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Agro and Horticultural Wastes as Low Cost Adsorbents for Removal of Heavy Metals from Wastewater: A Review

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Abstract

In recent years the adsorption process has been recognized as an effective and economic method for the removal of heavy metals from wastewaters as it offers flexibility in design and operation so as to produce high quality treated effluents of desired standards for disposal and moreover the adsorbents can be regenerated by suitable desorption. Activated carbon had been the most used adsorbent, nevertheless it is comparatively expensive. Today's demand for safe, eco-friendly, easily available and low cost adsorbents for the removal of heavy metals from contaminated waters has necessitated research interest towards the production of low cost alternatives that is why it is an urgent that all possible sources of agro and horticultural based low cost adsorbents must be explored and their feasibility for the removal of heavy metals should be studied with various affecting parameters. This paper reviews the current methods to explore low cost adsorbents and their utilization techniques for various agro and horticultural waste by-products like sugarcane bagasse, rice husk, orange peels, almond shell, sawdust, soybean hulls, cottonseed hulls, rice bran, coconut tree sawdust, sago waste, banana pitch carbon, coconut husk, palm pressed fibre, clay and some bio adsorbents etc. which are abundantly and easily available in India for the elimination of heavy metals from wastewater.
International Refereed Journal of Engineering and Science (IRJES)
ISSN (Online) 2319-183X, (Print) 2319-1821
Volume 2, Issue 8 (August 2013), PP.18-27
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Agro and Horticultural Wastes as Low Cost Adsorbents for
Removal of Heavy Metals from Wastewater: A Review
Pushpendra Kumar Sharma1, Sohail Ayub2#, Chandra Nath Tripathi3
1Asistant professor, Department of Civil Engineering, HCST, Farah, Mathura, UP, India
2Associate Professor, Department of Civil Engineering, AMU, Aligarh, UP, India
3Associate Professor, Department of Environmental Engineering, HCST, Farah, Mathura, UP, India
Abstract:- In recent years the adsorption process has been recognized as an effective and economic method for
the removal of heavy metals from wastewaters as it offers flexibility in design and operation so as to produce
high quality treated effluents of desired standards for disposal and moreover the adsorbents can be regenerated
by suitable desorption. Activated carbon had been the most used adsorbent, nevertheless it is comparatively
expensive. Today’s demand for safe, eco-friendly, easily available and low cost adsorbents for the removal of
heavy metals from contaminated waters has necessitated research interest towards the production of low cost
alternatives that is why it is an urgent that all possible sources of agro and horticultural based low cost
adsorbents must be explored and their feasibility for the removal of heavy metals should be studied with various
affecting parameters. This paper reviews the current methods to explore low cost adsorbents and their utilization
techniques for various agro and horticultural waste by-products like sugarcane bagasse, rice husk, orange peels,
almond shell, sawdust, soybean hulls, cottonseed hulls, rice bran, coconut tree sawdust, sago waste, banana
pitch carbon, coconut husk, palm pressed fibre, clay and some bio adsorbents etc. which are abundantly and
easily available in India for the elimination of heavy metals from wastewater.
Keywords:- Adsorbate, eco-friendly, adsorption, adsorbents, sorption, agro and horticultural wastes, heavy
metals, wastewater, sago waste.
I. INTRODUCTION
Due to rapid industrialization and urbanization in developing countries like India heavy metal pollution
is a serious problem today and its treatment is of special concern due to their recalcitrance and persistence in the
environment. Like organic pollutants, most of these heavy metals do not undergo biological degradation,
resulting into harmless end products [1]. Many industries, like metal plating, mining operations, tanneries, chlor
alkali, radiator manufacturing, smelting, alloy industries and storage batteries industries, etc. release these
severely toxic heavy metal ions in their wastewaters contaminating natural streams where in disposed, which is
a major concern due to toxicity to many life forms [2].Though there are many treatment methods for removal of
heavy metals from wastewater like chemical precipitation, membrane filtration, ion exchange, coagulation and
flocculation, floatation, electrochemical treatment, adsorption and co-precipitation followed by adsorption etc.
yet various researchers have studied and revealed that physical adsorption is a highly effective and economic
technique for the removal of heavy metal from waste stream and from ancient times activated carbon has
extensively been used as an adsorbent [3] in the water and wastewater treatment plants, but it is found to be an
expensive material. Recently, an idea of the production of safe and low cost alternatives to this expensive and
commercially available activated carbon has attracted the researchers towards the low cost agro and
horticultural wastes and by-products such as sugarcane bagasse [3, 4, 5, 6, 7 and 8], rice husk [9, 10, 11, 12 and
13], sawdust [14, 15 and 16], coconut husk [3, 17], oil palm shell [18], neem bark [19], etc., for the removal of
heavy metals from wastewater and it has been investigated successfully.
A low cost adsorbent is one which needs a little processing before use, abundant in nature, a by-
product or waste material from another industry. Of course improved sorption capacity may compensate the
cost of additional processing [20]. Therefore it becomes very very important to investigate all possible agro and
horticultural based inexpensive adsorbents to be explored and their feasibility for the removal of heavy metalsto
be studied in all respects. The objective of this study is to contribute in the search for safe and low cost
adsorbents and their utilization possibilities for various agro and horticultural waste by-products, which would
have been the sources to pollute our natural streams in many cases.
II. RELEVANT LITERATURE
Let us review some agricultural waste by-products used as economic adsorbents for the elimination of
heavy metal ions from wastewater in literature.
Rice husk
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It is an agricultural waste by-product abundantly available in rice producing countries, especially in Asia
continental. It is reported that the annual world rice production is approximately 500 million metric tons, of
which 10 20% is rice husk. Dry rice husk contains 70 85% of organic matter (lignin, cellulose, sugar, etc)
and the remainder consists of silica, present in the cellular membrane [21]. Now a day the researchers have
focused on the utilization of unmodified or modified rice husk as an adsorbent for the removal of pollutants
[22]. It was reported that tartaric acid modified rice husk is a potentially useful adsorbent in batch studies for the
removal of Copper and Lead from aqueous solutions, the various affecting parameters such as pH, initial
concentration of adsorbate, particle size, temperature, contact time etc were also studied. The rapid uptake and
high adsorption capacity make the rice husk a very attractive and alternative adsorbent. The uptake of Cu and
Pb was maximum when pH was increased from 2 to 3, and thereafter remained relatively constant. [11] reported
that adsorption of Ni (II) and Cd (II) was greater when PRH was used as adsorbent. Adsorption of Cd (II) was
dependent on contact time, concentration, temperature, adsorbent doses and pH of the solution. It was also
reported that the maximum adsorption (> 90%) was obtained at a pH value of 12 [9]. Removed chromium by
rice husk carbon, prepared by carbonization of rice husk with sulphuric acid followed by CO2 activation
resulting 88% removal of total chromium and greater than 99% removal of hexavalent chromium. Column
studies showed capacity of 8.9 mg/g and 6.3 mg/g for rice husk and commercial carbons respectively, for Cr
(VI) removal [12]. Study on the use of dyestuff-treated rice husk for removal of heavy metal from waste water.
Rice hulls, when coated with the reactive dye of Procion Red or Procion Yellow, was found to be highly
effective for removal of many metal ions from aqueous solutions both in batch and column methods. The high
removals for red dyestuff-treated husk are on lead (II) and cadmium (II) at 99.8% and 99.2% respectively, for
yellow dyestuff-treated husk are on lead (II) and mercury (II) at 100% and 93.3% respectively [10]. Removed
toxic metals from wastewater using rice husk reported, at optimal conditions, the chromium, zinc, copper and
cadmium ion from aqueous solution and stated as 79%, 85%, 80% and 85% respectively [23]. Studied
adsorption of heavy metals by green algae and ground rice hull and reported that, metal adsorption by algal and
rice hull biomass, was greater than 90% for all the metals tested, (Sr, Cd, Ni, Pb, Zn, Co, Cr, As) except Ni,
with 80% removal [24]. Studied on adsorption of Cr(VI) on micro- and mesoporous rice husk-based activated
carbon and reported that the rice husk carbon is a good sorbent for theremoval of Cr(VI) from aqueous solution
rangefrom 5 to 60 mg/l with adsorbent dose of 0.8 g/lat pH < 5 under the minimum equilibration time of 2
hours and above pH 5.0 a sharp decreased adsorption with further higher pH range almost negligible adsorption.
Maximum reported adsorption is 95% removal of Cr (VI)[25].Characterized and evaluated two types of
sorbents made from rice husk. The efficiency of both sorbents in the removal of the complex matrix containing
six heavy metal was nearly 100%. These metals are Fe, Mn, Zn, Cu, Cd, and Pb, which are found in the drain
containing the agricultural and sewage wastewater [26]. Indicated that the maximum removal (66%) of Cr(VI)
for raw rice husk was obtained at pH 2, when it is given adsorbent dose of 70 g/l for 2 hours and good fit to
Freundlich isotherm with 1/n value of 2.863.
Table1. Types of rice husk as adsorbent for heavy metal
Source Adsorbent Heavy metal removal efficiency %
Cr(V) Ni(II) Cu(II) Zn(II) Cd(II) Hg(II) Pb(II)
[9] Rice husk carbon >90 - - - - - -
[10] Rice husk
water and HCl washed 79 - 80 85 85 - -
[11] Phosphate-treated - - - - >90 - -
[12] rice hulls
Dyestuff-treated (red) 39.7 61.6 78.8 75.1 99.2 92.7 99.8
Dyestuff-treated (yellow) 39.1 60.8 70.0 61.3 83.3 93.3 100
[22] Rice husk
Tartaric acid modified - - >80 - - - >95
[23] Rice hull biomass 98.93 - - - 97.96 - 99.43
[25] Rice husk carbon - - 100 100 100 - 100
[26] Raw rice husk 66 - - - - - -
Sugarcane Bagasse
It is a waste product from sugar mill mainly composed of cellulose, pentosan, and lignin [4]. [27]
Reported that the Pb (II) adsorption process obeys Langmuir’s model and Cd (II) presents adsorption in
multilayer, especially when the temperature >30ºC. When ionic strength increases, the maximum adsorption
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capacity decreases. The carboxymethylated lignin from sugar cane bagasse can absorb Pb (II) selectively rather
than Cd (II) under special conditions (pH 6.0, 30ºC, and ionic strength of 0.1 mol/dm3), when both ions are
present in the mixture. Factorial analysis of Pb (II) adsorption suggests that temperature is the most important
factor in single system and adsorption increases with increasing temperature. [4] Carried out research on single-
and multicomponent adsorption of cadmium and zinc using activated carbon derived from bagasse and reported
that the removal of Cd (II) and Zn (II) is found to increase as pH increases beyond 2 and at pH > 8.0 the uptake
is 100%. It is also evident that the sorption affinity of the derived activated carbon towards Cd (II) and Zn (II) is
comparable or better than other available adsorbents. Therefore cost wise the activated carbon prepared would
be cheaper than the commercially available ones. [5] Reported that at an adsorbent dose of 0.8 g / 50 ml is
sufficient to remove 80 100% Cr (VI) from aqueous solution having an initial metal concentration of 20 mg/l
at a pH value of 1 but the efficiency reduced sharply to 15% at pH 3. [3] Investigated the effect of solution pH,
Cr (VI) concentration, adsorbent dosage and contact time using adsorption based on bagasse and coconut jute in
a batch experiment. The removal was most effective at low pH values and low Cr (VI) concentration. Activated
coconut jute carbon was the most active among the four adsorbents studied. It was fairly stable even at higher
pH. This was followed by activated bagasse carbon, raw bagasse and bagasse ash respectively. The maximum
removal reported around 99.8 percent at pH 2. The data for all the adsorbents well fit to the Freundlich
isotherm.
Table2. Types of sugar cane bagasse as adsorbent for heavy metal
Source Adsorbent Heavy metal removal efficiency %
Cr (VI) Zn (II) Cd (II)
[3] Bagasse ash 53.4 - -
Activated bagasse carbon 99.97 - -
[3] Raw bagasse 93.5 - -
[3] Activated coconut jute carbon 99.7 - -
[4] Sugarcane bagasse activated carbon - 100 100
[5] Raw sugarcane bagasse 80-100 - -
Sawdust [14] studied that Phosphate treated sawdust (PSD) showed remarkable increase in sorption capacity of
Cr (VI) as compared to untreated sawdust. Adsorption of Cr (VI) on PSD is highly pH dependent. The
maximum adsorption of Cr (VI) was observed at pH 2. The adsorption of Cr (VI) remains at maximum (100%)
even at a pH less than 2. The adsorption densities in general decrease as the adsorbent dose is increased from
0.2 to 3g. 100% removal of Cr (VI) from synthetic wastewater as well as from actual electroplating waste
containing 50 mg/l Cr (VI) was achieved by batch as well as by column process. The adsorbed chromium can
be recovered by using 0.01 M NaOH solution. [16] Removed Cr (VI) from aqueous solution by adsorption onto
activated carbon prepared from coconut tree sawdust for the removal of Cr (VI) from aqueous solution. Batch
mode adsorption studies were carried out by varying agitation time, initial Cr (VI) concentration, carbon
concentration and pH. Langmuir and Freundlich adsorption isotherms were applied to model the adsorption
data. Adsorption capacity was calculated from the Langmuir isotherm and was 3.46 mg/g at initial pH of 3.0 for
particle size 125-250 μm. The adsorption of Cr(VI) was pH dependent and maximum removal was observed in
the acidic pH range. Saw dust types and its efficiency summarized in (Table 3).
Table 3. Types of saw dust as adsorbent for heavy metal
Source Adsorbent Heavy metal removal Efficiency %
Cr (VI) Ni (II) Cu (II) Zn (II)
[14] Phosphate treated tree sawdust 100 83 86 86.o
[14] Untreated tree sawdust - 91 86 75.7
[15] Coconut tree saw dust carbon 98.84 - - -
Soybean hulls, cottonseed hulls, rice bran and straw
[28] adsorbed heavy metals by citric acid modified soybean hulls, extracted with 0.1 N NaOH, modified with
different citric acid (CA) concentration (0.1 1.2 M) at 120ºC for 90 minutes, with adsorption capacities for
Cu2+ from 0.68 to2.44 m moles/g>>unmodified hulls (0.39 m moles/g), probably due to the increase in
carboxyl group imparted onto the hulls by reaction with citric acid. [29] analyzed soybean hulls containing
(mg/g dry weight basis) protein, lipid ash, lignin, cellulose, hemicelluloses and silica which are 109, 10.0, 36.4,
49.1, 676, 137, and < 10 respectively and reported adsorption capacities for Zn (II) in decreasing orderas
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soybeanhulls, cottonseed hulls, rice straw, sugarcane bagasse with varying capacities from 0.52 to 0.06meq/g
dry weight of byproduct. [30] Evaluated defatted rice bran, soybean and cottonseed hulls for both synthetic and
metal plating wastewater for theirability to adsorb heavy metals. NaOH and HCl washed soybean and
cottonseed hulls were better adsorbents than water-washed (control) hulls, heat treated cottonseed and soybean
hulls were inferior adsorbents than water-washed hulls. Reuse of these agricultural wastes after one
adsorption/desorption cycle was not satisfactory.
Table 4. Types of soybean hulls, cottonseed hulls, rice bran and straw as adsorbent for heavy metals
Source Adsorbent Heavy metals removal Efficiency%
Cr (III) Ni (II) Cu (II) Zn (II)
[29] Soybean hulls 98.1 95.6 99.7 96.40
Cottonseed hulls 97.6 96.7 98.8 96.60
Soybean hulls
-Water washed - 53.0 83.0 51.60
-NaOH washed - 55.8 61.0 71.40
-HCl washed - 69.8 89.6 90.30
-900heattreat - 52.5 80.0 59.80
-1450heat treat - 31.7 71.0 33.33
Cottonseed hulls
-Water washed - 47.6 58.8 59.50
-NaOH washed - 72.8 37.4 69.50
[30] -HCl washed - 51.6 81.5 70.30
-900heattreat - 46.5 54.9 56.10
-1450heattreat - 44.1 52.6 50.30
Defated rice brans(pH5)
-Non stabilized, defatted at
Southern Regional Research - 29.2 71.5 38.40
Centre SRRC
-extrusion stabilized,
defatted at SRRC - 36.6 83.2 75.00
-extrusion stabilized,
defatted at Riceland Foods Inc.RF - 38.3 75.6 96.80
-expander stabilized, defatted at RF - 20.4 64.7 20.50
[15] Prepared activated carbon from various agricultural solid wastes such as, silk cotton hulls, coconut tree
sawdust, sago waste, maize cob, and banana pitch etc. and used for the removal of colour and metal ions from
aqueous solution. [17] Used coconut husk and palm pressed fibres in batch and column studies for removal of
chromium (VI) from solution and investigated the optimum pH for maximum removal of 80% is 2.0. [32]
Prepared activated carbon from waste Parthenium and used as adsorbent for removal of Ni (II) from aqueous
solution. They assessed kinetic and equilibrium parameters in batch study, varying time of contact, adsorbate
concentration, carbon concentration, pH, temperature and desorption. They modeled sorption data using
Langmuir and Freundlich classical isotherm. The adsorption capacity (Qo) from the Langmuir isotherm was
54.35 mg Ni (II) /g of AC at pH 5.0 and temp 20ºC, particle size range 250 500 μm. Increase in pH from 2 to
10 increase percent removal of metal ion. [31] Used sago waste, a pollutant as the adsorbent for lead and copper
ions from aqueous solutions with respect to the equilibria and kinetics, best fitting the Langmuir and the
Freundlich Models, with optimum pH 4-5.5 and reported a considerable adsorption capacity for lead (46.6
mg/g), copper (12.4 mg/g) respectively.
Table5. Other types of agricultural wastes as adsorbent for heavy metal
Source Adsorbent Heavy metals removal Efficiency %
Cr (VI) Ni (II) Cu (II) Hg (II) Pb (II)
[15] Silk cotton carbon - 64 - 100 -
Coconut tree sawdust carbon - 84.3 - 100 -
Sago waste carbon - 100 - 100 -
Maize cob carbon - 100 - 100 -
Banana pitch carbon - 96.4 - 100 -
[17] Coconut husk >80 - - - -
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Palm pressed fibre >80 - - - -
[31] Sago waste - - >75 - >95
[
33] Investigated the mechanism of the metal biosorption by means of the Langmuir adsorption model with
chemically pretreated coniferous barks as adsorbent losing their metal binding capacities. Under the physico-
chemical condition the metal affinity of bark was found in the following decreasing order Lead, Chromium,
Nickel, Zinc, Copper. [34] Prepared activated carbons from Casurinaequisetifolia leaves carbonised and treated
with sulphuric acid (1:1), phosphate salt (10%) or zinc chloride (25%) at different temperatures to removeCr
(VI) from wastewater and the conditions optimised for the most effective carbons. The equilibrium data fitted
well with the Freundlich adsorption isotherm. Desorption studies showed that 65 80% of adsorbed chromium
could be desorbed by alkali followed by acid treatment. Activated Carbons could be reused without change in
the adsorption capacity.
[35] Reported that the Nile rose plant powder adsorbed 80% and bone powder removed 98.8 % of lead at lead
concentration of 4 mg/l and pH 6. [36] Investigated that for single heavy metal ion solutions, phosphoric acid
treated peanut shells were better metal ion adsorbents as compared to citric acid treated ones. For multiple metal
ion solutions, the metal uptake from solution by adsorbents was strongly dependent on selective affinity to other
competing metal ions. The acid-treated samples exhibited a high selectivity for Cu (II) ions; 42% for citric acid-
treated and 28% phosphoric acid-treated. The study revealed that Citric acid-treated samples were significantly
better adsorbents as compared to the phosphoric acid-treated samples. [39] Reviewed the adsorption of a few
heavy metals on natural and modified kaolinite and montmorillonite. [40] Reviewed agricultural waste material
as potential adsorbent for sequestering heavy metal ions from aqueous solutions.[41] reviewed the removal of
heavy metal ions from wastewater by chemically modified plant wastes as adsorbents.[42] reviewed the use of
low cost adsorbents for heavy metals uptake from contaminated water. [43] Investigated the kaolinite clay
obtained from Longyan, China to remove heavy metal ions Pb(II), Cd(II), Ni(II) and Cu(II) from wastewater.
The uptake is rapid with maximum adsorption being observed within 30 minutes and kaolinite clay was used for
removing metal ions from real wastewater containing Pb(II), where its concentration was reduced from 160.00
mg/L to 8.00 mg/L. [44] Reported Zinc and Copper removal from aqueous solutions using brine sediments,
sawdust and mixture of both materials. The maximum adsorption capacity was found to be 4.85, 2.58 and 5.59
mg/g for Zinc and 4.69, 2.31 and 4.33 mg/g for Copper respectively, using an adsorbent/solution ratio of 1/40.
Biosorption of heavy metals from aqueous solution is a relatively new process that has been confirmed a very
promising process for the heavy metal contaminated wastewater treatment. The major advantages of biosorption
are its high effectiveness in reducing the heavy metal ions and the use of inexpensive bioadsorbents.
Biosorption process are particularly suitable to treat dilute heavy metal wastewater [37]. Typical bioadsorbents
can be derived from three sources as follows:(1) non-living biomass such as bark, lignin, shrimp, krill, squid,
crab shell, etc.; (2) algal biomass; (3) microbial biomass, e.g. bacteria, fungi and yeast[45]. Different forms of
inexpensive, non-living plant materials such as potato peels [46], sawdust [47], black gram husk [48], egg shell
[49], seed shells [50], coffee husk [51], sugar-beet pectin gels [52], and citrus peels [53] etc., have been widely
studied with various affecting parameters in detail and investigated by various researchers as potential
biosorbents for heavy metals removal from aqueous solutions. [54] investigated removal efficiency of waste tea
from nickel containing aqueous solutions by fixed-bed columns with liquid flow rate (520 mL/min), initial
Ni(II) concentration (50200 mg/L), bed height (1030 cm), pH of feed solution (2.05.0) and particle size
(0.150.25 to 1.03.0 mm) of adsorbent using the bed depth service time model and the Thomas models and
found that longest breakthrough time and maximum of Ni(II) adsorption was at pH 4.0 with decrease in the
particle size from 1.03.0 to 0.150.25mm resulted in significant increase in the treated volume, breakthrough
time and bed capacity. The best results were at lowest flow rate and column bed capacity, exhaustion time
increased with increasing bed height. When the initial Ni(II) concentration is increased from 50 to 200 mg/L,
the corresponding adsorption bed capacity appeared to increase from 7.31 to 11.17 mg/g. [55] used Azadirachta
indica (neem) leaf powder as an adsorbent for the removal of chromium from aqueous solutions in a batch
process with various process parameters that include agitation time, adsorbent size and dosage, initial chromium
concentration, volume of aqueous solution and pH of the aqueous solutions and studied adsorption behavior
following Freundlich and Langmuir isotherms. The adsorption mechanism was described by a pseudo second
order kinetics. [56] Summarized the performances of various biological compounds, minerals, modified
activated carbons, as well as industrial and agricultural wastes as low cost and simple adsorbents in both
synthesis and implementation. [57] Reviewed that a number of plant wastes like rice husks, spent grain,
sawdust, sugarcane bagasse, fruit wastes, weeds and others modified by numerous chemicals such as mineral
and organic acids, bases, oxidizing agent, organic compounds, etc. exhibit higher adsorption capacities than
unmodified forms for Cd, Cu, Pb, Zn and Ni. [58] Prepared a low cost adsorbent from tamarind seeds activated
by heat treatment and with concentrated sulfuric acid and conducted batch studies for Cr(VI) removal from
aqueous solutions and studied the parameters such as initial pH, contact time, initial Cr(VI) concentration, and
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adsorbent dosage. The adsorption of Cr (VI) was found to be maximum at low values of initial pH in the range
of 13. The adsorption process of Cr (VI) was tested with Langmuir and Freundlich isotherm models.
Application of the Langmuir isotherm to the systems yielded maximum adsorption capacity of 29.08 mg g1.
The adsorption process followed second order kinetics and the corresponding rate constant was found to be
0.0026 g mg1 min1. [59] Karanja Seed Oil Cake, a by-product after oil extraction, which otherwise goes waste
or as fertilizers, was used as Precursor for Activated Carbon Preparations. Adsorbent from Karanja seed oil cake
was prepared in laboratory by various Chemical and Physical Activation Processes and was studied for
adsorptions of Dyes and Waste Water Treatment. [60] Used a Prunus Amygdalus (Almond nut shell) as a low
cost adsorbent for removal of Cr (VI) from aqueous solutions and the uptake capacity of this adsorbent was
studied as a function of contact time, pH, adsorbate concentration and adsorbent dose. From the time variation
experiments, the equilibrium contact time was found to be 6 hr. Cr (VI) uptake capacity of the adsorbent
increased with decrease in pH with optimum pH 1.8. The adsorption capacity of the adsorbent was found to
increase with increase in adsorbate concentration, whereas it decreased with increasing in adsorbent dose. [61]
Used thermally synthesized low cost adsorbent i.e aegel marmelos fruit shell which is a waste remains after the
conversion of pulp into jam, jelly, squash, marmalade or syrup, etc @ carbonization temperature of 300oC,
specific surface area 1.2433±0.0414 m2/g and studied for adsorption of Cr (VI) from aqueous solution for
various concentrations & doses and as a result of experimental analysis concluded that the adsorbent developed
in the study was fairly effective. [62] Compared the efficiency of various low cost adsorbents as in the order of
PAC>Bagasse>FA>SD>WSD>Coconut coir. The effect of chromium solution PH, contact time , adsorbent
dosage, initial chromium concentration and adsorbent mesh size on adsorption were studied in a batch
experiment. Fly ash, Bagasse, W.S.D, SD, &Coconut coir were the most active at pH-6 , which is closer to pH
of chromium bearing industrial waste as compared to the pH 2.0 of PAC. The equilibrium data for the
adsorption of chromium were analysed in the light of Langmuir and Freundlich isotherm models. The ultimate
adsorption capacity for the adsorbents PAC, Bagasse, FA, S.D., W.S.D & Coconut coir were found as 4.97
mg/gm, 4.91mg/gm, 4.90mg/gm, 4.89 mg/gm, 4.77mg/gm and 4.56 mg/gm by column studies respectively. [63]
Compiled, an extensive list of sorbent literature to summarize available information on a wide range of low-
cost agricultural product and by-product sorbent and their modification for removing heavy metals from water
and wastewater. [64] Studied the adsorption of hexavalent chromium from aqueous medium by physically
activated rice husk carbon and optimised 150 minutes , 20 mg/l , 2 ,and 5g/l for time contact, initial
concentration, PH and adsorbent dose respectively along with a result of 95.2% adsorption of Cr(VI). [65]
studied the feasibility of sugar cane bagasse to remove chromium (VI) from the aqueous solutions by designed
batch experiments evaluating the impact of various parameters, such as adsorbent does, contact time, initial
concentration and pH on chromium removal efficiency, the results indicated a prominent effect of pH on the
chromium reduction by the adsorbent used. [66] Reviewed the chromium occurrence, transformation, in
different environments and the possible and currently practicing remedial measures and the evaluation of their
efficacy to minimize the toxic effects.[67] Studied the potential of Pinus roxburghii bark as an adsorbent for the
removal of heavy metals such as Cr(VI), Ni(II), Cu(II), Cd(II) and Zn(II) from aqueous solution at ambient
temperature and found adsorption capacity of the material was found to be 4.15, 3.89, 3.81, 3.53 and 3.01 mg g-
1 for Cr(VI), Zn(II), Cu(II), Ni(II) and Cd(II), respectively, at an initial metal ion concentration of 50 mg L-1 at
pH 6.5. The effect of concentration, contact time, adsorbent dose, solution pH, adsorbent particle size, salinity
and hardness on the adsorption of Cr (VI) were also studied in detail in batch experiments. The equilibrium
contact time for Cr (VI) adsorption was found to be 1 h. Adsorption equilibrium data fit well to the Freundlich
isotherm in the concentration range studied. The maximum adsorption (96.2%) was recorded at pH 3 for the
initial Cr (VI) concentration of 50 mg L-1. The adsorbed metal ions from industrial wastewater were recovered
using 0.1 M HCl solution. The column operation was found to be more effective compared to batch process.
The percent recovery of Cr (VI) from industrial wastewater by column operation and batch process was found
to be 85.8 and 65%, respectively. The results showed that Pinus roxburghii bark can be used as a cost-effective
adsorbent for the removal and recovery of Cr(VI) from wastewater. [68] compared efficiency of activated
coconut shell and activated coconut coir in removing toxic hexavalent chromium from its synthetic solution and
tannery industrial effluent in batch mode with respect to pH, adsorbent dose, contact time & initial metal ion
concentration and the applicability of adsorption isotherms. Activated coconut shell exhibited more adsorption
potential as compared to Activated coconut coir and maximum removal exhibited by ACS was 88% and 83.0 %
for 0.3 mm and 1.0 mm in case of synthetic solution & 76%(0.3mm) and 66%(1.0mm) in case of tannery
effluent at optimized conditions (pH =2, dose=1.0g/100ml, contact time=60 minutes & initial metal ion
concentration=10 ppm). In general ACS was observed to be better adsorbent than ACC while adsorbents of
particle size 0.3 mm have greater efficiency than 1.0 mm. On application of adsorption kinetics, Adsorption of
Cr (VI) by ACS and ACC followed the pseudo first order and pseudo second order model and investigated that
the activated coconut coir is an efficient adsorbent for hexavalent chromium removal. [69] Used Archis
Hypogea (ground nut) shells, a lingo cellulosic waste biomass in three different forms natural, beads and
Agro and Horticultural Wastes as Low Cost Adsorbents for Removal…
www.irjes.com 24 | Page
activated carbons as low cost adsorbent and evaluated sequestering of Cr (VI) from synthetic wastewater in
batch experiments. They investigated that the removal of metal ions was dependent on physic-chemical
characteristics of the adsorbent, adsorbate concentration and other process parameters at an optimum pH 2.0.
The experimental data were analyzed based on Freundlich and Langmuir adsorption isotherms. Kinetic studies
indicated that the adsorption of metal ions followed a pseudo second order equation. [70] Used compost
generated from Carnation flowers waste as a low cost adsorbent for removal of chromium (VI) from aqueous
solutions and reported 99% removal at pH 2.0 @ 10 mg/l of Cr (VI) solution @ 10 g/l of compost @ 3 hours
contact time. Under the above conditions the kinetic adsorption isotherms were examined varying the Cr(VI)
concentrations from 15-200 mg/l. The maximum sorption capacity at equilibrium (Qm) from the Langmuir
model was reported to be 6.25 mg/g. To date, though hundreds of studies on the use of low cost adsorbents have
been published. Agricultural wastes, horticultural wastes and bye products, industrial by-products and wastes
and natural substances have been studied as adsorbents for the heavy metal wastewater treatment. Several
reviews are available that discuss the use of low cost adsorbents for the treatment of heavy metals wastewater
[37]. Yet, there is a need to explore some further more new low cost adsorbents which are abundant in nature
and may cause pollution if released in streams or land without treatment.
III. CONCLUSION
The present literature review study of various agro and horticultural adsorbents over here shows a great
potential for the removal of heavy metals from wastewater. The sorption capacity depends on the type of the
adsorbent investigated and the nature of the wastewater treated as well. The use of expensive and commercially
available activated carbon for the removal of the heavy metals from aqeous solution can possibly be replaced by
using low cost, more effective, abandant and readily available agricultural wasteby-products as adsorbents.
There is an urgent need of more detailed studies to be carried out so as to better understand the process of more
effective and economic adsorption hence therefore to developsuch a technology that matters truly and
effectively.
As presented through (Tables 1 to 5), various agricultural adsorbents show a high degree of removal
efficiency for heavy metals such as chromium, nickel, lead, copper, mercury, zinc, cadmium etc.
To date, though hundreds of studies on the use of low cost adsorbents have been published. Yet, there is a need
to explore some further more new low cost adsorbents which are abundant in nature and may cause pollution if
released in streams or land without treatment and this way there will be a two way pollution control so called
“Aam kea am guthalion ke daam”
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... There is therefore need to design new microbiological media which are both efficient and affordable (Sidana and Farooq, 2014). This may be achieved by using materials that are very much available especially in the form of low cost agro and horticultural wastes (Sharma et al., 2006;Ahluwalia and Goyal, 2007) and by-products such as sugarcane bagasse (Kong et al., 2014), rice husk, sawdust, coconut husk, oil palm shell, neem bark, etc. (Sharma et al., 2013) as raw materials for microbial media production. Although not all potentially applicable waste materials have been systematically examined yet, sugarcane bagasse could also be adapted as an alternative material for designing a new medium (Dhokpande and Kaware, 2013) as it is readily available in large volumes in the environment. ...
... Although not all potentially applicable waste materials have been systematically examined yet, sugarcane bagasse could also be adapted as an alternative material for designing a new medium (Dhokpande and Kaware, 2013) as it is readily available in large volumes in the environment. Use of sugarcane bagasse as a source of nutrients for growth of the microbial biomass would also help to reduce the nuisance caused by this material to the environment, as it constitutes a major source of environmental pollution as mentioned by Sharma et al. (2013) and Sidana and Farooq (2014). Sugarcane Bagasse is a by-product of sugarcane (Saccharum officinarum). ...
... As an agricultural by-product, it is generated in large quantity in countries that produce it, and requires no special treatment or processing before it is used as substrate material (Parani et al., 2016). Sugarcane bagasse mainly composes of cellulose, hemicellulose, pentosan, and lignin (Sharma et al., 2013), as well as other components like ash, moisture and reducing sugars (Zafar, 2015). Sugarcane bagasse is very useful, and has been employed in many agricultural and industrial processes. ...
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... Based on this study, oil palm is a major contributor in the agricultural sector to the GDP, which is 37.9% followed by other agricultural crops (25.1%) [21]. Besides, Malaysia is also the top 10 coconut-producing countries in the world where coconut is the fourth important crop after the oil palm, rubber, and rice [22,23]. The cultivation area of coconut is about 82,917 ha in the year 2017 and the per capita consumption of coconut as fruit in Malaysia is the highest (17.0 kg/y) [22,23]. ...
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... In the state of Punjab in India these agricultural wastes are burnt on spot at agricultural fields only called as 'Parali' burning creating lot of smoke, CO 2 emission and chemical fog in national capital range of Delhi. Many researchers have reported that instead of burning the agricultural wastes at spot, there may be an alternative to convert them in to value added wastes which can be the potential adsorbents for removal of heavy metals from aqueous solutions [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Various researchers have proved these horticultural and agro wastes to be potential adsorbents in last recent years [2][3][4][5][6][7][8][9][10][11][12][17][18][19][20][21]. ...
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... Agricultural wastes are generally dense with a low percentage of ash content, making them simple to transform to activated carbon, which has a superior possibility for adsorbing heavy metals [58]. Numerous investigations have revealed that agricultural wastes have strong adsorption capability for various contaminants [76,[160][161][162][163][164]. ...
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The release of massive pollutants amounts continuously because of urbanization and industrialization has caused a big ecological problem worldwide. Due to their activities, effluents of many industries: mining operations, paper/pulp, and batteries, release different heavy metals, including Copper (Cu), Lead (Pb), and Nickel (Ni), into the environment. Heavy metals are of big concern due to their high toxicity, big bioaccumulation susceptibility, and serious threat to humans and ecosystems. Compared to organic pollutants, which are highly influenced by biological and chemical degradation, heavy metals have no degradation into end products using these methods. Therefore, the removal of such metals is considered a big challenge in water purification. For metals removal, different techniques have been applied, such as precipitation, ultrafiltration, and coagulation. However, those applications have many drawbacks: low efficiency, high consumption of reagents, and generation of toxic sludge. In contrast, adsorption considers an effective method for metal removal, owing to the method’s simplicity, economic and versatility, making it the most convenient way for toxic metals removal. Many conventional adsorbents, such as activated carbon and alumina, have been effectively employed. Nevertheless, the biggest disadvantages of using such adsorbents appear to be their price due to high activation costs and limited reusability. Biosorption has lately emerged as a method with several advantages, including minimal cost, ease of use, and great efficacy, even for trace amounts of metallic ions. This paper aims to review the relevant literature regarding the adsorption method for heavy metals removal from wastewater. Different treatments of heavy metals from wastewater and their related features are highlighted. The metals’ toxicity and hazards to health and the environment are also discussed. The application of various materials as bioadsorbents is explored, such as natural adsorbents and industrial and agricultural wastes.
... Bio-sorption technique is an emerging technology that utilizes low cost materials such as: agricultural wastes (Sharma et. al., 2013;Abia and Igwe 2006;Ahalyaet. al., 2003), activated carbon from natural sources (Youssef et. al., 2013), industrial waste materials (Mohammed et. al.,2014); etc., to remove heavy metals from aqueous medium. The use of agricultural wastes such as: kola-nut testa, coconut coir, sugarcane bagasse, beans husks, rice husks, etc., as bio-sorben ...
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The modification of kola-nuttesta with 0.2M sulphuric acid and 39.9%(v/v) formaldehyde was carried out at 50 0 C. The formaldehyde modified kola-nut testa (FMKT) and unmodified kola-nut testa (UKT) were characterized by specific gravity, point of zero charge, melting point, solubility and FTIR spectroscopy. The adsorption capacity of the formaldehyde modified kola-nut testa(FMKT)for Cu 2+ and Fe 2+ ions in aqueous solution at equilibrium conditions and room temperature were: 2.24 mg/g for Cu 2+ , 1.97 mg/g for Fe 2+ .The unmodified kola-nut testa(UKT) gave adsorption capacities of 2.05 mg/g for Cu 2+ and 2.12 mg/g for Fe 2+ metal ions. Percentage removal of the metal ions from a single metal ion aqueous solution were carried out under various adsorption conditions such as temperature, pH, contact time, adsorbent dose and initial metal ion concentrations. The Fe 2+ metal ion gave better results with optimal average percentage removal above 90%, using the formaldehyde modified kola-nut testa when compared to Cu 2+ metal ion with an average of 70% percentage removal. Similarly, the unmodified kola-nut testa followed a similar trend. Thus an indication that both unmodified and formaldehyde modified kola-nut testa holds promising potentials in the treatment of industrial effluents containing heavy metals.
... Various treatments are used for tannery wastewater like physico-chemical methods such as sedimentation [11], electro-flotation [12] coagulation-flocculation [13], filtration [13], membrane, and adsorption [14], while the chemical and biological methods are considered very expensive in terms of energy and reagents consumption. Among them, the treatment of effluents containing heavy metals revealed that adsorption is a very effective technique [16]. In addition, the quantities of fly and bottom ashes produced annually by the Jorf Lasfar TAQA Thermal Power Plant (Morocco) are significant, respectively around 400.000 and 40.000 tones [17] and pose many problems related to their storage, which requires their management. ...
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This work aims to treat the raw effluents from a tannery using raw coal waste (fly ash and bottom ash) and bentonite clay as less expensive adsorbents and percolating agents. Their combination constitutes effective filters to retain heavy metals, dyes, and organic matter. After analysis of the raw wastewater, a significant pollutant load was detected; the chemical oxygen demand (COD) is around 3,400 mg·L-1 , the biological oxygen demand about 240 mg·L-1 and suspended matter of 490 mg·L-1. These waters are also heavily loaded with heavy metals especially chromium with a high value of 981 mg·L-1 , and they have an acidic pH of 4.2, which greatly exceed the specific limit discharges values , applicable to discharges from Moroccan tannery industries. Their treatment with fly ash, bottom ash, and bentonite clay leads to an almost complete elimination of Cr, Fe and Zn with a discolor-ation of 96% where the pH becomes neutral to slightly alkaline. The COD analysis gives an abatement rate of more than 72% while suspended matters are considerably reduced with a turbidity rate of 99%. Thus, the treated water can be used for irrigation or as wash water in industries.
... However, the high cost and difficult regeneration and separation processes of activated carbons limit their usefulness in water treatment [7]. A variety of renewable materials, such as rice husk, sugar beet pulp, soybean, hulls, clay, and tea waste, have developed as alternative, abundant adsorbents for heavy metals and organic compound removal [8,9]. Due to their accessibility, eco-friendliness, and affordability, these materials have attracted a lot of interest. ...
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Groundwater highly contaminated with organic substances and heavy metal ions in the Kariangau Industrial Area, Balikpapan, East Kalimantan is indicated by the comparatively high COD. Therefore, the technology for treating wastewater to remove various toxins before releasing it into the environment needs to be advanced. Here, we present a green synthetic method of a composite adsorbent (SF/SS) using soursop seeds and silkworm cocoons. SEM, FTIR, and BET were used to analyze the physicochemical characteristics of the adsorbent. Mechanistic investigation of the SF/SS adsorbent performance for the removal of Cu2+ metal ions and crystal violet (CV) was conducted, while taking into account variables affecting adsorption properties. The Freundlich and Langmuir isotherm adsorption models were used to fit the adsorption equilibrium, while pseudo-first and second-order models were used to assess the adsorption kinetics. The mesoporous SF/SS adsorbent exhibited the highest adsorption capacities of 78.6 and 69.2 mg‧g-1, respectively. The pseudo-first model showed the best fit for CV removal with a kinetic rate of 0.0634 min-1, while the Freundlich model exhibited the best fitting for both of CV and Cu2+ removal. The results showed that SF/SS can be applied as an efficient adsorbent for both of heavy metal and organic dye removal.
... These adsorbents' adsorption capacity is not very high but economically feasible, particularly for India's rural areas [2]. Researchers are effectively used green adsorbents for wastewater treatment [1,[3][4][5][6][7][8][9][10][11][12][13][14][15][16]. ...
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Rice bran, a green and low-cost adsorbent, is used for Chromium (VI) and Copper (II) remotion from its aqueous solution. The influence of different process parameters in a fixed-bed on the removing efficiency has been investigated. The results show that the removal efficiency is higher at a minimum flow rate, low metal ion concentration, and higher bed height. The adsorption studies show that the rice bran has a better affinity to Chromium (VI) than Copper (II). Different kinetic models are used for the prediction of the column performance. This study shows that rice bran could be a potential and eco-friendly adsorbent for chromium (VI) and copper (II) removal and is suitable for developing countries like India. Multiple linear regression and ANN-based genetic algorithm modelling have been applied successfully to predict both metal ions' percentage removal separately.
... Several research reports on the effective removal of fluoride using low-cost and herbal materials are available [1]. The tested materials include activated alumina, neem, tulasi, tamarind seeds, Moringa olifera seeds, amorphous alumina, activated carbon, calcite, zeolite clay, charcoal, bleaching earth; red mud etc. [1][2][3][4][5][6][7][8][9][10][11][12]. Vetiver is an indigenous material which finds its use in many medicinal and engineering applications. ...
Conference Paper
Uncontaminated water is at last turning into an extravagance for humankind. Pollution from various sources has led to the degradation of the standard of water. The presence of contaminants has made water treatments as need of the hour. Fluoride is one such element which despite of being a vital component can cause serious ailments when present in excess quantity. This study focuses on the power of Vetiver (Vetiveriazizanioides) root, an indigenous material, to scale back fluoride levels within the water. During this study, a low-cost household filter model has been developed using sand, gravel and locally available vetiver roots without any chemical activation and tested for Defluorination efficiency Impact of detainment time and thickness of the layers were examined. The filtered water was tested for pH, turbidity, fluoride level and Escherichia coli count. Statistical analysis of the data was done using WASP software to verify the obtained results. The results showed that influent fluoride concentration of 12ppm was brought down to 0.82 ppm by a filter bed of 1cm thickness for a detention period of 1 hour. The filter was also found effectively reducing the coliform bacterial levels in the water (58 % reduction). Thus, vetiver can be proposed as domestic low-cost water filtering material with excellent defluoridation and purifying potential.
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Sago processing waste, which is both a waste and a pollutant, was used to adsorb lead and copper ions from solution. The sorption process was examined in terms of its equilibria and its kinetics. The effect of pH, contact time, sorbate concentration, particle size and sorbent mass were also studied. The most effective pH range was found to be 4 to 5.5 for both metals. The equilibrium data for both metals fitted both the Langmuir and the Freundlich models and, based on the Langmuir constants, the sago waste had a greater sorption capacity for lead (46.6 mg/g) than for copper (12.4 mg/g). The kinetic studies showed that the sorption rates could be described better by a second-order expression than by the more commonly applied Lagergren equation.
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Activated Carbon is predominantly amorphous solid that has extraordinary large internal surface area and pore volume. These unique pore structures play an important role in many different liquid and gas phase applications because of their association with adsorptive properties. Although most types of industrial activated carbons are produced from naturally occurring carbonaceous materials such as coal, wood and coconut shells by activation Process. Here some Agro-industrial by-products can be used as precursor material for preparing activated carbons in the laboratory. Karanja Seed Oil Cake is by-product after oil extraction, which otherwise goes waste or as fertilizers, is used as Precursor for Activated Carbon Preparations. Adsorbent from Karanja seed oil cake is prepared in laboratory by various Chemical and Physical Activation Processes and is studied for adsorptions of Dyes and Waste Water Treatment.
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The industrial estates in India are dominated by small and medium scale industries, which are posing a serious threat to the environment by virtue of discharging effluents of a polluting nature. The problems become severe due to the presence of heavy metals in the effluents. Chromium is widely used in a number of industries such as electroplating, metal finishing, cooling towers, dyes, paints, anodising and leather tanning industries. The toxicity of chromium (VI) is well known and is considered a hazard to the health of humans and animals. The presence of chromium (VI) in aquatic environments at high concentrations is also lethal to marine species. The treatment of chromium bearing effluents have been reported through several methods, such as chemical reduction, precipitation, ion exchange, electrochemical reduction, evaporation, reverse osmosis and adsorption. However among these, adsorption is found to be highly effective, inexpensive and an easy method to operate. India is an agricultural country and generates a considerable amount of agricultural wastes such as sugar cane bagassess, coconut jute, nut shell, rice straw, rice husk, waste tea leaves, ground nut husk, crop wastes, peanut hulls and fertilizer wastes. Successful studies on these materials could be beneficial to developing countries and could be easily applied as adsorbents for the removal of chromium from wastewater. Most of the previous work highlights the use of commercial activated carbon but these adsorbents are relatively expensive and less feasible to be used in developing countries. Keeping these in view batch experiments have been designed to study the feasibility of sugar cane bagasse to remove chromium (VI) from the aqueous solutions. While evaluationg the impact of various parameters, such as adsorbent does, contact time, initial concentration and pH on chromium removal efficiency, the results indicate a prominent effect of pH on the chromium reduction by the adsorbent used in the present study.
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Arachis hypogea shells (ground nut shells), a lignocellulosic waste biomass, was evaluated for sequestering of Cr(VI) from synthetic wastewater. Arachis hypogea shells (AHS) were used in three different forms, viz. natural (AHSN), immobilized in the form of beads (AHSB), and in the form of activated carbon (AHSC). Batch experiments were performed for the removal of hexavalent chromium. Effects of pH adsorbent dose, initial metal ion concentration, stirring speed, and contact time were investigated. The removal of metal ions was dependent on the physico-chemical characteristics of the adsorbent, adsorbate concentration, and other studied process parameters. Maximum metal removal for Cr(VI) was observed at pH 2.0. The experimental data were analyzed based on Freundlich and Langmuir adsorption isotherms. Kinetic studies indicated that the adsorption of metal ions followed a pseudo-second-order equation.
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The adsorption process is being widely used by various researchers for the removal of heavy metals from waste streams and activated carbon has been frequently used as an adsorbent. Despite its extensive use in the water and wastewater treatment industries, activated carbon remains an expensive material. In recent years, the need for safe and economical methods for the elimination of heavy metals from contaminated waters has necessitated research interest towards the production of low cost alternatives to commercially available activated carbon. Therefore there is an urgent need that all possible sources of agro-based inexpensive adsorbents should be explored and their feasibility for the removal of heavy metals should be studied in detail. The objective of this study is to contribute in the search for less expensive adsorbents and their utilization possibilities for various agricultural waste by-products such as sugarcane bagasse, rice husk, oil palm shell, coconut shell, coconut husk etc. for the elimination of heavy metals from wastewater. ABSTRAK Penjerapan adalah teknik yang digunakan secara meluas oleh para penyelidik untuk perawatan air sisa yang dicemari oleh logam berat dan karbon teraktif banyak digunakan sebagai penjerap. Walaupun karbon ini banyak kegunaannya dalam perawatan air dan air sisa industri, ianya masih suatu bahan yang mahal. Baru-baru ini keperluan untuk kaedah yang selamat dan ekonomi untuk perawatan logam berat telah menumpukan minat penyelidik-penyelidik ke arah bahan yang lebih murah dan kedapatan karbon teraktif yang komersial. Satu keperluan untuk mengkaji sisa pertanian sebagai bahan ganti karbon teraktif komersial telah wujud dan penyelidikan yang terperinci akan tindakan mereka terhadap logam berat mesti dilakukan. Objektif kajian ini adalah untuk menyumbang kepada kajian dalam mencari penjerap yang murah dan kebolehgunaan bahan ini seperti hampas tebu, hampas padi, tempurung kelapa sawit, tempurung kelapa, sabut kelapa dll. untuk merawat logam berat dalam air sisa.