample sizes or more effective analyte pre-concentration, and with new instrumentation. Procedures for extraction included the use of nanoparticles in various ways and the single-drop methodology with one example exploiting 1-dodecanol, a material that shifts between liquid and solid states at around room temperature. Hand held instrumentation is commonplace in some application areas but less so within the sector covered by this Update. However an XRF device was used to carry out limit tests for harmful metals in pharmaceutical agents. The potential for expansion of in vivo testing is now on the horizon with the development of a portable XRF instrument. Other features to mention are the larger than usual number of topics reviewed and the publication of several reference ranges for trace elements in biological fluids and also results from market-basket surveys. Application areas that were mentioned more than usual were studies involving the brain, CSF and neural function, and measurements of iodine including one method that involved vapour generation for ICP-AES. New approaches to establishing the authenticity of foods and food labelling were reported and examples of discrepancies between amounts measured and the stated contents were identified. A new writer, John Marshall, is welcomed to the team with primary responsibility for preparing the foods and beverages table.
Metallic elements in hair were assessed in human subjects randomly sampled from six villages in Hubei province, PR China, known to differ in industrial pollution. Metallic elements assessed included copper, zinc, lead, and cadmium. Subjects sampled included adults and children of both sexes. Soil and rice samples from the villages were also examined for contents of metallic elements. Soil and rice contents of copper, lead, and cadmium were higher in the villages closer to the pollution source (copper smeltery). Hair contents of copper, lead, and cadmium were higher in subjects from the polluted villages compared with subjects from the nonpolluted areas. No differences were found in hair zinc content among the villagers. Cadmium contents in rice and human hair were linearly correlated. For lead and copper a logarithmic relation was found. No difference was found between the two genders with respect to hair metallic contents. With regard to age, hair cadmium content was highest in the older age groups in the polluted villages and may reflect chronic exposure. No other systematic age effects were observed. It was concluded that contents of cadmium, lead, and copper in human hair do reflect the degree of environmental pollution.
Mining is one of the oldest activities in human civilization. Mining industry is a vital economic sector for many countries, but it is also one of the most hazardous activities, both occupationally and environmentally. Mining operations comprise a series of stages involving the discovery and extraction of mineral lying under the surface of the earth. During these processes several toxic wastes are produced and released into the surrounding environment causing pollution of air, drinking water, rivers and soils, changes in topography, hydrogeology, and chemistry of terrestrial and aquatic ecosystems. Mining activities cause several health impacts in miners and communities living near the mine site that may continue to be experienced even when the mine has gone. Abandoned mines are one of the most important issues as they pose a real or potential threat to human safety and health, and an environmental hazard. Numerous initiatives have been made to reduce risk and maximize benefits but much more needs to be done. Laws and regulations need to be improved to better protect the health and safety of people working in, living near, and those otherwise impacted by historic, current, and proposed mines.