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Journal of Hazardous Materials 157 (2008) 220–229

Review

Heavy metal adsorption onto agro-based waste materials: A review

Ayhan Demirbas ∗
Sila Science, Trabzon, Turkey
Received 13 August 2007; received in revised form 7 January 2008; accepted 8 January 2008
Available online 17 January 2008

Abstract
Adsorption has been proved to be an excellent way to treat industrial waste effluents, offering significant advantages like the low-cost, availability,
profitability, easy of operation and efficiency. Biosorption of heavy metals from aqueous solutions is a relatively new process that has proven very
promising in the removal of contaminants from aqueous effluents. Biosorption is becoming a potential alternative to the existing technologies for
the removal and/or recovery of toxic metals from wastewater. The major advantages of biosorption technology are its effectiveness in reducing
the concentration of heavy metal ions to very low levels and the use of inexpensive biosorbent materials. Metal adsorption and biosorption onto
agricultural wastes is a rather complex process affected by several factors. Mechanisms involved in the biosorption process include chemisorption,
complexation, adsorption–complexation on surface and pores, ion exchange, microprecipitation, heavy metal hydroxide condensation onto the
biosurface, and surface adsorption.
© 2008 Elsevier B.V. All rights reserved.

Keywords: Heavy metal ion; Agro waste material; Adsorption; Biosorption

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
2. Chemical properties of agricultural waste materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
3. Adsorption models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4. Metal adsorption and biosorption studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
4.1. Mechanism of metal biosorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225

1. Introduction The heavy metal ions are stable and persistent environmental
contaminants since they cannot be degraded and destroyed.
Nowadays heavy metals are among the most important pol- These metal ions can be harmful to aquatic life and water con-
lutants in source and treated water, and are becoming a severe taminated by toxic metal ions remains a serious public health
public health problem. Industrial and municipal waste waters problem for human health. Heavy metals removal from aqueous
frequently contain metal ions. Industrial waste constitutes the solutions has been traditionally carried out by chemical precipi-
major source of various kinds of metal pollution in natural water tation [7]. Numerous methods exist to remove detrimental metal
[1–4]. The application of biosorption in environmental treatment ions from aqueous solutions. Activated carbon has been the most
has become a significant research area in the past 10 years. Heavy used adsorbent, nevertheless it is relatively expensive. In order to
metal ions are reported as priority pollutants, due to their mobil- obtain cheaper adsorbents, lignocellulosics materials have been
ity in natural water ecosystems and due to their toxicity [5,6]. studied [8].
The presence of cupper, zinc, cadmium, lead, mercury, iron,
nickel and others metals, has a potentially damaging effect
∗ Tel.: +90 462 230 7831; fax: +90 462 248 8508. on human physiology and other biological systems when the
E-mail address: ayhandemirbas@hotmail.com. tolerance levels are exceeded. Many methods of treatment

0304-3894/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2008.01.024
 A. Demirbas / Journal of Hazardous Materials 157 (2008) 220–229 221

for industrial wastewater have been reported in literature [9]. towards electrophiles. In natural lignin the positions on the aryl
Amongst these methods are neutralization, precipitation, ion rings para- and ortho- to the hydroxyl groups are usually occu-
exchange and adsorption. For low concentrations of metal ions pied by alkoxy or alkyl substituents [50].
in wastewater, the adsorption process is recommended for their Lignin has an aromatic, three-dimensional polymer structure
removal. The process of adsorption implies the presence of an with apparent infinite molecular weight [51]. The cellulose is
“adsorbent” solid that binds molecules by physical attractive located predominantly in the secondary cell wall [52]. Lignin
forces, ion exchange, and chemical binding. It is advisable that is covalently linked with xylans in the case of hardwoods and
the adsorbent is available in large quantities, easily regenerable, with galactoglucomannans in softwoods. Even though mechani-
and cheap [10]. cally cleavable to a relatively low molecular weight, lignin is not
Biosorption of heavy metals from aqueous solutions is a rela- soluble in water. Lignin has strong resistance to chemical reac-
tively new process that has proven very promising in the removal tions, a high surface area (180 m2 /g) [53]. Molecular weight of
of contaminants from aqueous effluents. Adsorbent materials the polymeric lignin changes from 2000 to 15,000 g/mol [54].
derived from low-cost agricultural wastes can be used for the These properties of lignin reveal that it has a potential to be used
effective removal and recovery of heavy metal ions from wastew- as a possible adsorption material to remove heavy metals from
ater streams [11,5,12–19]. waste waters.
The sorption capacity of lignocellulosics for metal ions is The removal of heavy metal ions using low-cost abundantly
generally described as adsorption. The major advantages of available adsorbents: agricultural wastes such as tea waste and
biosorption technology are its effectiveness in reducing the coffee [55], hazelnut shells [56–58], peanut hull [59,21], red
concentration of heavy metal ions to very low levels and the fir [60] and maple [61] sawdusts [62,63], pinus bark [64–67]
use of inexpensive biosorbent materials. The major advantages and different bark samples [68–77], palm kernel husk [78] and
of biosorption over conventional treatment methods include: coconut husk [79,80], peanut skins [81], modified cellulosic
low-cost; high efficiency; minimization of chemical and/or materials [82,83], chemically modified cotton [84], corncobs
biological sludge; regeneration of biosorbent; no additional [85] and modified corncob [86], rice hulls [87], apple wastes
nutrient requirement; possibility of metal recovery [20]. The [88], coffee grounds [89], bark [90,91], modified bark [37],
cost advantage of biosorption technology would guarantee a wool fibers [92], tea leaves [93], and wool, olive cake, pine nee-
strong penetration of the large market of heavy metal polluting dles, almond shells, cactus leaves, charcoal [94], modified lignin
industries. [48,95,96], banana and orange peels [97], modified sugar beet
In general, raw lignocellulosic biosorbents were modified by pulp [98], modified sunflower stalk [25], palm fruit bunch [99],
various methods to increase their sorption capacities because maize leaf [20] and different agricultural by-products [100–107]
metal ion binding by lignocellulosic biosorbents is believed were used and investigated.
to take place through chemical functional groups such as car-
boxyl, amino, or phenolics. More recently, great effort has been 2. Chemical properties of agricultural waste materials
contributed to develop new adsorbents and improve existing
adsorbents. Many investigators have studied the feasibility of The term biomass (Greek, bio, life + maza or mass) refers
using low-cost agro-based waste materials [21–29]. to wood, short-rotation woody crops, agricultural wastes, short-
Many conventional techniques such as chemical precipita- rotation herbaceous species, wood wastes, bagasse, industrial
tion, membrane filtration, electrolysis, ion exchange, carbon residues, waste paper, municipal solid waste, sawdust, biosolids,
adsorption and co-precipitation/adsorption are used for the grass, food processing waste, aquatic plants, algae animal
removal of heavy metals in wastewater treatment, but they are wastes, and a host of other materials [108]. It is a rather sim-
suitable for high concentrations of metals [30–41]. At low con- ple term for all organic materials that seems from plants, trees,
centrations, these techniques fail in certain cases. Also they crops and algae. Two larger carbohydrate categories that have
are not cost-effective. For this reason, low-cost adsorbents have significant value are cellulose and hemicelluloses (holocellu-
been evaluated for the removal of heavy metals from aqueous lose). The lignin fraction consists of non-sugar type molecules
solutions [42]. [109].
Modified lignin obtained from lignocellulosic materials is Cellulose is a remarkable pure organic polymer, consist-
used for the removal of trivalent and hexavalent chromium, lead ing solely of units of anhydroglucose held together in a giant
and zinc from aqueous solutions [1,43–48]. Lignin is known to straight chain molecule [110]. These anhydroglucose units are
adsorb many heavy metal ions [49]. bound together by ␤-(1,4)-glycosidic linkages. Due to this link-
Agricultural by-products usually are composed of lignin and age, cellobiose is established as the repeat unit for cellulose
cellulose as major constituents and may also include other polar chains (Fig. 1). Cellulose must be hydrolyzed to glucose before
functional groups of lignin, which includes alcohols, aldehydes, fermentation to ethanol.
ketones, carboxylic, phenolic and ether groups. These groups By forming intramolecular and intermolecular hydrogen
have the ability to some extent to bind heavy metals by donation bonds between OH groups within the same cellulose chain and
of an electron pair from these groups to form complexes with the surrounding cellulose chains, the chains tend to be arranged
the metal ions in solution [16]. parallel and form a crystalline supermolecular structure. Then,
The alkali lignin produced by the alkaline pulping of soft- bundles of linear cellulose chains (in the longitudinal direction)
wood consequently contains a low content of positions reactive form a microfibril which is oriented in the cell wall structure [29].
222 A. Demirbas / Journal of Hazardous Materials 157 (2008) 220–229

Fig. 1. The structure of cellulose. Anhydroglucose is the monomer of cellulose, cellolbiose is the dimmer (Ref. [29]).

Fig. 2. Schematic illustration of xylans: (A) Partial xylan structure from hardwood and (B) Partial xylan structure from softwood (Ref. [29]).

Cellulose is insoluble in most solvents and has a low accessibility soluble in alkali and, as such, are more easily hydrolysed
to acid and enzymatic hydrolysis. [112–114].
Unlike cellulose, hemicelluloses consist of different Lignins are polymers of aromatic compounds. Their func-
monosaccharide units. In addition, the polymer chains of hemi- tions are to provide structural strength, provide sealing of water
celluloses have short branches and are amorphous. Because of conducting system that links roots with leaves, and protect plants
the amorphous morphology, hemicelluloses are partially soluble against degradation [115]. Lignin is a macromolecule, which
or swellable in water. Hemicelluloses (arabinoglycuronoxylan consists of alkylphenols and has a complex three-dimensional
and galactoglucomannans) are related to plant gums in composi- structure. Lignin is covalently linked with xylans in the case of
tion, and occur in much shorter molecule chains than cellulose. hardwoods and with galactoglucomannans in softwoods [116].
Hemicelluloses are derived mainly from chains of pentose sug- The basic chemical phenylpropane units of lignin (primarily
ars, and act as the cement material holding together the cellulose syringyl, guaiacyl and p-hydroxy phenol) as shown in Fig. 3
micells and fiber [111]. are bonded together by a set of linkages to form a very complex
Among the most important sugar of the hemicelluloses matrix. This matrix comprises a variety of functional groups,
component is xylose. In hardwood xylan, the backbone chain such as hydroxyl, methoxyl and carbonyl, which impart a high
consists of xylose units which are linked by ␤-(1,4)-glycosidic polarity to the lignin macromolecule [29,117]. Cellulose and
bonds and branched by ␣-(1,2)-glycosidic bonds with 4-O- lignin structures were extensively investigated in the earlier
methylglucuronic acid groups [29]. In addition, O-acetyl groups studie s [118,119,51,120–122].
sometime replace the OH groups in position C2 and C3 (Fig. 2A).
For softwood xylan, the acetyl groups are fewer in the back- 3. Adsorption models
bone chain. However, softwood xylan has additional branches
consisting of arabinofuranose units linked by ␣-(1,3)-glycosidic Isotherm adsorption models have been used in waste stream
bonds to the backbone (Fig. 2B). Hemicelluloses are largely treatment to predict the ability of a certain adsorbent to remove
 A. Demirbas / Journal of Hazardous Materials 157 (2008) 220–229 223

The Freundlich isotherm can also be linearized by the following:

 
X 1
ln = ln KF + ln Ce (5)
M n
where KF and n are adsorption capacity and affinity, respecti-
vely.
The Langmuir and Freundlich isotherm models are only
applicable to batch adsorber systems where sufficient time is
provided to allow equilibrium between the pollutant in solution
and the pollutant adsorbed on the media to occur. During the
Fig. 3. Schematic illustration of building units of lignin. flow through the adsorbent, many of the pollutants are expected
to come into contact with active surface sites and thus be retained
on the surface of the adsorbing media. Table 1 shows the Lang-
a pollutant down to a specific discharge value. When a mass of muir and Freundlich constants for the adsorption of Cu(II) and
adsorbent and a waste stream are in contact for a sufficiently long Cd(II) from aqueous solution onto rice husk and modified rice
time, equilibrium between the amount of pollutant adsorbed and husk.
the amount remaining in solution will develop. For any system The bed depth-service time (BDST) model, this is based
under equilibrium conditions, the amount of material adsorbed on the Bohart and Adams quasi-chemical rate law [125]. The
onto the media can be calculated using the mass balance of Eq. assumption behind the equation (Bohart and Adams Equation,
(1): 1920) is that equilibrium is not instantaneous and therefore, the
X V rate of the sorption reaction is proportional to the fraction of
= (Co − Ce ) (1) sorption capacity still remaining on the media. The linearized
M M
BDST model equation is as follows [125–127]:
where X/M (typically expressed as mg pollutant/g media) is the  
No 1 Co
mass of pollutant per mass of media, Co is the initial pollutant tb = D− ln −1 (6)
1000ενCo kCo Cb
concentration in solution, Ce is the concentration of the pollutant
in solution after equilibrium has been reached, V is the volume where tb is the time until breakthrough (min), Co is the initial
of the solution to which the media mass is exposed, and M is the concentration of pollutant (mg/L), Cb is breakthrough concen-
mass of the media. tration of pollutant (mg/L), ν is the fluid velocity or loading rate
Adsorption data for wide range of adsorbate concentrations (m/min), ε is the porosity of the filter, k is quasi-chemical rate
are most conveniently described by adsorption isotherms, such constant from Bohart and Adams theory (L/mg s), No is capacity
as the Langmuir [123] or Freundlich [124] isotherms. The gen- of the media for each pollutant in a multi-component solution
eral Langmuir model defined by Eq. (2): (mg pollutant per cubic meter of filter volume), and D is depth
of the filter bed.
X KL Ce Several empirical models proposed in the literature
= (2)
M 1 + a L Ce (Bohart–Adams, Yan, Belter and Chu models) were investigated
in order to obtain the best fit of column data, describing in a
were KL and aL are the isotherm constants. KL and aL values can simple manner the breakthrough curves [128].
be determined using linear regression. The Langmuir isotherm
can be linearized to the following equation: 4. Metal adsorption and biosorption studies
1 1 aL
= + (3) Adsorption has been proved to be an excellent way to
X/M K L Ce KL
treat industrial waste effluents, offering significant advantages
The general Freundlich equation is: like the low-cost, availability, profitability, easy of operation
and efficiency, in comparison with conventional methods espe-
X cially from economical and environmental points of view
= KF (Ce )1/n (4)
M [29,129–131]. A search for a low-cost and easily available

Table 1
Langmuir and Freundlich constants for the adsorption of Cu(II) and Cd(II) from aqueous solution onto rice husk and modified rice husk
Adsorbent Heavy metal KL R2L Ce KF 1/n R2F

Rice husk Cu 2.48 0.996 0.143 0.693 0.288 0.968

Cd 8.82 0.936 0.066 0.630 0.454 0.993
Modified rice husk Cu 9.36 0.994 0.080 0.866 0.480 0.931
Cd 11.03 0.993 0.069 1.265 0.495 0.952

From Ref. [161]. KL , Ce and R2L are Langmuir constants. KF , n and R2F are Freundlich constants.
224 A. Demirbas / Journal of Hazardous Materials 157 (2008) 220–229

adsorbent has led to the investigation of materials of biological 4.1. Mechanism of metal biosorption
origin as potential metal biosorbents. Biosorption is becoming a
potential alternative to the existing technologies for the removal Metal biosorption is a rather complex process affected by
and/or recovery of toxic metals from wastewater [132,133]. several factors. Mechanisms involved in the biosorption process
The study of biosorption is of great importance from an include chemisorption, complexation, adsorption–complexation
environmental point of view, as it can be considered as an alter- on surface and pores, ion exchange, microprecipitation, heavy
native technique for removing toxic pollutants from wastewaters metal hydroxide condensation onto the biosurface, and surface
[134,135]. adsorption [155–157].
In general, raw lignocellulosic biosorbents were modified by In order to understand how metals bind to the biomass, it is
various methods to increase their sorption capacities because essential to identify the functional groups responsible for metal
metal ion binding by lignocellulosic biosorbents is believed to binding. Most of the functional groups involved in the binding
take place through chemical functional groups such as carboxyl process are found in cell walls. Plant cell walls are generally con-
or phenolics. Mechanisms and measurement of chemical mod- sidered as structures built by cellulose molecules, organized in
ification were studied by Kunin et al. [136]. Simple classical microfibrils and surrounded by hemicellulosic materials (xylans,
pyrolysis technologies that only apply heating will result in con- mannans, glucomannans, galactans, arabogalactans), lignin and
version of lignin mainly to solid coke with high surface area pectin along with small amounts of protein [68,158,159].
and gas in a disproportionation process [118,120]. These prop- The behavior of cellulose as a substrate is highly depen-
erties of lignin reveal that it has a potential to be used as a dent upon the crystallinity, specific surface area, and degree of
possible adsorption material to remove heavy metals from waste polymerization of the fibers being studied [160]. The cellulose
waters. is located predominantly in the secondary cell wall. Bundles
Chemical modification became popular and many researchers of cellulose molecules are aggregated together in the form of
devised elaborate modification procedures [137]. Biomass microfibrils in which highly ordered (crystalline) regions exist
chemical modifications include delignification, esterification with less ordered (amorphous) regions. The proportions of crys-
of carboxyl and phosphate groups, methylation of amino talline and amorphous regions in cellulose vary depending upon
groups, and hydrolysis of carboxylate groups. Odozi et al. the type of the sample and the method of measurement. Cotton
[138] polymerized corncob, sawdust and onion. Sawamiap- cellulose is usually more crystalline than wood cellulose [119].
pan and Krishnamoorthy [139] replaced phenol-formaldehyde Laszlo and Dintzis [144] have shown that lignocellulosics
cationic matrices with sulfonated bagasse. Freeland et al. [140] have sorption capacity, which are derived from their constituent
used polyethylenimine-modified wood to adsorb mercury. Sny- polymers and structure. The polymers include extractives, cel-
der and Vigo [141] modified cotton ethylenediamine with lulose, hemicelluloses, pectin, lignin and protein. These are
chlorodeoxycellulose to remove mercury. Gasparrini et al. [142] adsorbents for a wide range of solutes, particularly divalent metal
captured mercury ions using cellulose derivatives. Marchant cations [144].
[143] removed mercury using cellulose modified by changing Lignocellulosics are hygroscopic and have an affinity for
the pH from 1 to 9. Treatment of soybean hulls and sugar beet water. Water is able to permeate the non-crystalline portion of
fiber with epichlorohydrin to improve cation-exchange capacity cellulose and all of the hemicellulose and lignin. Thus, through
was studied by Laszlo and Dintzis [144]. absorption and adsorption, aqueous solution comes into contact
Randall et al. [145] chemically modified peanut skins using with a very large surface area of different cell wall compo-
formaldehyde for heavy metal removal in aqueous waste solu- nents. Because of its disordered structure, amorphous cellulose
tions. The work of Kumar and Dara [146] included bagasse, should be much more accessible to reagents than highly struc-
acacia bark, husk, paddy straw, wheat flour, and waste peanut tured crystalline cellulose. Cellulose can also sorb heavy metals
skin, and Kumar and Dara [147] included onion skin. from solution [162].
The role of lignin in removal of copper is controversial and The molecular structure and supramolecular structure have
inconclusive. Camire and Clydesdale [148] found that lignin and a strong influence on sorption properties. Water adsorption of
pectin have a high metal binding capability. They also tested the fibers, orientated in one particular direction, invariably causes
effect of pH and heat on removal of the copper ions. Varma et swelling. The bigger the amount of water adsorption, the bigger
al. [149,150] removed copper between the pH 4.4 and 5.0. is the swelling. Swelling also depends on the fiber’s structure,
Platt and Clysdale [151] studied binding of iron by lignin on the degree of crystallinity and on the amorphous and void
in the presence of other ions. Nasr and MacDonald [152] did regions [163]. Swelling occurs when polar solvents such as
stoichiometric studies with carboxylic acids groups on lignin water and alcohols are contacted with wood [164]. Wood swelled
compounds toward aluminum and iron ions at lower pHs. extremely fast at high temperatures. The polar solvent molecules
Lignin was used in removal of copper at pH 5.5, cadmium at are attracted to the dry solid matrix and held by hydrogen bond-
pH 6.5. ing forces between the –OH or –COOH groups in the wood
Carbonized coir pith was used as an adsorbent for the removal structure.
of toxic ions, dyes and pesticides from wastewaters [153]. More recently sorption potential of pretreated crab and arca
Removal of copper(II) by adsorption onto peanut hull carbon shell biomass for lead and copper from aqueous media was
from water and copper plating industry wastewater was investi- explored. The effects of pH, initial concentration, biosorbent
gated [154]. dosage and contact time were studied in batch experiments
 A. Demirbas / Journal of Hazardous Materials 157 (2008) 220–229 225

Table 2
Removal capacity of copper(II) ion (mg/g substrate) at pH 5.5
Common name Botanical name Classification Lignin (%) Capacity

Sugar cane, bagasse Saccharum officinarum Straw fiber 19.9 0.3

Oak Quercus spp. Hardwood fiber 23.2 0.5
Aspen Populus grandidentata Hardwood fiber 21.8 0.9
Spruce Eastern Picea orientalis Softwood fiber 26.3 1.3
Coconut, shell Cocos nucifera Shell 35.5 2.6
Flax Linum usitatissimum Bast fiber 2.9 5.5
Kudzu, bark Pueraria lobata Bast fiber 19.3 8.2
Kenaf, fiber Hibiscus cannabinus Bast fiber 9.9 8.5
Hemp Cannabis sativa Bast fiber 3.0 9.5
Tobacco, fiber Nicotina tabacum Bast fiber 16.5 10.5
Tobacco, bark Nicotina tabacum Bast fiber 9.5 14.3

[165]. Effects of common ions like Na, K, Ca and Mg on the exchange capacity at 40 mg/L and 6 days of residence time.
sorption capacity of pretreated crab and arca biomasses were Residence time had the greatest effect on the rate of copper
also studied. At equilibrium, the maximum uptake by crab shell removal. The rate of removal increased with length of residence
biomass was 19.83 ± 0.29 and 38.62 ± 1.27 mg/g for lead and time. These results suggest that at higher ion concentrations,
copper, respectively. In case of arca shell biomass the maximum removal rate increases with an increase in residence time [168].
uptake capacity was 18.33 ± 0.44 mg/g and 17.64 ± 0.31 mg/g Removal capacities of different agro wastes for copper(II) ion
for lead and copper, respectively. are given in Table 2.
Cellulose is a natural polymer. Cellulosic graft copolymers
were prepared by the reaction of bast fibers of the kenaf plant
(Hibiscus cannabinus) with acrylonitrile and methacrylonitrile 5. Conclusion
monomers in aqueous media initiated by the ceric ion–toluene
redox pair. The cellulose–polyacrylonitrile (Cell–PAN) and In this review, the inexpensive and effective metal ion adsor-
cellulose–polymethacrylonitrile (Cell–PMAN) graft copoly- bents from agro waste materials to offer these adsorbents as
mers were used for the removal of Zn(II) and Cr(III) ions replacements for existing commercial materials were investi-
from aqueous solutions at 303 K. Zn(II) ion was more sorbed gated.
than Cr(III) ion by both copolymers by an average factor of Agricultural by-products and in some cases appropriately
1.80 ± 0.40. For each metal ion, the Cell–PAN graft copolymer modified have shown to have a high capacity for heavy metal
was a more effective sorbent than the Cell–PMAN derivative adsorption. Toxic heavy metals such as Pb(II), Cd(II), Hg(II),
[166]. Chemical modification has either been too expensive or it Cu(II), Ni(II), Cr(III), and Cr(VI), as well as some elements from
has caused other problems, such as bleeding of excessive quan- lanthanide and actinides groups have been successfully removed
tities of colored organic compounds, odor, or further pollution from contaminated industrial and municipal waste waters using
through the use of toxic chemicals. different agro waste materials.
The fiber with the highest level of heavy metal removal was Biosorption is a relatively new process that has proven
kenaf bast that had a very low level of lignin, showing that very promising in the removal of contaminants from aque-
removal of heavy metals does not correlate with lignin con- ous effluents. Chemical modification improves the adsorption
tent. Cotton, with about 1% lignin, was very low in metal ion capacity and stability of biosorbents. Biosorption experiments
sorption while all of the fibers containing lignin did remove over Cu(II), Cd(II), Pb(II), Cr(III), and Ni(II) demonstrated that
heavy metal ions showing that lignin does play a role in metal biomass Cu(II) adsorption ranged from 8.09 to 45.9 mg/g, while
ion sorption [167]. Cellulose, a homopolysaccharide of glucose Cd(II) and Cr(VI) adsorption ranged from 0.4 to 10.8 mg/g and
units, is the most abundant lignocellulosic material and a stable from 1.47 to 119 mg/g, respectively [155].
compound. Cotton with high cellulose content shows very low The Langmuir and Freundlich isotherm models are only
sorption capacity. applicable to batch adsorber systems where sufficient time is
Agro-based fibers such as kenaf, roselle, and tobacco have provided to allow equilibrium between the pollutant in solution
been shown to be effective in sorption of heavy metal ions from and the pollutant adsorbed on the media to occur.
stormwater filtration systems. In contrast, most wood-based
fibers have a relatively low capacity for filtering heavy metals References
[168]. Although researchers have tried to increase the sorption
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more success has been achieved with bark and marine fibers from various biomass, Mater. Energy Edu. Sci. Technol. 13 (2004)
[144,169–171]. 97–104.
[2] A. Demirbas, E. Pehlivan, F. Gode, T. Altun, G. Arslan, Adsorption behav-
Kenaf was most effective at removing cadmium ion. Alfalfa ior of Cu(II), Zn(II), Ni(II), Pb(II), and Cd(II) from aqueous solution
was most effective at removing cadmium, copper and zinc ions. on Amberlite IR-120 synthetic resin, J. Colloid Interface Sci. Surf. 282
As individual ions, all three ions had about the same ion- (2005) 16–21.
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[3] A. Celik, A. Demirbas, Removal of heavy metal ions from aqueous solu- [29] A. Hashem, R.A. Akasha, A. Ghith, D.A. Hussein, Adsorbent based on
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