Review

Biosorption of heavy metal ions using wheat based biosorbents A review

of the recent literature
Umar Farooq
a,b,
*
, Janusz A. Kozinski
a
, Misbahul Ain Khan
b,c
, Makshoof Athar
c
a
College of Engineering, University of Saskatchewan, SK, Canada S7N 5A9
b
Department of Chemistry, The Islamia University of Bahawalpur, Bahawalpur, Pakistan
c
Institute of Chemistry, University of the Punjab, Lahore, Pakistan
a r t i c l e i n f o
Article history:
Received 16 September 2009
Received in revised form 3 February 2010
Accepted 7 February 2010
Available online 12 March 2010
Keywords:
Triticum aestivum
Straw
Bran
Biosorption
Metal ions
a b s t r a c t
Conventional technologies for the removal/remediation of toxic metal ions from wastewaters are proving
expensive due to non-regenerable materials used and high costs. Biosorption is emerging as a technique
offering the use of economical alternate biological materials for the purpose. Functional groups like car-
boxyl, hydroxyl, sulphydryl and amido present in these biomaterials, make it possible for them to attach
metal ions from waters.
Every year, large amounts of straw and bran from Triticum aestivum (wheat), a major food crop of the
world, are produced as by-products/waste materials. The purpose of this article is to review rather scat-
tered information on the utilization of straw and bran for the removal/minimization of metal ions from
waters. High efciency, high biosorption capacity, cost-effectiveness and renewability are the important
parameters making these materials as economical alternatives for metal removal and waste remediation.
Applications of available adsorption and kinetic models as well as inuences of change in temperature
and pH of medium on metal biosorption by wheat straw and wheat bran are reviewed. The biosorption
mechanism has been found to be quite complex. It comprises a number of phenomena including adsorp-
tion, surface precipitation, ion-exchange and complexation.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Heavy metal ions have lethal effects on all forms of life and these
enter the food chain through the disposal of wastes in water chan-
nels. From among various metal ions, lead, mercury, cadmium and
chromium(VI) are at the top on the toxicity list (Volesky, 1994). Due
to non-biodegradability, metal ions accumulate and their amounts
are increased along the food chain. Hence, their toxic effects are
more pronounced in the animals at higher trophic levels. Sources
and toxicity of certain metal ions are listed in Table 1.
Owing to the toxic effects, the industries are advised that the
waste waters be treated systematically to remove/minimize the
metal contents in their wastes. A number of methods are already
at operation and Table 2 compares selective techniques used for
the purpose. Adsorption by activated carbon is the most efcient
classical way as it removes more than 99% of certain metal ions
but the cost of its production is prohibitive and it can not be regen-
erated and recycled. Generally, the materials employed in these
methods are highly expensive and capital costs are much too high
to be economical. These methods mostly treat the metal ions as a
waste only and eliminate recycling of materials. Some of the
methods (e.g., precipitation and coagulation) produce concen-
trated and further toxic wastes, creating yet another disposal prob-
lem. Moreover, there are concentration limits to which these
methods are economical and become ineffective or too expensive
to treat wastes having metal ions in concentrations of 100 mg/L
or below (Ceribasi and Yetis, 2001). Hence, there is a constant need
to search for an optimal technology while considering its cost,
materials employed and its efciency.
2. Biosorption an alternative solution
Biosorption is the removal of materials (compounds, metal ions,
etc.) by inactive, non-living biomass (materials of biological origin)
due to high attractive forces present between the two (Volesky
and Holan, 1995).
Living as well as dead (metabolically inactive) biological mate-
rials have been sought to remove metal ions. It was found that var-
ious functional groups present on their cell wall offer certain forces
of attractions for the metal ions and provide a high efciency for
their removal (Ashkenazy et al., 1997; Kuyucak and Volesky,
1988). The mechanisms of uptake by living materials (bioaccumu-
lation) and removal by dead ones (biosorption) are entirely
different. Use of dead materials has several advantages because
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.02.030
* Corresponding author. Address: College of Engineering, University of Saskatch-
ewan, SK, Canada S7N 5A9.
E-mail address: umar.farooq@usask.ca (U. Farooq).
Bioresource Technology 101 (2010) 50435053
Contents lists available at ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech
there is no need of growing, no growth media is required and these
materials are available as wastes or by-products. Biomass from al-
gae (Hamdy, 2000; Seki and Suzuki, 1998), fungi (Guibal et al.,
1992; Kapoor et al., 1999), bacteria (Ozturk, 2007; Pumpel et al.,
1999), sea-weeds (Elangovan et al., 2008; Murphy et al., 2008),
some higher plants (Joshi et al., 2003; Rahman et al., 2005), all of
these have been effectively and successfully utilized in metal re-
moval studies.
Volesky has shared his views about the biosorption process in
his recent review(Volesky, 2007). He stated that currently biosorp-
tion of metals is only the tip of the ice-berg and in future, it must
focus on utilization for purication and recovery of high valued pro-
teins, steroids and drugs, that cost in thousands of dollars per gram.
He termed this form to be the best biosorption. Apart from Vole-
skys groups, a number of review articles have been published by
several researchers. Recently, Sud et al. (2008) reviewed the use
of certain cellulosic agricultural waste materials for the removal
of heavy metal ions. Ahluwalia and Goyal (2007) have collected
the dispersed information, covering from 1981 to 2006, about the
use of microbial and certain plants derived biomass types. Simi-
larly, use of Saccharomyces cerevisiae was compiled by Wang and
Chen (2006). A number of other reviews are available in the litera-
ture (Davis et al., 2003; Lodiero et al., 2006; Nurchi and Villaescusa,
2008; Romera et al., 2006; Shukla et al., 2002).
Research in biosorption suggests the following advantages over
other techniques (Modak and Natarajan, 1995).
Table 1
Sources and toxic effects of heavy metals on human beings.
Metal Source Toxic effect References
Lead Electroplating, manufacturing of batteries,
pigments, ammunition
Anaemia, brain damage, anorexia, malaise, loss of
appetite, diminishing IQ
Gaballah and Kilbertus (1998), Low et al.
(2000), Volesky (1993)
Cadmium Electroplating, smelting, alloy manufacturing,
pigments, plastic, mining, rening
Carcinogenic, renal disturbances, lung insufciency,
bone lesions, cancer, hypertension, ItaiItai disease,
weight loss
Chen and Hao (1998), Godt et al. (2006), Low
et al. (2000), Sharma (1995), Singh et al. (2006)
Mercury Weathering of mercuriferous areas, volcanic
eruptions, naturally-caused forest res,
biogenic emissions, battery production, fossil
fuel burning, mining and metallurgical
processes, paint and chloralkali industries
Neurological and renal disturbances, impairment of
pulmonary function, corrosive to skin, eyes, muscles,
dermatitis, kidney damage
Boening (2000), Manohar et al. (2002), Morel
et al. (1998)
Chromium
(VI)
Electroplating, leather tanning, textile, dyeing,
electroplating, metal processing, wood
preservatives, paints and pigments, steel
fabrication and canning industry
Carcinogenic, mutagenic, teratogenic, epigastric pain
nausea, vomiting, severe diarrhoea, producing lung
tumors
Dupont and Guillon (2003), Granados-Correa
and Serrano-Gmez (2009), Kobya (2004),
Singh et al. (2009)
Arsenic Smelting, mining, energy production from
fossil fuels, rock sediments
Gastrointestinal symptoms, disturbances of
cardiovascular and nervous system functions, bone
marrow depression, haemolysis, hepatomegaly,
melanosis, polyneuropathy and encephalopathy, liver
tumor
Chilvers and Peterson (1987), Dudka and
Markert (1992), Robertson (1989)
Copper Printed circuit board manufacturing,
electronics plating, plating, wire drawing,
copper polishing, paint manufacturing, wood
preservatives and printing operations
Reproductive and developmental toxicity,
neurotoxicity, and acute toxicity, dizziness, diarrhoea
Chuah et al. (2005), Papandreou et al. (2007),
Yu et al. (2000)
Zinc Mining and manufacturing processes Causes short term metal-fume fever,
gastrointestinal distress, nausea and diarrhoea
WHO (2001)
Nickel Non-ferrous metal, mineral processing, paint
formulation, electroplating, porcelain
enameling, copper sulphate manufacture and
steam-electric power plants
Chronic bronchitis, reduced lung function, lung
cancer
Akhtar et al. (2004), Ozturk (2007)
Table 2
Some methods to remove metal ions from Wastewaters.
Method Advantages Disadvantages
Chemical Precipitation v Simple
v Inexpensive
v Most of metals can be removed
v Large amounts of sludge produced
v Disposal problems
Chemical coagulation v Sludge settling
v Dewatering
v High cost
v Large consumption of chemicals
Ion-exchange v High regeneration of materials
v Metal selective
v High cost
v Less number of metal ions removed
Electrochemical methods v Metal selective
v No consumption of chemicals
v Pure metals can be achieved
v High capital cost
v High running cost
v Initial solution pH and Current density
Adsorption
Using activated carbon v Most of metals can be removed
v High efciency (>99%)
v Cost of activated carbon
v No regeneration
v Performance depends upon adsorbent
Using natural zeolite v Most of metals can be removed
v Relatively less costly materials
v Low efciency
Membrane process and ultralteration v Less solid waste produced
v Less chemical consumption
v High efciency (>95% for single metal)
v High initial and running cost
v Low ow rates
v Removal (%) decreases with the presence of other metals
Source: (OConnell et al. 2008).
5044 U. Farooq et al. / Bioresource Technology 101 (2010) 50435053
v The materials can be found easily as wastes or by-products and
at almost no cost.
v There is no need of costly growth media.
v The process is independent of physiological constraints of living
cells.
v Process is very rapid, as non-living material behaves as an ion-
exchange resin, metal loading is very high.
v The conditions of the process are not limited by the living bio-
mass, no aseptic conditions required.
v Process is reversible and metal can be desorbed easily thus recy-
cling of the materials is quite possible.
v Chemical or biological sludge is minimized.
However, there are certain disadvantages as well;
v Irrespective of the value of the metal, it needs to be desorbed
from the material to be further re-employed.
v The characteristics of the biosorbents can not be biologically
controlled.
3. Wheat based materials new biosorbents
Among biological materials, agricultural materials usually play
an important role due to being widely and easily produced. Food
crops are being cultivated all over the world (e.g., sugar cane, rice,
corn, wheat, etc.) and the parts other than fruit, grain, juice etc. are
available for biosorption experimentation. In 2007, world wheat
production was 610.6 million tonnes including a share of 23.3 mil-
lion tonnes from Pakistan and 20.1 million tonnes from Canada
(Annual Report, 2009). The straw and bran of wheat, Triticum aes-
tivum, are two main wastes produced in large amounts. Its straw
has found use as fodder and in paper industry to produce low qual-
ity boards or packing materials. The stems are burnt directly in
some parts of the world for energy purposes, adding seriously to
atmospheric pollution and wastage of resources.
Ali et al. (1991) and Lawther et al. (1995) are among the
researchers who have been investigating the composition and
structure of wheat straw. The main components found, are cellu-
lose (3739%), hemicellulose (3035%), lignin (-14%) and sugars
as well as other compounds carrying different functional groups
like carboxyl, hydroxyl, sulphydryl, amide, amine etc. The percent-
age composition of different substances varies in different parts of
the world, although the substances are almost similar. Cellulose is
a proven adsorbent and has been employed previously for adsorp-
tion chromatographic studies (Acemioglu and Alma, 2001; Grover,
1974; Peterson and Sober, 1956). The scanning electron micro-
graph (SEM) of wheat straw (gure not shown) reveals that the
surface is porous and thus suitable for adsorption of metal ions.
Presence of different functional groups, large amounts of cellulose
and the porosity of surface demand that such a material should be
used for biosorption studies.
Determining metal uptake by a biosorbent is required in order
to express its quality. Different research groups have used two dif-
ferent scales i.e., percent removal (R%) and q or q
e
(mg/g) value.
R(%) =
C
0
C
e
C
0
100 (1)
and
q(q
e
) =
C
0
C
e
m
v (2)
where C
0
and C
e
are initial and equilibriummetal ion concentrations
(mg/L), v is the volume (L), m is dry weight of biomass used (g) and
q (or q
e
) is the mount of metal ions sorbed per gram of biomass (mg/
g). Between the two, q value is considered a better tool to express
and compare the capacities of different biomass types. Units of q de-
pend upon the purpose of exercise. Engineers use mg per gram of
dry sorbent and chemists use mmol per gram or meq per gram
for stoichiometric purposes, but there is no denitive rule. Percent-
age removal gives no information about the amount of biomass
used and, sometimes, can be misleading while comparing different
biomaterials (Volesky and Holan, 1995).
This article offers a review of the use of bran and straw from
Triticum aestivum for the removal/minimization of metal ions.
4. Applications of wheat straw (WS) in metal removal
Straw from wheat has successfully been used to study its bio-
sorptive behaviour from aqueous solution of single metal ions (Ta-
ble 3). Chojnacka (2006) studied the feasibility of using ground
straw to remove less toxic metal Cr(III) ions. The process was quite
fast and equilibrium reached in less than 20 min (Chojnacka et al.
2005). Farooq et al. (2007) reported a study for the removal of
Pb(II) ions using ground straw. More than 85% of metal ions pres-
ent were removed in just 15 min. The mechanism proposed was
based on adsorption along with a strong contribution from Hydro-
gen ion-exchange mechanism. Doan et al. (2008) observed the
sorptive removal of Zn(II) and Ni(II) ions in a xed bed of wheat
straw using single metal as well as bi-metal solutions. They ob-
served that Zn(II) ions caused the biosorption of Ni(II) to decrease
up to 14% when a bi-metal solution was used. Tan and Xiao (2009)
as well as Dang et al. (2009), independently, studied the sorption of
Cd(II) ions. The process was, again, found to be a quick removal of
most of the metal contents in less than 20 min, although equilib-
rium was attained after a longer time (24 h). The amount of metal
sorbed was almost comparable in both of the results. Dang et al.
(2009) also studied the sorption of Cu(II) ions. They were able to
remove 11.4 mg of copper per gram of WS. They further stated that
WS capacity for Cd(II) was 27% higher than that of Cu(II). The sorp-
tion of different metal ions by straw shows promising results and
needs for further investigation.
Table 3
Use of straw from Triticum aestivum for the removal of metal ions in a batch system.
Metal ion Optimum time (min) pH Removal (%) Amount of metal sorbed (mg/g) References
Cd(II) 210 6 14.56 Dang et al. (2009)
60 5 11.60 Tan and Xiao (2009)
Pb(II) 15 6 >85 Farooq et al. (2007)
Cu(II) 210 6 11.43 Dang et al. (2009)
Cr(III) 1020 5 21.0 (36 C) Chojnacka (2006)
Ni(II)
a
Doan et al. (2008)
Zn(II)
a
Doan et al. (2008)
a
Using continuous ow reactor.
U. Farooq et al. / Bioresource Technology 101 (2010) 50435053 5045
5. Applications of wheat bran (WB) in metal removal
Bran is another by-product obtained from wheat crops that has
been studied to explore its biosorption properties towards metal
ions in single metal solutions. There is more literature available on
the use of WB than WS (Tables 3 and 4). Bulut and Baysal (2006) re-
ported the use of WB against Pb(II) ions having capacity of 87 mg/g,
inalmost 60 min. Removal of cadmiumions has been studied by dif-
ferent groups (Nouri et al., 2007; Nouri and Hamdaoui, 2007; Singh
et al., 2006). The sorption capacity was found to be different in each
case. Nouri and Hamdaoui (2007) reported the use of ultrasonics
(40 kHz, 9.5 W) in Cd-biosorption, with and without stirring the
contents of biosorption system. It was observed that ultrasounds
had no effects on the equilibriumtime and optimumpH but caused
a drastic change in the activation energy of Cd-WB physiosorption
from +11.19 to 14.71 kJ/mol. As a result, the monolayer sorption
capacity (maximum amount of metal sorbed) increased from
22.78 to 51.81 mg/g. Chromium (VI) ions were also removed using
WBbydifferent researchgroups (Dupont andGuillon, 2003; Nameni
et al., 2008; Singh et al., 2009; Wang et al., 2008). The capacity of WB
was reported to be different in each case. This variation in metal
capacities corresponds to variation in the structure of WB used in
different studies, along with other parameters. The differences in
the origin, area, soil andkindof wheat fromwhere WBwas obtained,
may explain such a variation in results.
Biosorption of Cu(II) ions using WB was reported by several
authors (Aydn et al., 2008; Basci et al., 2004; Dupont et al.,
2005; Farajzadeh and Monji, 2004; Ozer et al., 2004; Wang et al.,
2009). A variation in the biosorption capacity can be seen in Ta-
ble 4. It can be explained in a similar way as discussed above, in
case of Cr(VI) ions. Ozer et al. (2004) reported that dehydrating
the WB caused an increase in the copper sorption capacity. Dupont
et al. (2005) studied sorption of Cu(II) and Zn(II) on a lignocellu-
losic substrate extracted from WB and found that it exhibited com-
parable afnity for the metal ions. Farajzadeh and Monji (2004)
reported the use of WB for a number of metal ions from their aque-
ous solutions. The results were very promising. The comparatively
fast process and encouraging results urge the use of WB for further
investigations.
The equilibrium times for metal biosorption by both WS and
WB have been found to be relatively shorter than widely utilized
algae, sea-weeds (Dnmez et al., 1999; Suzuki et al., 2005; Vald-
man and Leite, 2000).
6. Equilibrium models
The equilibrium models are extensively used to investigate the
amounts of metal ions sorbed by a certain biomass. The distribution
of metal ions between solution and biomass is a measure of the po-
sitionof equilibriumandcanbe expressedbyoneor moreisotherms.
Lanmguir model, Freundlich model, Tempkin model and Dubinin
Radushkevich (DR) model are some examples and among these
most common are the monolayer adsorption developed by Lang-
muir and the muilti-layer adsorption Freundlich models.
According to Langmuir, the sorption occurs at the surface of the
sorbent in a homogeneous way and the atoms/ions form a mono-
layer, having no mutual interactions, on the sorbent surface.
Although it gives no information about the mechanism, it is still
used to obtain the uptake capacities of the sorbents. It is shown as
q
e
=
q
max
bC
e
1 bC
e
(3)
where q
e
is the amount of metal sorbed at equilibrium (mg/g),
q
max
is the monolayer sorption capacity (mg/g), b is Langmuir
constant, C
e
is concentration of metal ions in solution at equilib-
rium. The linear form is
C
e
q
e
=
C
e
q
max

1
bq
max
(4)
There must be a straight line with slope of (1/q
max
) and an intercept
of (1/b q
max
) when a plot of (C
e
/q
e
) versus C
e
is drawn. Langmuir
model can be further used to calculate the specic surface area
S
L
(m
2
/g) for the monolayer coverage of certain metal ion on a
Table 4
Use of bran from Triticum aestivum for the removal of metal ions.
Metal ion Optimum time (min) pH Removal (%) Amount of metal sorbed (mg/g) References
Cd(II) 110 8.6 87.15 (20 C) Singh et al. (2006)
b
60 5 51.58 Nouri and Hamdaoui (2007)
25 5 15.71 (20 C) Nouri et al. (2007)
20 5 21.0 Farajzadeh and Monji (2004)
Pb(II) 60 47 87.0 (60 C) Bulut and Baysal (2006)
20 5 62.0 Farajzadeh and Monji (2004)
Cr(VI)
c
24 h
a
>4 35 Dupont and Guillon (2003)
12 h
a
1 40.8 Wang et al. (2008)
110 2 310.58 Singh et al. (2009)
60 2 87.8 0.942 Nameni et al. (2008)
Cr(III) 20 5 93.0 Farajzadeh and Monji (2004)
Cu(II)
c
24 h
a
4.5 12.7 Dupont et al. (2005)
3 h
a
6 17.42 (60 C) Aydn et al. (2008)
120 5 8.34 Basci et al. (2004)
60 5 6.85 Wang et al. (2009)
d
30 5 51.5 (60 C) Ozer et al. (2004)
20 5 15.0 Farajzadeh and Monji (2004)
Zn(II)
c
24 h
a
6.5 16.4 Dupont et al. (2005)
Ni(II) 20 5 12.0 Farajzadeh and Monji (2004)
Hg(II) 20 5 70 Farajzadeh and Monji (2004)
a
Time in hours.
b
Using ultrasounds and stirring simultaneously.
c
Using lignocellulosic substrate from wheat bran.
d
Using dehydrated wheat bran.
5046 U. Farooq et al. / Bioresource Technology 101 (2010) 50435053
specic biosorbent (Ho et al. 2002). For q
max
being the biosorption
capacity (mg/g), N the Avogadro number (6.022 10
23
), A the
cross sectional area of metal ion ( A
/
2
) and M the molecular mass
of metal ion, it can be calculated as follows
S =
q
max
NA
M
(5)
Freundlich isotherm model considers the non-ideal sorption on
heterogeneous surfaces in a multilayer way. It is shown as
q
e
= K
f
C
1=n
e
(6)
where K
f
and 1/n are Freundlich constants. The linear form is as
under
lnq
e
= lnK
f

1
n
lnC
e
(7)
A plot of ln q
e
versus ln C
e
should yield a straight line with 1/n as
slope and ln K
f
as intercept.
Equilibrium models followed by metal-WS and metal-WB sys-
tems are listed in Tables 5 and 6. It can be observed that in most
of the cases, Langmuir model was successfully applied pointing
to the most metal ions sorbed in monolayer fashion and that
adsorption played an important role in the mechanism of biosorp-
tion. The feasibility of Langmuir isotherm can be expressed by a
dimensionless constant separation factor or the equilibrium
parameter R
L
dened as
R
L
=
1
1 bC
0
(8)
b being the Langmuir constant and C
0
the initial concentration of
metal (mg/L). It indicates the shape as well as the feasibility of
the isotherm (McKay et al., 1982). The value of R
L
indicates the type
of isotherm to be unfavourable (R
L
> 1), linear (R
L
= 1), irreversible
(R
L
= 0) or favourable (0 > R
L
> 1) (Hall et al., 1966). A plot of R
L
vs.
C
0
will show the type of isotherm. R
L
values further indicate the or-
der of preference or selectivity for biosorption of certain metal ions
by some specic biosorbent (Ho et al. 2002). This may be helpful in
designing the study (experiments) for multi-metal ion systems.
The physical or chemical nature of adsorption can be deter-
mined by calculating the mean free energy of adsorption E using
the following equation
E =
1

2 b
p (9)
The value of b can be determined from DubininRadushkevich (D
R) model as follows,
q
e
= q
max
exp(be
2
) (10)
where b is a coefcient related to the mean free energy of adsorp-
tion (mol
2
/J) and e is Polanyi potential (J/mol) that can be written
as
e = RT ln 1
1
C
e

(11)
Linear form of DR model can be written as
lnq
e
= lnq
max
be
2
(12A)
or
lnq
e
= lnq
max
b RT ln 1
1
C
e

2
(12B)
The slope of the plot of ln q
e
vs e
2
will give the value of b. The
value of E will decide the nature of adsorption. The adsorption pro-
cess will be a physical adsorption for E < 8 kJ/mol and it will be a
chemical adsorption or chemisorption for 8 < E < 16 kJ/mol. This
Table 5
Isotherm, kinetic and thermodynamic data for the use of straw from Triticum aestivum for the removal of metal ions.
Metal ion Equilibrium model Kinetic model Thermodynamic parameters References
DH (kJ/mol) DS (J/mol K)
Cd(II) Langmuir Pseudo second order Tan and Xiao (2009)
Langmuir Pseudo second order Dang et al. (2009)
Pb(II) Freundlich Farooq et al. (2007)
Cu(II) Langmuir Pseudo second order Dang et al. (2009)
Cr(III) Freundlich Pseudo second order Chojnacka (2006)
Table 6
Isotherm, kinetic and thermodynamic data for the use of bran from Triticum aestivum for the removal of metal ions.
Metal ion Equilibrium model Kinetic model Thermodynamic parameters References
DH (kJ/mol) DS (J/mol K)
Cd(II) Langmuir First order 38.535 115.585 Singh et al. (2006)
a
Lanmuir Pseudo second order Nouri and Hamdaoui (2007)
Langmuir Pseudo second order 22.17 141.3 Nouri et al. (2007)
Pb(II) Langmuir Pseudo second order 11.55 60 Bulut and Baysal (2006)
Cr(VI) Langmuir Pseudo second order 22.514 79.452 Singh et al. (2009)
Langmuir Pseudo second order Nameni et al. (2008)
Freundlich 143.105 451.395 Wang et al. (2008)
b
Langmuir Dupont and Guillon (2003)
Cr(III)
Cu(II) Langmuir Pseudo second order 10.60 108.02 Wang et al. (2009)
c
Langmuir Pseudo second order 2.85 95.44 Ozer et al. (2004)
Basci et al. (2004)
Langmuir Pseudo second order 18.791 105 Aydn et al. (2008)
b
Langmuir Dupont et al. (2005)
Zn(II)
b
Langmuir Dupont et al. (2005)
a
Using ultrasounds and stirring simultaneously.
b
Using lignocellulosic substrate from wheat bran.
c
Using dehydrated wheat bran.
U. Farooq et al. / Bioresource Technology 101 (2010) 50435053 5047
will help understanding the mechanism of biosorption (Dang et al.,
2009).
An important key factor that helps in explaining the metal bio-
sorption is the available surface area of biosorbent. The surface
area is calculated by employing BrunauerEmettTeller (BET)
adsorption isotherm using nitrogen as the adsorbate (Brunauer
et al., 1938).
1
v[(P
0
=P) 1[
=
c 1
v
m
c
P
P
0

1
v
m
c
(13)
where P and P
0
are the equilibrium and saturation pressure of nitro-
gen at temperature of adsorption respectively, v is adsorbed gas
quantity, v
m
is monolayer adsorbed quantity and c is BET constant.
The values of v
m
=
1
AI

and c = 1
A
I

are determined from the
slope A and intercept I of BET plot. Total (S
BET Total
) and specic
surface areas (S
BET
) are calculated as
S
BET;Total
=
v
m
Ns
V
(14)
and
S
BET
=
S
BET;Total
a
(15)
where N is Avogadros number, s is adsorption cross section area
(0.16 nm
2
for nitrogen at 77 K), V is molar volume of nitrogen and
a is the molar mass of nitrogen.
The specic surface areas of activated carbons and some biosor-
bents are given in Table 7 in comparison with that of WS. Gener-
ally, the greater the surface area of a specic biosorbent, the
greater the metal biosorption is, provided that all other parameters
inuencing the process are kept constant. Activated carbon has
much higher specic surface area than any biosorbent (Table 7)
but the cost-effectiveness and re-usability of biosorbents make it
possible for them to compete activate carbons in remediation of
metal-contaminated waters.
7. Biosorption kinetics
Kinetic data are often used for the scale-up of biosorption sys-
tems. Elovich model is the simplest model, initially applied to de-
scribe the biosorption kinetics. It is shown as
q
t
=
ln(a b)
b

ln(t t
0
)
b
(16)
where a, b and t
0
are constant and q
t
represents the quantity of ad-
sorbed species at a given time t. a gives an idea of reaction rate con-
stant whereas b represents the rate of adsorption at zero coverage.
Pseudo rst and pseudo second order kinetic models originally
appeared as an alternative to the Elovich model to describe adsorp-
tion kinetics of gas on solids. Pseudo rst order model can be ex-
pressed as
dq
t
dt
= k
1
(q
e
q
t
) (17)
where q
e
and q
t
are the amounts of metal sorbed at equilibrium and
a given time t respectively, k
1
is the rst order rate constant. The
linear form is
ln(q
e
q
t
) = lnq
e
k
1
t (18)
A plot of ln (q
e
q
t
) vs. t should generate a straight line with
intercept of ln q
e
and slope of k
1
. Value of q
e
can be calculated
and compared with that experimental.
Pseudo second order model can be shown as
dq
t
dt
= k
2
(q
e
q
t
)
2
(19)
where k
2
is second order rate constant. The linear form is
t
q
t
=
1
k
2
(q
2
e
)

t
q
e
(20)
A plot of (t/q
t
) vs. t should generate a straight line with intercept of
1/k
2
q
2
e
and slope of 1/q
e
. Value of q
e
can be calculated and compared
with that obtained via experiment.
The shape of graph and comparison of experimental and calcu-
lated q
e
values can help deciding which kinetic model is followed
by biosorption. Another, very important, factor that inuences
such a decision is coefcient of determination R
2
. Its value indi-
cates the correlation of the two quantities and a value of
R
2
> 0.98 shows that the model is suitable for describing the kinet-
ics (Al-Garni, 2005).
Most of the literature available for wheat-metal biosorption to-
day shows the use of pseudo rst- and second order models. Tables
5 and 6 show the kinetic models followed by wheat-metal biosorp-
tion systems and it is clear that mostly pseudo second order model
is followed. The great advantage of this model is its great accuracy
in describing the whole kinetic experimental data.
According to Dang et al. (2009), the required amount of biomass
m
D
to treat a nite volume of metal-contaminated solution v
D
in
batch studies can be estimated as follows,
m
D
=
(C
0
C
e
)v
D
q
(21)
8. Effect of temperature thermodynamic control
Temperature is found to be an important parameter for the
sorption of metal ions dealing with the thermodynamics of the bio-
sorption process. It is directly related to the kinetic energy of the
Table 7
Specic surface area values of some commonly used materials in comparison with WS.
Material Particle size (10
6
m) Average pore diameter (10
10
m) Specic surface area (m
2
/g) References
Granular activated carbon (Filtrasorb 400) 1100 Ozacar and Sengil (2002)
Activated carbon from pine wood 120200 33.2 902 Tseng et al. (2003)
Yellow passion-fruit shell (Brazil) <500 40 Jacques et al. (2007)
Wheat straw 100200 127.8 8.17 Unpublished data
Sargassum sp. 34.76 8.13 Sheng et al. (2008)
Wood 3.86.4 Poots et al. (1976)
Moringa oleifera 105 4.01 Kumari et al. (2006)
Lamarck seeds
Spirogyra sp. 6090 1.31 Gupta and Rastogia (2008)
Waste pomace of olive oil factory 150250 1.24 Nuhoglu and Malkoc (2009)
Soy meal shell <125 0.76 Arami et al. (2006)
Rubber tree leaves <500 154.6 0.48 Ngah and Hanaah (2008)
Rice bran 150425 320 10
4
0.46 Montanher et al. (2005)
5048 U. Farooq et al. / Bioresource Technology 101 (2010) 50435053
metal ions. Thus, it can account for the diffusion process. An in-
crease or decrease in temperature should cause a change in the
amount of metal removed or sorbed by the biomass. As the bio-
mass is porous in nature, possibilities of diffusion along with
adsorption cannot be ruled out as a mechanism for metal removal.
The change in temperature causes a change in thermodynamic
parameters like DG, DH and DS. These parameters contribute to
help understand the sorption mechanism. Temperature data are
used to determine these parameters (Horsfall and Spiff, 2005; Saw-
alha et al., 2006).
DG

= RT lnK
D
(22)
where DG is standard free energy change, R is universal gas con-
stant, T temperature in Kelvin and K
D
is the equilibrium constant
and it is calculated from
K
D
=
q
e
C
e
(23)
Values of DH and DS can be determined from the following
equation;
lnK
D
=
DS

R

DH

RT
(24)
A plot of ln K
D
versus 1/T gives the straight line and DS and DH
can be determined. On rearranging the equation
RT lnK
D
= DH

TDS

(25)
DG

= DH

TDS

(26)
A plot of DG versus T also yields a straight line and the values of
DS and DH can be easily determined.
Parameters like DG, DS and DH provide valuable information
about the sorption process. DG addresses the possibility and fea-
sibility of a certain reaction. The negative value of DG shows the
process is feasible and spontaneous. The increase in DG value,
on a negative scale, with temperature shows the increased proba-
bility of the sorption process. DH shows the route of energy in the
system. A positive value shows an endothermic process and a neg-
ative value indicates an exothermic process. This also contributes
to deciding whether a certain biomass can be used for the removal
of metal ions at elevated temperature or not. Tables 5 and 6 show
the thermodynamic parameters of certain wheat-metal biosorp-
tion systems.
The studies performed using WS have not accounted for the val-
ues of thermodynamic parameters, yet they describe the role of
temperature as causing an increase in the metal biosorption. The
process was found to be endothermic. On the other hand, these
parameters were determined in WB studies. Almost all the studies
showed the endothermic nature of the sorption process. DG val-
ues were negative and showed the spontaneity of the process. Neg-
ative values of DS showed a decreased randomness or increased
orderness at the metalbiomass interface. The positive value
showed a change in biomass structure during the sorption process,
causing an increase in the disorderness of the system (Ajmal et al.,
2003).
Singh et al. (2009) determined that in the process of Cd(II)-WB
sorption, all above-mentioned three thermodynamic parameters
were negative. On one hand, this indicated the feasibility and spon-
taniety of the process, and on the other, the process was exother-
mic and increase in temperature caused a decrease in the
sorption capacity. They further calculated the heat of adsorption
(DH) for the process as;
lnb = lnb
/
DH=RT (27)
where b is Langmuir constant related to energy of adsorption, b
/
is
a constant and R and T are the gas constant and temperature (in Kel-
vin). The value of DH was calculated from ln b versus 1/T plot and
was found to be 8.267 k cal/mol. This conrmed that Cd(II) bio-
sorption by WB, under studied conditions, was exothermic.
9. Effect of pH
Among all other parameters, pH of solution has been found to
be the most important one. It not only inuences the speciation
of metal ions but also the charges on the sorption sites of biomass
type (Gao and Wang, 2007; Lee et al., 1998; Marques et al., 2000).
So, it is very important to consider the ionic states of the functional
groups of the biosorbent as well as the metal solution chemistry at
different pH values.
Biosorbents, in general, and specically WS and WB, are consid-
ered to contain various functional groups like hydroxyl, carboxyl,
sulphydryl etc. (Lawther et al., 1995; Wang, 2002). With the
change in pH of solution, the behaviour of each of these functional
group changes. For example, the ionization constants of various
carboxyl groups have been reported to be around 34 (Eccles and
Hunt, 1986). In highly acidic pHs, these are protonated and act as
positively charged species (Gardea-Torresdey et al., 1990). Depro-
tonation of these functional groups occur on increasing pH and
these behave as negatively charged moieties. It starts attracting
the positively charged metal ions and there is a competition be-
tween hydrogen ions and positively charged metal ions and the
winner can be estimated through the amount of metal sorbed at
a certain pH value. As the pH is increased from highly acidic to
slightly acidic region, the positive character of biomass is con-
verted to negative one.
To assess the ideal pH for metal biosorption, it would be very
helpful to determine the point of zero charge pH of the biosorbent.
Point of zero charge pH (pH
pzc
) is a pH of the solution at which the
overall observed charge on the surface of the biomass type is zero.
When biomass is kept in a solution having pHless than pH
pzc
of bio-
mass, the protonation of certain functional groups occur and the
biomass behaves as a positively charged polymatrix (Ofomaja and
Ho, 2007; Suksabye et al., 2007). This attracts the negatively
charged ions, present in the solution. Usually metal ions are posi-
tively charged except the oxyanions of certain metals like chro-
mate, arsenate etc. which are negatively charged. At this stage,
the biomass type attracts these negative ions. This explains and jus-
ties the removal of chromate ions and less or no removal of posi-
tively charged ions in highly acidic conditions (Dupont and Guillon,
2003; Nameni et al., 2008; Singh et al., 2009; Wang et al., 2008). An
increase in pH above this point makes the functional groups on the
biomass type deprotonate and act as negative species and thus it
binds the positive metal ions. This can be shown as
BH B BH
2
below pH
pzc
above pH
pzc
where BH represents the biomass type bearing zero charge. More-
over it can be concluded that sorbed positive metal ions can be re-
moved by decreasing the pH of the system and the biosorbent can
be regenerated, re-used and thus, pH contributes directly to the
economics of the biosorption process. In most sorption processes,
pH
pzc
gives the lower pH limit.
Certain functional groups such as amino, contain lone pairs of
electrons and thus can contribute towards the formation of coordi-
nate bond with the metal ions. The complexation process is highly
pH dependent and occurs only at some specic pH. Thus, a change
in pH can affect the complex formation and can cause a change in
biosorption efciency of the biomass.
The solution chemistry is also inuenced by pH. In acidic pHs,
metal ions are generally positively charged and are attracted by
negatively charged biomass. When the pH is increased, the amount
U. Farooq et al. / Bioresource Technology 101 (2010) 50435053 5049
of OH
-
ions is increased in the solution. Metal ions react with these
OH

ions and are precipitated as metal hydroxide at some pH va-

lue, depending upon the K
sp
values of the metal hydroxides. In gen-
eral, metal ions are precipitated out in alkaline pH range and do not
contribute towards the biosorption. This gives the upper limit of
pH to be studied. Moreover, the chemical speciation of metal is
decided by solution pH. For example, lead is present as Pb
2+
as
dominant species at pHs < 5.5, as Pb(OH)
2
4
at pHs above 12.5
and as Pb(OH)
2
at 5.5 < pH < 12.5 as shown by Fig. 1. Similarly, cad-
mium is present as free Cd
2+
species along the whole acid pH
range. Above pH 7.5, it starts to precipitate as Cd(OH)
2
and thus,
no more available for biosorption (Basualto et al., 2006). Thus
pH has a direct inuence on the mechanism and uptake of metal
by biosorbent (Giraldo and Moreno-Pirajan, 2008).
Generally, when the pH of solution exceeds 8, metal ions are
precipitated out. It gives the upper limit of pH range to be studied.
Most of the studies performed for positively charged metal ion (as
is clear also from Tables 3 and 4) are carried out in this pH range.
There is an interesting case associated with change in pH. Dur-
ing the removal of Cr(VI) by WB (Singh et al., 2009), it was ob-
served that some Cr(VI) reduced to Cr(III) in highly acidic pH
following the route
Cr
2
O
2
7
6e

14H

2Cr
3
7H
2
O E
0
= 1:33 V
Cr(III) is present as a positive ion whereas Cr(VI) is an oxyanion.
In the highly acidic pH studied, the biomass (WB) was considered
as positive species and offers forces of attraction to the oxyanion of
Cr(VI) whereas Cr(III) are being repelled by protonated functional
groups. Thus, only Cr(VI) should be removed under these condi-
tions. A greenish layer was observed to be present on the surface
of WB, indicating the simultaneous adsorption of Cr(III). Although,
it is possible that Cr(VI) ions are reduced into Cr(III) ions at low pH,
Gupta and Rastogia (2008) and Kumari et al. (2006) reported that
the amount of total Cr and Cr(VI) at low pH is approximately same.
This indicates that the presence of Cr(III) in the nal solution of
Cr(VI) is insignicant. This indicates that although pH is a very
important and inuencing factor, yet it is not solely responsible
for the biosorption mechanism. A number of mechanisms are being
currently considered and the actual mechanism is a mixture of all
such processes.
10. Mechanisms proposed
Metal biosorption is the removal of metal ions by inactive, non-
living biomass due to highly attractive forces present between the
two (Volesky and Holan, 1995). Particularly, it is due to the pres-
ence of certain functional groups, such as amine, carboxyl, hydro-
xyl, phosphate, sulfhydryl etc., on the cell wall of the biomass
(Wang, 2002). The process involves a solid phase (biomass) and a
liquid phase containing metal ions (solution of metal ions/waste-
Fig. 1. Lead species as a function of pH (Giraldo and Moreno-Pirajan, 2008).
Fig. 2. Mechanism of biosorption (Sud et al., 2008).
5050 U. Farooq et al. / Bioresource Technology 101 (2010) 50435053
water). Metal ions are attracted and bound to the biomass by a
complex process that comprises of a number of mechanisms like
adsorption on the surface and pores, ion-exchange, surface precip-
itation, complexation and chelation and entrapment in capillaries
and spaces of polysaccharide network, due to the concentration
causing diffusion through the cell wall and membrane (Chojnacka
et al., 2005; Crist et al., 1981; Kuyucak and Volesky, 1989; Miretzky
et al., 2006; Muraleedharan and Venkobachar, 1990; Murphy et al.,
2009; Tsezos and Mattar, 1996; Veglio and Beolchini, 1997; Yang
and Volesky, 1999). The complex nature of the mechanism is
shown in Fig. 2.
To study the mechanism, it is necessary to have the exact infor-
mation about the cell wall structure of the biomass as well as the
solution chemistry. Biomass types from agricultural origin are
composed of lignin, cellulose, hemicellulose, extractives, lipids,
proteins, sugars, water and many more compounds having a vari-
ety of functional groups. The cell walls of the different biomasses,
fungi, algae, plants, sea-weeds for instance, differ signicantly from
one another. Thus the groups present, type and size of pores,
chains of polysaccharides etc. are ever-varying naturally in the
dead material and the structure of cell walls of these materials is
quite a complex one.
An emerging area of research being developed is the investiga-
tion of the role of different functional groups. Volesky (2007) has
listed major functional groups that contribute towards biosorption
through ion-exchange, adsorption, complexation etc. He has classi-
ed them using hard and soft acid base concept, the pK
a
values and
the electron pair donor atom. A study by Tan and Xiao (2009)
shows the contribution of carboxyl groups in the sorption of cad-
mium. When carboxyl groups were esteried, there was a decrease
in the metal biosorption capacity. This was due to minimization of
the number of carboxyl groups. After the material was hydrolyzed
again, an increase in the biosorption was observed. The structural
changes were also studied using spectroscopic techniques like
FT-IR, XPS etc. The role of different groups can be illustrated using
conventional techniques such as titration (Fourest et al. 1996) or
more advanced instrumental analyses such as FT-IR, Raman
microscopy, EDS, XPS, XRD, EPR, etc. (Nakbanpote et al. 2007). Each
one can reveal certain information and thus can contribute to ex-
plain the actual mechanism of biosorption.
11. Comparison of capacities with other biosorbents
Direct comparison of WS and WB with other sorbent materials
is difcult, since experimental conditions applied are different.
Hence, WS and WB have been compared with other sorbents based
on their maximum sorption capacities (q
max
, mg g
1
). The sorption
capacities of WS and WB are relatively smaller than some other
biomaterials like fungi and algae (Table 8). Unlike fungi, algae
etc., one needs not to grow wheat especially to obtain WS and
WB for such a purpose. This cuts short the initial cost and hence
WS and WB nd their signicantly important place in the list of
cost-effective and economical materials used for metal
sequestering.
12. Conclusions
The use of inexpensive and efcient materials, wheat straw and
wheat bran, for metal biosorption has been reviewed. Relatively
shorter contact time, endothermic nature of biosorption process
(in most cases), acidic pH range and high afnity for metal ions
was found. The use of WS needs further investigation as more lit-
erature is available for the use of WB. Biosorption requires investi-
gation in structural studies of biosorbents, multi-metal studies,
mechanistic modeling, recovery of metal ions, enhancement of bio-
sorption capacity through modication of biosorbents and contin-
uous ow studies. At present, information on these materials is
inadequate for process scale-up and design-perfection.
Acknowledgement
One of the authors (U. Farooq) would like to thank Higher Edu-
cation Commission of Pakistan for awarding an indigenous Ph.D.
scholarship as well as assistance for travel and research under-
taken at the University of Saskatchewan.
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