1-S2.0-S2213343713002662-Main (1) Ok Teoria

Journal of Environmental Chemical Engineering 2 (2014) 239259
Contents lists available at ScienceDirect
Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece
Biomass-derived biosorbents for metal ions sequestration: Adsorbent

modication and activation methods and adsorbent regeneration
Ravindra Kumar Gautam a, Ackmez Mudhoo b, Giusy Lofrano c, Mahesh Chandra Chattopadhyaya a,*
a
Environmental Chemistry Research Laboratory, Department of Chemistry, University of Allahabad, Allahabad 211 002, India
Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Mauritius, Reduit, Mauritius
c
Department of Environment, Salerno Province, 84132 Fisciano, SA, Italy
b
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 29 October 2013
Accepted 20 December 2013
Heavy metals released from industrial activities pose a signicant threat to the environment and public
health due to their reported toxicity even at trace levels. Although there are several available methods to
treat or remove heavy metals from water and wastewater, the research focuses on development of
technological solutions which sound environmental friendly and economically feasible, able to reduce
the costs and maximize the efciency. In this framework, the biosorption process, which uses cheap and
non-pollutant materials, may be considered as an alternative, viable and promising, technology for
heavy metal and metalloid ions sequestration and ultimately removal technology in the waste water
treatment. However, there is as yet little data on full-scale applications for the design and testing of
adsorption units using single biosorbents and their combinations to sequester heavy metal ions from
multi-metal systems. Immediate research and development is hence earnestly required in this specic
direction to further make progress this blooming technology and widen its scope of application to real
situations needing heavy metal pollution remediation. This review provides a comprehensive appraisal
of the equilibrium modeling of a number of biosorption processes as well as the structural, chemical and
morphological modications and activation of biosorbents. Further the relative merits of the methods
used to recover sequestered heavy metal ions and regenerate biosorbents through desorption routes and
their future applications are discussed.
2013 Elsevier Ltd. All rights reserved.
Keywords:
Biosorbent
Metal ions
Sequestration
Surface modication
Desorption
Recovery
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modeling of equilibrium biosorption processes .
Equilibrium adsorption isotherms . . . . . .
Kinetic studies and models . . . . . . . . . . .
Pseudo-rst-order models. . . . .
Pseudo-second-order model . . .
Thermodynamic analyses . . . . . . . . . . . . . . . . . .
Biomass and biosorption of metal ions. . . . . . . .
Agro biosorbents . . . . . . . . . . . . . . . . . . . .
Organometallic compounds biosorption .
Weed . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Medicinal herbs . . . . . . . . . . . . . . . . . . . .
Non-timber products . . . . . . . . . . . . . . . .
Modications and activation of biosorbents. . . .
Modication techniques . . . . . . . . . . . . . .
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* Corresponding author. Tel.: +91 9307663844; fax: +91 532 2541786.

E-mail addresses: ravindragautam1987@gmail.com (R.K. Gautam), ackmezchem@yahoo.co.uk (A. Mudhoo), glofrano@unisa.it (G. Lofrano),
mcchattopadhyaya@gmail.com (M.C. Chattopadhyaya).
2213-3437/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.12.019
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240
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R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259
240
Activation of adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . .
Activated carbon . . . . . . . . . . . . . . . . . . . . . . . . .
Activated seaweed. . . . . . . . . . . . . . . . . . . . . . . .
Activated sawdust . . . . . . . . . . . . . . . . . . . . . . . .
Activated bagasse . . . . . . . . . . . . . . . . . . . . . . . .
Activated carbon from agro-waste . . . . . . . . . . .
New activated biosorbents . . . . . . . . . . . . . . . . .
Recovery of metals, regeneration and desorption of biosorbents
Outlooks and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concluding notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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.
Introduction
Heavy metal contamination of aqueous media and industrial
efuents is one of the signicant environmental problems due to
the toxic nature and accumulation of these metal ions in the
food chain, because they are non-biodegradable [1,2]. Although
several adverse health effects of heavy metals have been known
for a long time, exposure to heavy metals continues, and is even
increasing in some parts of the world, in particular in less
developed countries, though emissions have declined in most
developed countries over the last 100 years. For example,
mercury is still used in gold mining in many parts of Latin
America. Arsenic is still common in wood preservatives, and
tetraethyl lead remains a common additive to petrol, although
this use has decreased dramatically in the developed countries.
Heavy metal contamination exists in wastewater of many
industries such as metal plating, mining operations, surface
nishing industry, tanneries, paper and pulp industries, chloralkali, fertilizer and pesticide industry, radiator manufacturing,
smelting, energy and fuel production, aerospace and atomic
energy installation, alloy industries, electroplating and batteries
industries [311].
While many of the heavy metals are needed by biological
systems at the micronutrient level, higher concentrations are
known to produce a range of toxic effects. A high exposure to lead
(Pb) causes encephalopathy, cognitive impairment, behavioral
disturbances, kidney damage, anemia and toxicity to the reproductive system [12]. Chromium (Cr) is widely accepted to exert
toxic effects in its hexavalent form due to its strong oxidation
properties [13,14]. Human exposure to Cr(VI) compounds is
associated with a higher incidence of respiratory cancers [15,16].
After it reaches the blood stream, it damages the kidneys, causes
irritation and corrosion of skin, the liver and blood cells through
oxidation reactions [17]. Cadmium (Cd) has been established as a
very toxic heavy metal. Due to its acute toxicity, Cd has recently
joined lead and mercury in the most toxic Big Three category of
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255
heavy metals with the greatest potential hazard to humans and the
environment [18]. Symptoms of acute poisoning include headaches, nausea, vomiting, weakness, pulmonary edema and
diarrhea. A disease known as ItaiItai in Japan is specically
associated with cadmium poisoning, resulting in multiple fractures
arising from osteomalacia. High dose of copper (Cu) concentrations
can lead to weakness, lethargy, anorexia and damage to the
gastrointestinal tract [19]. Human exposure to highly nickel (Ni)
polluted environments can cause skin allergies, lung brosis, and
cancer of the respiratory tract [20,21]. The exact mechanisms of
nickel-induced carcinogenesis are not known and have been the
subject of various epidemiologic and experimental investigations.
Table 1 summarizes the anthropogenic sources of heavy metals in
the environment.
There are several methods for removing heavy metal ions from
aqueous solutions and mainly consist of physical, chemical and
biological techniques and technologies. Conventional methods for
removing toxic metal ions from aqueous solution have been
recommended, such as chemical precipitation [37], ltration [38],
ion exchange [39], electrochemical treatment [40], membrane
technologies [41], oatation [42,43], adsorption on activated
carbon [44,45], evaporation and photocatalysis [4648,50].
Table 2 shows the treatment technologies for the removal of
heavy metals from wastewaters and related advantages and
disadvantages.
However, chemical precipitation and electrochemical treatment are ineffective, especially when metal ion concentrations in
aqueous solution are low, and also alongside these removal
techniques produce large quantity of sludge which require further
treatment [10]. Ion exchange, membrane technologies and
activated carbon adsorption process are extremely expensive
when treating large amount of industrial efuent and wastewater
containing heavy metal ions in low concentration, they cannot be
used at large industrial scale. Despite its extensive use in the water
and wastewater treatment technologies, activated carbon remains
an expensive material.
Table 1
Signicant anthropogenic sources of heavy metal in the environment.
Industry
Metals
Pollution arising
References
Electroplating
Batteries
Paints and pigments
Landll leachate
Electronics
Metalliferous mining
Fertilizers
Manures sewage sludge
Specialist alloys and steels
Paper and pulp
Cr, Ni, Zn, Cu

Pb, Sb, Zn, Cd, Ni, Hg
Pb, Cr, As, Ti, Ba, Zn
Zn, Cu, Cd, Pb, Ni, Cr, Hg
Pb, Cd, Hg, Pt, Au, Cr, As, Ni, Mn
Cd, Cu, Ni, Cr, Co, Zn, As
Cd, Cr, Mo, Pb, U, V, Zn
Zn, Cu, Ni, Pb, Cd, Cr, As, Hg
Pb, Mo, Ni, Cu, Cd, As, Te, U, Zn
Zn, Cu, Cd, Pb, Ni, Fe, Mn
Liquid efuents from plating processes

Waste battery uid, contamination of soil and groundwater
Aqueous waste from manufacture, old paint deterioration and soil pollution
Landll leachate, contamination of ground and surface water
Aqueous and solid metallic waste from manufacturing and recycling process
Acid mine drainage, tailings, slag heaps
Run-off, surface and groundwater contamination, plant bioaccumulation
Land spreading threat to ground and surface water
Manufacture, disposal and recycling of metals. Tailings and slag heaps
Wastewater efuents
[22,23]
[24]
[25]
[26,27]
[28]
[29,30]
[31,32]
[31,33]
[34,35]
[36]
241
Table 2
Treatment technologies for the removal of heavy metals from wastewaters and associated advantages and disadvantages.
Technology
Advantages
Disadvantages
References
Chemical precipitation
Process simplicity
Not metal selective
Inexpensive capital cost
Metal selective
Limited pH tolerance
High regeneration
Bacterial inactivation capability
Good sludge settling and dewatering
Characteristics
Metal selective
Low retention times
Removal of small particles
Low solid waste generation
Low chemical consumption
Small space requirement
Possible to be metal selective
No chemical required can be
engineered to tolerate suspended solids
Moderately metal selective
Induced separation and purication of
magnetically inuenced contaminants
Large amount of sludge containing metals

Sludge disposal cost
High maintenance costs
High initial capital cost
High maintenance cost
[49]
Chemical consumption
Increased sludge volume generation
[49]

High maintenance and operation costs
[42]

High maintenance and operation costs
Membrane fouling
Limited ow-rates
Production of hydrogen (with some processes)
Filtration process for ocs
The collection of particles depends strongly on
the creation of large magnetic eld gradients,
as well as on the particle size and magnetic
properties.
Performance depends on type of adsorbent
Physical or chemical activation to improve its
sorption capacity
[51,52]
Ion exchange
Coagulationocculation
Flotation
Membrane ltration
Electrochemical treatment
Magnetic separation and

purication technique
Adsorption
Wide variety of target pollutants

High capacity
Fast kinetics
Possibly selective depending on adsorbent
Recently, magnetic nanoparticles have been investigated for

their potential to remove heavy metal ions from aqueous solutions
[57,58]. Polyrhodanine-coated g-Fe2O3 magnetic nanoparticles
have been synthesized by one-step chemical oxidation polymerization and were applied to the process of removal of heavy metal
ions from aqueous solution [59]. These materials however have a
limited application in the removal of heavy metal ions because of
their magnetic properties. With time, the demand of safe drinking
water and need of economical methods for the elimination of
heavy metals from wastewater has dictated research interest
toward the production of low cost alternative bio-based adsorbents in preference to commercially available activated carbon.
Since environmental protection and stewardship is becoming
an important global concern and urging one and all to develop
greener remediation techniques and pollutant sequestration and/
or degradation routes, biosorption has become a promising
technique for metal removal, and heavy metal and metalloid ions
removal. Biosorption has been dened as the property of certain
biomolecules to bind and concentrate selected ions or other
molecules from aqueous solutions [18]. As opposed to a much
more complex phenomenon of bioaccumulation based on active
metabolic transport, biosorption by dead biomass is passive and
based mainly on the afnity between the sorbent and sorbate.
Materials such as various bacteria, yeast, fungi, algae, chitin and
chitosan have been used to prepare several types of biosorbents.
Biosorption of heavy metal ions has become a popular environmentally driven research topic and it represents only one
particular type of a concentration-removal aspect of the sorption
process [10]. In recent years, applying the biosorption technology
in controlling and removing heavy metal pollution has been
rewarded much attention, and has gradually become a keystone in
environmental remediation. Findings of studies on the development and potential use of different biosorbents have revealed the
merits of biosorption as an effective technique for cleaning toxic
metal ion-bearing efuents [60].
Over the past decades, many new processes have been tested
successfully, a lot of them have gone into operation and a great
number of papers have been published in this eld. We hope that
[39]
[53,54]
[55]
[56]
this review will help provide a better understanding and

orientation in the important and interesting eld of biomass
based activated biosorbents and biosorption of heavy metals. The
methodology of studying biosorption is based on an interdisciplinary approach to it, whereby the phenomenon can be studied,
examined and analyzed from different angles and perspectives
by chemists, chemical engineers as well as by environmentalists.
Modeling of equilibrium biosorption processes
Assessment of a solidliquid sorption system is usually based
on two types of investigations: equilibrium batch sorption tests
and dynamic continuous-ow sorption studies. Equilibrium
isotherm model equations such as Langmuir [61] and Freundlich
[62] are used to describe experimental adsorption data in batch
mode [63,64]. It is important to nd best-t isotherm to evaluate
the efcacy of the prepared adsorbent to develop suitable
industrial adsorption system designs.
Equilibrium adsorption isotherms
Equilibrium isotherm models are usually classied into the
empirical equations and the mechanistic models. The mechanistic
models are based on mechanism of metal ion biosorption, which
are able not only to represent but also to explain and predict the
experimental behavior. Some empirical models for single solute
systems are listed in Table 3. The Langmuir model (based on
monolayer adsorption of solute) and the Freundlich model
(developed for heterogeneous surfaces) are the most widely
accepted and used in literatures [6569]. The BrunauerEmmett
Teller (BET) model [70] describes the multi-layer adsorption at the
biosorbent surface and assumes that the Langmuir isotherm
applies to each layer. These models can provide information of
metal uptake capacity and difference in metal uptake between
various species.
Langmuir adsorption isotherms are widely used to describe the
relationship between the amount of adsorbate adsorbed on
adsorbent and its equilibrium concentration in aqueous solution.
242
Table 3
Summary of widely used isotherms for biosorption systems with their advantages and disadvantages.
Isotherm
Functional form
Langmuir
qe
qm K L C e
1K L C e
Freundlich
qe K F Ce
ln qe ln K F 1n ln C e
ln qe = VS ln Ce
Temkin
qe RT
lnK T C e
b
qe RT
ln K T RT
ln C e
b
b
qeVS ln Ce
Redlich
Peterson (RP)
qe
1=n
K RP C e
b
1aRP Ce
Linear form
Plot
Advantages
Disadvantages
Ce
qe
Ce
qe
Has Henry law and nite

saturation limit so valid
over a wide range of
concentration
Simple expression and
has parameter for surface
heterogeneity
Based on monolayer
assumption
ln
1
K L qm
h
K RP C e
qe
1
qm
Ce
i
1 ln aRP b ln C e
ln
Langmuir equation relates the coverage of molecules on a solid

surface to concentration of a medium above the solid surface at a
xed temperature. Langmuir isotherms are based on three
assumptions: (i) the surface of the adsorbent is in contact with
a solution containing an adsorbate which is strongly attracted to
the surface; (ii) the surface has a specic number of sites where the
solute molecules can be adsorbed; (iii) the adsorption involves the
attachment of only one layer of molecules to the surface, i.e.
monolayer adsorption [71,72].
At lower concentrations, an alternate isotherm developed by
Herbert F. Freundlich frequently describes the data better. The
Freundlich isotherm is an empirical equation. This equation is one
among the most widely used isotherms for the explanation of
adsorption equilibrium. Freundlich isotherm is capable of describing the adsorption of heavy metals on a wide variety of
biosorbents. On average, a favorable adsorption tends to have
Freundlich constant n between 1 and 10. Larger value of n (smaller
value of 1/n) implies stronger interaction between biosorbent and
heavy metal while 1/n equal to 1 indicates linear adsorption
leading to identical adsorption energies for all sites [72].
Sometimes, these empirical models do not reect any mechanisms
of sorbate uptake and hardly have a meaningful physical
interpretation for biosorption. It has been mentioned that the
results from empirical models cannot be extrapolated and no
predictive conclusions can be nd out for biosorption of heavy
metals from aqueous solutions operating under different environmental conditions [10]. Both simple basic models (Langmuir and
Freundlich models) also do not incorporate the effects of any
external variable environmental factors, although they are capable
of describing many biosorption isotherms in most cases. The
mechanistic conclusions from the good t of the models alone
should be avoided. Moreover, biosorption isotherms may exhibit
an irregular pattern due to the complex nature of both the
biosorbents and its varied multiple active sites, as well as the
complex solution chemistry of some metallic compounds.
For instance Mohan and Singh [44] evaluated the behavior of
modied bagasse, a waste product in sugar rening industry, for
the removal of aqueous cadmium and zinc from wastewater. The
adsorption studies were carried out both in single- and multicomponent systems. The data were better tted by the Freundlich
isotherm as compared to Langmuir in both the single- and multicomponent systems. The Freundlich and Langmuir constants
obtained at 40 8C for Cd(II) and Zn(II) were 5.43 (mg g1),
49.07 (mg g1), and 6.04 (mg g1), 54.00 (mg g1); respectively.
Equilibrium isotherms had been used to obtain the thermodynamic parameters and the obtained result showed that the
adsorption was endothermic in nature.
VS C e
h
K RP C e
qe
Simple expression
i
1 VS ln C e
Approaches Freundlich
at high concentration
Does not have Henry law

and no saturation limit,
not structured, not
applicable over wide
range of concentration
Same as Freundlich.
It does not have correct
Henry law limit and nite
saturation limit, not
applicable over wide range
of concentration
No special advantages
Rao et al. [73] have studied the removal of Cr(VI) and Ni(II) from
aqueous solution using bagasse and y ash as low-cost potential
adsorbents. Raw bagasse was pretreated with 0.1 N NaOH followed
by 0.1 N CH3COOH before its application. The equilibrium sorption
data were correlated with Langmuir, Freundlich and Bhattacharya
and Venkobachar adsorption models. The efciencies of adsorbent
materials for the removal of Cr(VI) and Ni(II) were found to be
between 56.2% and 96.2% and 83.6% and 100%, respectively.
In some cases the isotherm model such as Langmuir or
Freundlich fails to describe the biosorption behavior of metal
ions from aqueous solutions onto the biosorbent, and in most
cases, more than one model have been applied to illustrate the
biosorption mechanism. Several models initially developed for gas
phase adsorption can be implemented to correlate heavy metals
biosorption processes [74,75]. Some of these equations contain
two tting parameters such as Temkin isotherm [76], Flory
Huggins [77], and DubininRaduskevich equations [78], whereas
others can have more than two parameters RedlichPaterson [79]
and Sips isotherms [80]. Some other workers have given details
about these models [60,72,81].
Kinetic studies and models
Adsorption equilibria studies are important to conclude the
efcacy of adsorption. In spite of this, it is also necessary to identify
the adsorption mechanism type in a given system. Kinetic models
have been exploited to evaluate the mechanisms of biosorption of
heavy metals and its potential rate-controlling steps that include
mass transport and chemical reaction processes [82]. In addition,
information on the kinetics of metal uptake is required to select the
optimum condition for full-scale batch metal removal processes.
Predicting the rate of adsorption for a given system is among
the most important factors in adsorption system design, as the
systems kinetics determines adsorbate residence time and the
reactor dimensions [72]. As previously noted that various factors
govern the adsorption capacity, i.e., initial heavy metals concentration, temperature, pH of solution, biosorbent particle size, heavy
metals nature, a kinetic model is only concerned with the effect of
observable parameters on the overall rate.
Several adsorption kinetic models have been established to
understand the adsorption kinetics and rate-limiting step. These
include pseudo-rst and -second-order rate model, Weber and
Morris sorption kinetic model, AdamBohartThomas relation,
rst-order reversible reaction model, external mass transfer
model, rst-order equation of Bhattacharya and Venkobachar,
Elovichs model and Ritchies equation. The pseudo-rst- and second-order kinetic models are the most well liked model to
study the biosorption kinetics of heavy metals and quantify the

extent of uptake in biosorption kinetics.
Pseudo-rst-order models
The Lagergren rst-order rate expression based on solid
capacity is generally expressed as follows [83]:
dq
k1 qe q
dt
where q and qe are amounts of adsorbate adsorbed (mg g1) at
time, t (min) and at equilibrium, respectively, k1 is the rate
constant of adsorption (l min1). Integration of the above equation
with the boundary conditions: t = 0, q = 0, and t = t, q = q, gives
lnqe q ln qe k1 t
which can be represented as follows:
q qe 1 expk1 t
or it can be expressed as:
logqe qt logqe
k1
t
2:303
The equation applicable to experimental results generally differs

from a true rst-order equation mainly in two ways [84].
i. The parameter k1(qe qt) does not represent the number of
available sites.
ii. The parameter log(qe) is an adjustable parameter which is often
not found equal to the intercept of a plot of log(qe qt) against t,
whereas in a true rst-order sorption reaction log(qe) should be
equal to the intercept of a plot of log(qe qt) against t.
In order to t above equation to experimental data, the
equilibrium sorption capacity, qe, must be known. In many cases qe
is unknown and as chemisorption tends to become unmeasurably
slow, the amount sorbed is still signicantly smaller than the
equilibrium amount. In most cases in the literature, the pseudorst-order equation of Lagergren does not t well for the whole
range of contact time and is generally applicable over the initial
2030 min of the sorption process [84].
Furthermore, one has to nd some means of extrapolating the
experimental data to t = 1 or treat qe as an adjustable parameter to
be determined by trial and error. For this reason, it is necessary to
use trial and error to obtain the equilibrium sorption capacity, qe, in
order to analyze the pseudo-rst-order model kinetics.
The pseudo-rst-order kinetic model has been used extensively to describe the sorption of metal ions onto biosorbents
[85104]. The main disadvantages of this model are (i) that the
linear equation does not give theoretical qe values that agree with
experimental qe values, and (ii) that the plots are only linear over
the rst 30 min, approximately. Beyond this initial 30 min period
the experimental and theoretical data do not correlate well.
Various authors have made proposals for these deviations. One
suggestion for the differences in the qe values is that there is a
time lag, possibly due to a boundary layer or external resistance
controlling at the beginning of the sorption process [105]. This
time lag is difcult to quantify and does little to help rationalize
the differences in experimental and theoretical qe values. In terms
of the short time correlation between experimental and
theoretical data for the pseudo-rst-order model, it has been
proposed that another rst-order reaction supersedes the rst or
243
another reaction of another order becomes predominant

[83,106108]. No mechanisms have been proposed for this stage
by any authors. Several researchers [109113] have tested the
Lagergren pseudo-rst-order reaction model for Cu(II), Cr(VI) and
Cu(II), Pb(II), Cu(II) and for Cu(II). In general, most of the ts are
moderate to poor. In studies on the sorption of cadmium by
chitosan the pseudo-second-order kinetic model was much more
successful [114116]. However, it should be noted that the
limited model by Lagergren is generally restricted to only the
initial 20% to 40% of the adsorption capacity. The equation needs
further modication for longer sorption times and higher
fractional surface coverages. Hence, when the experimental data
are inspected several sets of results have very few data points in
the initial 2040% period and therefore the rejection of a pseudorst-order reaction model on the grounds of poor model tting
may not be the correct reason. A more logical approach would be
to analyze the likely mechanism of a rst-order metal ion
sorption uptake process on biosorbents, and compare this with a
model where involving a second-order or higher process seems
more likely. Nevertheless, there are several examples of the use of
the pseudo-rst-order kinetic analysis for other systems, such as,
Fe(II) on wollastonite, or Cd(II) and Ni(II) on peanut hull carbon
by copper-coated moss [117].
Pseudo-second-order model
Pseudo-second-order model is derived on the basis of the
sorption capacity of the solid phase, expressed as [111,112,118
120,252]:
dq
k2 qe q2
dt
Integration of above equation with the boundary conditions t = 0,
q = 0, and at t = t, q = q, results in
1
1
k2 t
qe q qe
This equation can be expressed as
t
t
1

q qe k2 q2e
where k2 is the equilibrium rate constant of pseudo-secondorder adsorption (g mg1 min1). The pseudo-second-order rate
constants can be determined experimentally by plotting t/q
versus t. As such, in comparison to pseudo-rst-order kinetic
this model is considered more appropriate to represent the
kinetic data in biosorption systems [72]. The pseudo-rst andsecond-order rate expressions have been and still in wide-use
for studying the biosorption of heavy metals from aqueous
solutions. In chemisorption process, the pseudo-second order is
superior to pseudo-rst order model as it takes into account the
interaction of adsorbentadsorbate through their valency forces
[72].
The pseudo-second-order kinetic model has been the most
widely celebrated model for the biosorption of metal ions from
aqueous solutions [112]. There are several examples where the
pseudo-second-order model was best tted for the biosorption of
metal ions onto biosorbents, i.e., copper [109,110,113,122],
cadmium [114116,123], and lead [124]. All the literature ts
using this method for chitosanmetal ion systems provide an
exceptionally high degree of correlation between the model
results and the experimental data over the whole range of the
sorption uptake capacity. The main deciency of this extremely
244
useful model stems from the fact that it is a pseudo-kinetic

model, so a specic but different rate constant is obtained for
each change in system variable [84]. So it is important to develop
an equation for correlating the pseudo-rate constant with each
variable [122].
The Weber and Morris sorption kinetic model [125] was
initially employed by Pasavant et al. [126]. The equation can be
expressed as:
energy (DG), enthalpy (DH), and entropy (DS) were determined

by using the following equation [130132]:
DG DH T DS
where C and Csi is the liquid phase concentration of sorbate in

the bulk solution at time t and concentration of sorbate in the
inner pore of sorbent, and KL and A is the liquidsolid mass
transfer coefcient and specic surface area of biomass;
respectively.
They observed that the external mass transfer coefcients can
be ordered from high to low values as Cu(II) > Pb(II) > Zn(II) > CCd(II), while the intraparticle diffusion coefcients were as
follows: Cd(II) > Zn(II) > Cu(II) > Pb(II).
The slope and the intercept of the plot of DG versus T were used to
determine the DS and DH values [133]. Malik et al. [134] reported
that the sorption of Hg2+ onto sunower stem was exothermic and
they observed DH value of 32 kJ mol1. The negative entropy
change, DS, conrmed the decreased randomness at the solid
solution interface during biosorption and reversibility of mercury
biosorption [135]. The results showed that the biosorption capacity
of Carica papaya for Hg2+ decreased with increase in temperature.
The saturated monolayer biosorption capacity, qmax, was found to
decrease from 185.62 to 119.56 mg g1 for an increase in solution
temperature from 293 to 323 K. That was a clear indication that the
biosorption of Hg2+ on C. papaya biosorbent was an exothermic
process. Conversely, the Langmuir isotherm constant decreased
from 0.00812 to 0.00502 L mg1, as temperature was varied from
293 to 323 K. Yasemin and Zek [130] have calculated the values of
standard free energy (DG) for the biosorption of Pb2+, Cd2+, and Ni2+
onto sawdust of walnut. The values of DG (calmol1) for biosorption
of Pb2+, Cd2+, and Ni2+ ions at temperatures 25, 45 and 60 8C were
1675.72, 1699.40, 1024.38; 1914.55, 2104.11, 1503.84;
and 2071.03, 2547.43, 2077.65, respectively. The values of DS
(calmol1 K) and DH (calmol1) for Pb2+, Cd2+, and Ni2+ at
temperature 45 8C were 11.33, 24.01, 29.76 and 1696.80, 5479.30,
7879.60, respectively. Positive values of DH suggested the
endothermic nature of the adsorption and the negative values of
DG indicated the spontaneous nature of the adsorption process.
However, the negative values of DG with an increase in temperature
indicated that the spontaneous nature of adsorption was inversely
proportional to the temperature. The positive values of DS showed
the increased randomness at the solidsolution interface during the
adsorption process [136]. It was stated that the adsorbed water
molecules, which were displaced by the adsorbate species, gain
more transitional energy than was lost by the adsorbate ions, thus
allowing the prevalence of randomness in the system. The
enhancement of adsorption at higher temperatures may be
attributed to the enlargement of pore size and/or activation of the
adsorbent surface [137].
Thermodynamic analyses
Biomass and biosorption of metal ions
Gibbs free energy (DG), change in enthalpy (DH), and change

in entropy (DS). Negative DG indicates the spontaneity of the
adsorption process. DH is used to identify the nature of adsorption
[127]. A positive value of DH indicates the reaction is endothermic, and the negative value of DH shows that the reaction is
exothermic [15,127]. A positive value of DS indicates increased
randomness of adsorbate molecules on the solid surface than in
solution [128]. The free energy of adsorption (DG) can be related
with the Langmuir equilibrium constant by the following
expression [129]:
Of the many types of biosorbents (i.e. fungi, bacteria, yeasts,

weeds, and industrial and agricultural wastes) recently investigated for their ability to sequester heavy metal ions, low-cost biomass
have proven to be highly effective as well as reliable and
predictable in the removal of, for example, Pb2+, Cu2+, Cd2+, Cr6+,
and Zn2+ ions from aqueous solutions. Uptake of metals by
different low-cost biosorbents is summarized in Table 4.
p
q K WM t
where q and KWM are the amount adsorbed at time t, and Weber
and Morris intraparticle diffusion rate constant, respectively. Ht
represents the square root of time t.
According to them, the biosorption by Caulerpa lentillifera
biomass for Cu(II), Cd(II), Pb(II), and Zn(II)was regulated by two
main mechanisms, i.e., intraparticle diffusion and external mass
transfer. The intraparticle diffusion can be estimated with

2
d p K WM
8640
qe
where D and dp is the intraparticle diffusion coefcient and mean

particle diameter, and KWM and qe is the amount adsorbed at time t
and amount of solute adsorbed at equilibrium condition;
respectively.
The external mass transfer process was determined by
dq
K 0L AC Csi
dt
DG RT ln K L
Enthalpy and entropy changes are also related to the Langmuir
equilibrium constant by the following expression:
ln K L
DS
R
DH
RT
Thus, a plot of ln KL versus 1/T should be a straight line. DH and DS

values could be obtained from the slope and intercept of this plot.
The thermodynamic parameters such as changes in standard free
Agro biosorbents
Recently Schiewer and Patil [96], investigated pectin-rich fruit
wastes as biosorbents for heavy metal ion removal. According to
their studies pectin-rich fruit materials and citrus peels were found
to be most suitable for cadmium biosorption. Equilibrium kinetics
was achieved within 3090 min, depending upon particle size. A
pseudo-second-order model was found to be more suitable than a
rst-order model to describe the kinetics. Isotherm studies showed
as the data were well tted to Langmuir model. It was also
observed that the metal uptake decreased with decreasing pH,
indicating competition of protons for binding to acidic sites.
Batch adsorption experiments were performed by Dhir and
Kumar (2010) [143] to study adsorption potential of agricultural
Table 4
Recently reported biosorption studies of biomass materials for the removal of heavy metals and metalloids.
Biomass material
Metal
Biomass type
Biosorption
capacity
(mg g1)
pH
Reaction
time (h)
Adsorbent
concentration
(g L1)
Remarks
References
Garcinia cambogia
Waste crab shells
Rice husk ash
As
As
Se
Plants
Animal
Crop
704.11
8.3
2.007
6
2.51
28
0.5
24
100
5
2.0
110
[148]
[149]
[138]
Saccharomyces cerevisiae
(brewers yeast) (from brewery)
Penicillium oxalicum var. Armeniaca (residue
from fermentation industry)
Tolypocladium sp. (residue
from fermentation industry)
Cystoseira baccata
Spirulina sp. (commercially available)
Saccharomyces cerevisiae (waste brewers yeast)
Bakers yeast (lab cultured)
Phomopsis sp. (lab cultured)
Hg
Fungi (yeast)
133.3
6.0
2.0
Immobilized beads of a tropical tree fruit native to India

Ground into particles, then washed with 1 M HCl
The rice husk ash obtained from burning of rice husk in electrical
oven at 700 8C for 3 h
Magnetically modied Brewers yeast cells
Hg
Fungi
269.3
56.2
72
0.1, 0.2
Hg
Fungi
161.0
72
0.1, 0.2
Hg
Cd
Cd
Cd
Cd
Algae
Bacteria
Fungi (yeast)
Fungi (yeast)
Fungi
329
99.5
15.4
11.63
29 1
6.0
7
4
6.0
4
0.5
3
0.5
24
2.5
1
2
1
2.0
Ulva onoi
Ulva onoi
Cd
Cd
Algae
Algae
61.9
90.7
7.8
7.8
12
12
1
1
Gelidium sesquipedale
Olive pomace
Azolla liculoides
Cd
Cd
Cd
Algae
Plants
Plants
18.0 0.2
5.5 0.1
111132
5.3
5
5.5
10
2
10
2
Phragmites australis shoot
Cd
Plants
10.2 0.3
Parthenium hysterophorous
Cd
Weed
27
34
0.333
10
Oryza sativa
Cd
Plants
20.70
0.166
16
Spirodela polyrhiza (L.) Schleiden biomass
Cd
Aquatic plant
36.0
6.0
120
0.1
Orange peels
Pb
Plants
400
35
0.51.5
Orange peels
Pb
Plants
1.22
4.56.0
1.67
Gloeocapsa gelatinosa
Penicillium chrysogenum (lab cultured)
Pb
Pb
Pb
Bacteria
Fungi (yeast)
Fungi
256.41
85.6
204
4
4
5.5
0.5
3
6
0.1
2
1
Penicillium oxalicum var. Armeniaca

(residue from fermentation industry)
Sargassum sp.
Azolla liculoides
Pb
Fungi
47.4
72
0.1, 0.2, 0.3
Pb
Pb
Algae
Plants
303
264297
5
5.5
6
10
1
2
Pb
Plants
17.2
Streptomyces rimosus
Pb
Bacteria
135
24
Sargassum sp.
Pb
Algae
266
27
[150]
Treated with 10 M NaOH under boiling; ground and passed through

125 mm screen
Ground and passed through 125 mm screen
[151]
Ground and passed through 0.51 mm screen

Lyophilized bacterial cells
Modied by crosslinking cystine with glutaraldehyde
Mycelium boiled with 0.5 M NaOH, dried at 60 8C, ground and
passed through 100 mm screen
Soaked in 0.1 M NaOH for 1 h, then ground and passed through
14 mm screen
Ground and sieved (0.251 mm in size)
Dried, ground and washed by distilled water
2.0 mm in size; activated by alkali and CaCl2/MgCl2/NaCl (2:1:1,
molar ratio); experiments conducted at 1040 8C
Ground and passed through 90 mm screen, then treated with 0.1 M
NaOH; optimal pH for adsorption: near neutral
Weed can be utilized for the treatment of Cd(II). Recovery of 82%
Cd(II) in the solution of 0.1 M HCl had been obtained
Dried rice straw was grinded and sieved to pass 4060 mesh. The
biomass was mixed with urea in 1:2 by mass and irradiated in a
microwave oven for a period of 12 min
The huge biomass generated from Spirodela polyrhiza can be
successfully utilized for wastewater treatment
Protonation was carried out by suspending the sorbent material in
0.1 M HNO3 for 3 h, rinsing, and drying for 12 h at 40 8C
Effects of alkaline saponication, different concentrations of citric
acid and different temperatures on the preparation of orange peel
biosorbents were investigated
Lyophilized cells with capsular polysaccharide (CPS)
Modied with polyethylenimine and crosslinked with
glutaraldehyde
Treated with 10 M NaOH under boiling; ground and passed through
125 mm screen
Treated with 0.2% formaldehyde
NaOH
Streptomyces rimosus biomass treated with 0.1 M NaOH was used in
granulated form
The brown seaweed Sargassum sp. was harvested from the sea,
washed with distilled water to remove particulate material, and oven
dried at 343 K for 24 h. Dried biomass was cut and sieved. The fraction
with 0.30.7 mm was selected for use in the sorption studies.
[152]
[153]
[154]
[155]
[156]
[151]
[158]
[159]
[160]
[161]
[146]
[251]
[255]
[162]
[163]
[164]
[154]
[165]
[157]
[157]
[151]
[166]
[160]
[161]
[167]
[168]
245
246
Table 4 (Continued )
Biomass material
Metal
Biomass type
Biosorption
capacity
(mg g1)
pH
Reaction
time (h)
Adsorbent
concentration
(g L1)
Remarks
References
Spirodela polyrhiza (L.) Schleiden biomass
Pb
Aquatic plant
137
4.0
120
0.1
[255]
Saccharomyces cerevisiae
(waste brewers yeast)
Penicillium chrysogenum (lab cultured)
Ni
Fungi (yeast)
6.34
The huge biomass generated from Spirodela polyrhiza can be

successfully utilized for wastewater treatment
Ni
Fungi
55 1
5.5
[165]
Sargassum sp.
Azolla liculoides
Ni
Ni
Algae
Plants
71.6
70.380.1
5
5.5 0.2
6
10
1
2
Ni
Plants
7.92 0.06
Rice husk ash
Zn
Crop
9.588
28
1
110
Phomopsis sp. (lab cultured)
Zn
Fungi
10.3 0.3
24
Ulva onoi
Zn
Algae
74.6
7.8
12
Azolla liculoides
Zn
Plants
64.184.4
5.5 0.2
10
Zn
Plants
5.75 0.07
Magnetic biochar
Zn
1.4
10
0.09
Oedogonium hatei
Cr
Empty food
branch
Algae
31.0
14
0.172.67
0.11
Oedogonium hatei
Cr
Algae
35.2
14
0.172.67
0.11
Spirulina sp.
Bengal gram (Cicer arientinum) seed husk
Soybean hulls
Cr
Cr
Cr
Cr
Bacteria
Fungi (yeast)
Plants
Plants
185
12.8
91.64
58 2
7
4
2.0
3
0.5
18
5
24
1
2
10
10
Sugarcane bagasse
Cr
Plants
103 9
24
10
Corn stover
Cr
Plants
84 10
24
10
Mucor hiemalis
Cr
Fungi
53.5
1.5
Spirulina sp.
Sphaerotilus natans
Aspergillus niger
Sargassum sp.
Olive pomace
Cu
Cu
Cu
Cu
Cu
Cu
Bacteria
Bacteria
Fungi
Algae
Plants
Plants
196
60
26
87.1
10 1
9.91 0.06
7
6
6
5
5
0.5
0.5
24
2
1
3
2
1
10
1
Acrylic acid functionalized

poly(N isopropylacrylamide)
hydrogel
Quercus coccifera shell
Cu
Biomass based material
67.25
5.0
0.5
Modied with polyethylenimine and crosslinked with

glutaraldehyde
NaOH
The rice husk ash obtained from burning of rice husk in electrical
oven at 700 8C for 3 h.
Mycelium boiled with 0.5 M NaOH, dried at 60 8C, ground and
passed through 100 mm screen
Soaked in 0.1 M NaOH for 1 h, then ground and passed through
14 mm screen
NaOH; optimal pH for adsorption
Empty food branch was grinded to 150 mm and treated by ferric
chloride with impregnation ratio of 0.5
Algal biomass was washed in running tap water followed by Milli-Q
water 45 times, kept on a lter paper to reduce the water content,
then sun dried for four days followed by drying in an oven at 70 8C
for 24 h
Raw biomass of Oedogonium hatei was treated with 0.1 M HCl and
then stirred the mixture at 200 rpm for 8.0 h, centrifuged, washed
with the physiological saline solution and dried in an oven at 60 8C.
Lyophilized cells
Available in tropical countries; dried at 105 8C for 24 h
Modied by crosslinking with dimethyloldihydroxyethylene urea
and quaternary amine
M. hiemalis was cultured in potato dextrose broth and the biomass
was harvested after 7 days. Harvested biomass was washed
thoroughly and was killed by autoclaving at 121 8C and a pressure of
15 lb.
Lyophilized cells
Lyophilized cells
Treated with 1% formalin; particles (0.751.0 mm in size)
Dried, ground and washed by distilled water
NaOH; optimal pH for adsorption
Poly(N isopropylacrylamide-co-acrylic acid) hydrogels can be
utilized for copper ion adsorption from aqueous solutions
Co
Plants
33
311
1.5
[166]
[160]
[161]
[138]
[156]
[157]
[160]
[161]
[250]
[169]
[169]
[153]
[154]
[170]
[171]
[171]
[171]
[15]
[153]
[172]
[173]
[166]
[159]
[161]
[256]
[174]
A mixture of formalin 30% and 0.1 N HCl was added to the biomass
to obtained formaldehyde treated biomass
[154]
residues viz. rice straw, wheat straw and Salvinia plant biomass for
removal of heavy metals such as Cr, Ni, and Cd. Heavy metal
removal efciency was more at low metal concentration
(35 mg L1). Salvinia biomass possessed higher efciency for
removing heavy metals such as Cr, Ni and Cd followed by a
combination where three materials (rice straw, wheat straw,
Salvinia biomass) were taken together in comparison to other
combinations. An attempt at the use of rice husk ash, an
agricultural waste, as an adsorbent of Zn(II) and Se(IV) from their
aqueous solution was carried out by El-Said et al. [138] as a
function of contact time, metal ion concentration, adsorbent dose,
and pH at 25 8C. Its adsorption capability and adsorption rate were
considerably higher and faster for Zn(II) ions than for Se(IV) ions.
Zn(II) removal was found fast reaching equilibrium within 1 h
while Se(IV) adsorption was slow reaching equilibrium within
100 h. The authors used the Bangham equation to express the
mechanism of adsorption. The adsorption of metal ions increased
with an increase in the biosorbent dosage from 1 to 10 g L1 and
with a decrease in initial metal ions concentrations. The afnity of
Rice husk ash for Zn(II) ions was greater than that for Se(IV) ions.
Equilibrium adsorption of Zn(II) and Se(IV) ions by rice husk ash
followed typical adsorption isotherms and ts both the Langmuir,
Freundlich, and Temkin adsorption isotherms.
Ho and Ofomaja [139] used coconut copra meal, a waste
product of coconut industry for its potential use as a biosorbent for
cadmium ions from aqueous solution. They examined a comparison of linear least-squares method and a trial and error non-linear
method of three widely used isotherms, Langmuir, Freundlich, and
RedlichPeterson. Langmuir isotherm parameters obtained from
the four Langmuir linear equations by using linear method were
not similar, but were the same when nonlinear method was used.
The biosorption process was spontaneous and exothermic process
in nature.
Recently, Schiewer and Iqbal [140] investigated the role of
pectin in Cd2+ metal binding by citrus peels, native orange peels,
protonated peels, depectinated peels, and extracted pectic acid.
Kinetic experiments showed that equilibrium was achieved in
1 h. The magnitude of the negative surface charge determined
from potentiometric titrations decreased in the order
PP > PrP > DP > NP, showing that carboxyl groups of pectin
was a major contributor to the surface charge. Mostly, metal
binding experiments have been carried out at optimized pH 5.
Langmuir isotherm model provided the best t. Metal binding
kinetics was better described by the rst-order model than by the
second-order model.
Vaghetti et al. [141] reported the feasibility of pecan nutshell
(Carya illinoensis) as an biosorbent to remove Cr(III), Fe(III) and
Zn(II) metallic ions from aqueous solutions. The adsorption
potential of pecan nutshell to remove these metallic ions was
investigated by using batch mode. The effects of several
parameters, such as pH and the biosorbent dosage on the
adsorption capacities of pecan nutshell were studied. Five kinetic
models were tested; the adsorption kinetics being the better tted
one to the fractionary-order kinetic model. Taking into account a
statistical error function, the data were best tted to Sips isotherm
models. The maximum biosorption capacity of pecan nutshell were
93.01, 76.59, and 107.9 mg g1 for Cr(III), Fe(III), and Zn(II),
respectively.
247
afnity of CH3HgCl > C2H5HgCl > Hg2+, with the maximum

sorption capacities of 79, 67, and 61 mg g1, respectively.
Weed
The efciency of Parthenium hysterophorous weed for the removal
and recovery of Cd(II) ions from wastewater have been studied by
Ajmal et al. [146]. The authors reported that the kinetics data for the
adsorption process obeyed second-order rate equation. The
adsorption process was found to be endothermic and spontaneous
in nature. The maximum adsorption capacity of Cd(II) ions was 99.7%
in the pH range 34. The desorption studies conrmed 82% recovery
of Cd(II) when 0.1 M HCl solution was used as eluent.
Medicinal herbs
Rao et al. [147] have tested the biosorption potential of Fennel
biomass (Foeniculum vulgari) a medicinal herb for the effective
removal of Cd(II) ions. The biosorption was maximum (92%) at pH
4.3. Maximum biosorption capacities of Cd(II) at 30, 40 and 50 8C
temperatures were 21, 24 and 30 mg g1, respectively. The
biosorption of Cd(II) was concentration dependent and increased
from 0.49 to 9.3 mg g1 with increase in concentration from 5 to
100 mg L1. Biosorption followed Freundlich isotherm at 50 8C.
Mean free energies at different temperatures were in between 7.1
and 11.95 kJ mol1 indicating chemical nature of biosorption
process. Kinetics studies showed that pseudo second order kinetics
model was applicable to the data. The process was endothermic
and spontaneous in nature, the spontaneity of the process
increases with increase in temperature.
Non-timber products
Lalhruaitluang et al. [121] have applied activated charcoal
prepared from Melocanna baccifera raw charcoal, the most
abundant and economically important non-timber product in
the tropical countries, by chemical treatment and used in various
experiments to test its functions as adsorbents for removal of Ni(II)
and Zn(II) from aqueous solution. Freundlich and Langmuir
isotherms constants (mg g1) for the adsorption of Ni(II) and
Zn(II) onto Melocanna baccifera raw carbon and M. baccifera
activated carbon were 2.93, 9.45 and 28.53, 52.91, and 3.87, 4.723
and 27.01, 40.485, respectively. The correlation coefcients (R2) of
Ni(II) for the pseudo-second-order kinetics model onto M. baccifera
raw carbon and M. baccifera activated carbon were 0.999 and 0.999,
respectively and the experimental qe values were agreed well with
the calculated qe values. Similarly, the correlation coefcients (R2)
of Zn(II) for the pseudo-second-order kinetics model onto M.
baccifera raw carbon and M. baccifera activated carbon were 0.987
and 0.999, respectively and the experimental qe values were also
agreed well with the calculated qe values. On the other hand, the
correlation coefcients of the pseudo-rst-order kinetics model
were lower than the pseudo-second-order kinetics model in M.
baccifera raw carbon and M. baccifera activated carbon for Ni(II)
and Zn (II) and the calculated qe values from pseudo-second-order
kinetics were agreed well with the experimental qe values than the
pseudo-rst-order. Therefore, it had been concluded that the
adsorption system followed a pseudo-second-order reaction rather
than pseudo-rst-order reaction.
Organometallic compounds biosorption

Modications and activation of biosorbents
A few biosorbents have been reported for the adsorption of
heavy metals not only in the form of metallic ions but also
organometallic compounds. Saglam et al. [142] have prepared the
biosorbents by the biomass of Phanerochaete chrysosporium which
adsorbed inorganic mercury and alkylmercury species with an
Various factors such as specic surface area, pore-size

distribution, pore volume and presence of surface functional
groups inuence the adsorption capacity of adsorbents prior to
their modication; so that they may be tailored to have the desired
248
Table 5
Technical advantages and disadvantages of existing modication techniques.
Modication
Treatment
Advantages
Disadvantages
Chemical characteristics
Acidic
Increases acidic functional groups on activated

carbon surface enhances chelation ability with
metal species
Enhances uptake of organics
May decrease BET surface area and pore volume
Basic
Physical characteristics
Biological characteristics
Impregnation of
foreign materials
Heat
Bioadsorption
Enhances in-built catalytic oxidation capability

Increases BET surface area and pore volume
Prolongs activated carbon bed life by rapid
oxidation of organics by bacteria before the
material can occupy adsorption sites
May, in some cases, decrease the uptake of

metal ions
May decrease BET surface area and pore volume
Decreases oxygen surface functional Groups
Thick biolm encapsulating activated carbon
may impede diffusion of adsorbate species
Carbon surface can be modied to develop desirable physicochemical properties by adequate choice of activation procedures. It
is even possible to prepare carbons with designated proportions of
micro-, meso-, and macropores. The techniques of modication of
carbon/activated carbon can be categorized into three broad
groups: modication of chemical, physical and biological characteristics. Among these three methods, modication with
chemical compounds has been more frequently employed to
increase the adsorption and hence removal capacity of activated
carbon or similar biosorbents. In order to facilitate a more focused
discussion, only studies on modication with chemical compounds
of activated carbons have been visited in this review. Table 5 lists

and compares the advantages and disadvantages of existing
modication techniques with regard to technical aspects.
As the biosorption process involves sequestration of metal ions
on the cell surface, the modication of cell wall can greatly alter the
binding of metal ions. A number of methods have been employed
for cell wall modication of microbial cells in order to enhance the
metal binding capacity of biomass and to elucidate the mechanism
of biosorption. The physical treatments include heating/boiling,
freezing/thawing, drying and lyophilization. The various chemical
treatments used for raw biomaterials modication include
washing the biomaterial with detergents, acid or alkali treatment.
The pretreatments could modify the surface characteristics/groups
either by removing or masking the groups or by exposing more
metal binding sites [176]. Physical methods include vacuum and
freeze-drying, boiling or heating, autoclaving and mechanical
disruption. Chemical methods include treatment with various
organic and inorganic compounds, such as acid and caustic,
methanol, formaldehyde, etc. Fig. 1 shows the sequence of steps in
the preparation of different types of biosorbents from biomass
sources.
[(Fig._1)TD$IG]
Activation of adsorbents
Fig. 1. Biosorbents preparation routes from biomass using chemical and physical
methods.
Activated carbon
Activated carbon biosorbents constitutes one of the most
important types of industrial carbon and is prepared by modication and activation of a large number of raw biomass. Because of its
high adsorption capacity it is used extensively in environmental
applications for the removal of impurities from gases and liquids, it
needs to possess a well developed pore structure, which is
recognized to be the most important property of activated carbon
[177,178]. The high adsorptive capacities of activated carbons are
mainly associated with their internal pore properties such as pore
surface area, pore volume, and pore size distribution [179181].
Generally, activated carbons are mainly microporous, but in
addition to micropores they contain meso and macropores, which
are very important in facilitating access of the adsorbate molecules
to the interior of the carbon particle and in many of the adsorption
applications in liquid phase [182].
Most of the activated carbons are produced by a two-stage
process carbonization followed by activation [124]. The rst step is
to enrich the carbon content and to create an initial porosity and
the activation process helps in enhancing the pore structure.
Basically, the activations are two different processes for the
preparation of activated carbon: physical activation and chemical
activation. There are two important advantages of chemical
activation in comparison to physical activation. One is the lower
temperature in which the process is accomplished. The other is
that the global yield of the chemical activation tends to be greater
since burn off char is not required. The structure and volume of
micropores and transitional pores developed during activation
physical and chemical attributes to enhance their afnities toward

metal ion uptake from aqueous solutions. Usually, adsorption
capacity increases with increase in specic surface area due to the
availability of a number of adsorption sites, while pore size and
micropore distribution are closely related to the composition of the
adsorbents and the type of biomass raw material supplied for their
synthesis [175].
Modication techniques
249
Table 6
The classication of pretreatment methods for the production of activated biosorbents. Data has been compiled from Refs. [129,144,145,186191,247,257].
Physical methods
Chemical and Physicochemical methods
Biological methods
Milling:
- Ball milling
- Two-roll milling
- Hammer milling
Irradiation:
- Ultrasound irradiation
- Gamma-ray irradiation
- Electron-beam irradiation
- Microwave irradiation
Others:
- Hydrothermal
- High pressure steaming
- Extrusion
- Pyrolysis
Explosion:
- Steam, Ammonia, CO2, SO2, Acids
Alkali:
- CaO, ZnCl2, NaOH, NH3, (NH4)2SO3
Acid:
- H2SO4, HCl, HNO3 and H3PO4 acids
Gas:
- ClO2, NO2, SO2
Oxidizing agents:
- H2O2
- O3
-Wet oxidation
Solvent extraction of lignin:
- Ethanolwater extraction
- Benzenewater extraction
- Butanolwater extraction
Fungi and actinomycetes:

- Lignin peroxidase, manganese peroxidase, laccase
- White-rot and brown-rot fungi
depend upon the nature of the starting material and the conditions
of activation. The changes that occur in micropore volume, pore
size, and surface area during activation of various types of carbon
have been reviewed by several authors [183].
Knowledge of different variables during the activation process
is very important in developing the porosity of carbon sought for a
given application. Among the numerous dehydrating agents, zinc
chloride in particular is the widely used chemical agent in the
preparation of activated carbon for the removal of metal ions from
aquatic environment [124,184]. Chemical activation by zinc
chloride improves the pore development in the carbon structure,
and because of the effect of chemicals, the yields of carbon are
usually high [185]. Table 6 shows the classication of pretreatment
methods for the production of activated biosorbents. Pretreatment
action may results in modication of the structure, increased
surface area, increased pore sizes, partial hydrolysis of hemicelluloses etc. Fig. 2 shows the pretreatment action on the
biomaterials. Extensive drying of the lignocellulosic materials
should be avoided because it may results to pore shrinking which
may leads to limits the diffusion of metal ions. Several
sophisticated instruments such as SEM, TEM, IR spectroscopy,
FTIR, XRD, BET surface area analyzer, XPS, TGADTA, DSC, AFM,
NMR, Element analyzer, etc. have applied for the characterization
of biomass activated biosorbents. Fig. 3 shows the SEM images of
raw and activated biomass based biosorbents. Activate carbon
[(Fig._2)TD$IG]
Fig. 2. Action of pretreatment on biomass materials for the production of

biosorbents.
have been developed by treating raw mustard husk with conc.

sulfuric acid in 1:1 ratio (Fig. 4).
Alkaline treatments on biomass have been reported to enhance
the metal ion adsorption capacity in many cases [192198].
Calcium oxide have been used as activating agents for preparation
of activated carbon biosorbents and used as a nonconventional
adsorbent for the removal of Cu(II) and Ni(II) ions from aqueous
solutions [199]. The introduction of alkali or alkaline earth metals
on the surface of the adsorbent provides basic sites that have a
high afnity for adsorption. CaO has a low charge to radius ratio
and can provide strong basic sites to the surface of the adsorbent
[200].
The purpose of activation of charcoal is to create pores and
develop larger surface area in the carbon material and thereby
increase the adsorptive capacity. The adsorption capacity of
chemically activated charcoal biomass from Bamboo with various
concentrations of KOH had been investigated by Lalhruaitluang
et al. [121]. The KOH concentration of 50% and 60% treatment
showed highest adsorption of Ni(II) and Zn(II) from aqueous
solutions, respectively. Among the alkali metal salts, KOH is the
most effective activating agent in producing activated carbon
materials. The KOH activation was reported to be effective for
increasing micropore volume [201,202]. The reaction between
KOH and carbon precursor can result in the formation of functional
groups such as OK using oxygen of the alkali salt. The presence of
such potassium and oxygen bond in the char leads to the oxidation
of cross linking carbon atoms in the adjacent lamella during the
process of activation. Surface functional groups can be created at
the edges of the lamella. As a result of removal of cross linking
between adjacent lamella and also the formation of new functional
groups on individual lamella, the lamellas of the crystallite were
disturbed from their normal form into a slightly wrinkled or folded
or puckered form. Also the potassium metal produced in the
process of activation, in situ, intercalates in to the lamella of the
crystallite. At the same time, the lamella cannot return to their
original state, creating interlayer voids. The lamella remains apart
causing porosity and yielding high surface area carbon [203]. Thus
during activation with KOH, amorphous carbon as well as silica are
removed from the carbon precursor resulting in porous structure
and a corresponding increase in the surface area.
The oxidative treatment in an oxidized gas atmosphere or a
reaction with strong acid such as H2SO4, HNO3 and HCl could
increase the total amount of acidic functional groups on biomass
surface [157,204,205]. It is worthwhile to mention that every
treatment for improving surface chemistry of activated carbon
may change its textural characteristics [197]. For example,
impregnation of urea may enhance the development of carbon
[(Fig._3)TD$IG]
250
porosity [206], and oxidation may decrease specic surface area

and pore volume [207,208].
Activated seaweed
The adsorption capacity for metal ions was signicantly
improved with acidbase modication [157,209,210]. Both SBET
and surface chemistry were changed dramatically due to acid and
acidbase treatment, which resulted in extremely different
adsorption preference [197]. Suzuki et al. [157] have removed
the heavy metals from aqueous solution by non-living Ulva
seaweed as biosorbent. The dried biomass was pretreated with
0.1 M HCl for 1 h and rinsed with distilled water until the pH of the
rinsing water was more than 4.5. In the case of the alkalipretreated material, the dried biomass was soaked in 0.1 M NaOH
for 1 h, and rinsed with distilled water until the pH of the rinsing
water was less than 10. The prepared biomass material was applied
for the adsorption of Cd from aqueous solution in batch mode. It
has been showed that treated Ulva have excellent ability for
adsorption of heavy metals. The isotherm model was well tted to
most celebrated monolayer Langmuir model with sorption
capacity of 6090 mg g1.
Activated sawdust
Sawdust is one of the promising materials which can be used to
adsorb heavy metals. The sorption characteristics of sawdust
strongly depend on its charging status controlled by the types and
numbers of functional groups on its surface [253].
Formaldehyde treated sawdust of Pinus sylvestris have been
studied for the removal of Cd(II) and Pb(II) from aqueous solutions
[211]. Biosorption of cadmium from aqueous solution using
Mulberry wood sawdust treated with hydrochloric acid has been
studied [205]. The Mulberry sawdust was chemically treated with
1.0 mol L1 HCl solutions for 24 h. The biosorption of Cd(II) ions
was pH dependent and maximum biosorption was achieved at pH
6 after 30 min shaking. The maximum biosorption capacity of
chemically treated sawdust obtained from Langmuir isotherm was
403.73 (mg g1) for Cd(II) ions, which showed a great adsorption
capacity of the treated biomass. The experimental data showed
that the pseudo-second-order model was the best tted kinetic
model for description of biosorption of Cd(II) ions on treated
Mulberry sawdust. The same authors have reported that they have
[(Fig._4)TD$IG]
Fig. 3. SEM images of biomass based biosorbents, (A) raw mustard husk, (B)
activated mustard husk, (C) activated Pinus cone, and (D) activated Ficus fruit. All
the activated carbon had been obtained by treating concentrated sulfuric acid (ratio
of biomass with conc. sulfuric acid was 1:1).
Fig. 4. FTIR image of activated mustard husk. The mustard husk was activated by
applying concentrated sulfuric acid and the ratio of mustard husk with
concentrated sulfuric acid was 1:1.
[(Fig._5)TD$IG]
251
recovered maximum cadmium (92.79%) from loaded biosorbent by

using 1.5 mol L1 HCl solution.
Natural bamboo sawdust with celluloselignin polymeric
structure was used by Zhao et al. [253,254] as a raw adsorbent
to remove heavy metal in water. In contrast to most other plants
which need to grow for 10100 years, bamboo is a fast-growing
and renewable resource; which becomes mature in 46 years.
Additionally, the wood processing in industrial and agricultural
production often generates a massive amount of sawdust that
needs to be reused. The analysis of surface properties showed that
high proton afnity sites were mainly composed of phenolic and
alcohol hydroxyl, while low proton afnity sites mainly consisted
of carboxylic acid, silicon hydroxyl, aluminum hydroxyl and some
low densities of sulfhydryl and phosphoryl groups.
Activated bagasse
Adsorption of heavy metal ion from aqueous solution by
modied sugarcane bagasse has been well recognized [212214].
The sugarcane bagasse has been modied with succinic anhydride
to introduce carboxylic functions to sugarcane bagasse and the
chemical introduction of commercial linear polyamine via the
formation of amide functions [212]. It has been well established
that polyamines have powerful chelating properties, mainly
toward ions such as Cu2+, Zn2+, and Pb2+ [215,216].
Gurgel and Gil [217] have described the preparation of two new
chelating materials, MMSCB 3 and 5, derived from succinylated
twice-mercerized sugarcane bagasse (MMSCB 1). MMSCB 3 and 5
were synthesized from MMSCB 1 using two different methods. In
the rst method, MMSCB 1 was activated with 1,3-diisopropylcarbodiimide and in the second with acetic anhydride and later
both were reacted with triethylenetetramine in order to obtain
MMSCB 3 and 5. The capacity of MMSCB 3 and 5 to adsorb Cu2+,
Cd2+, and Pb2+ from aqueous single metal ion solutions was
evaluated at different contact times, pH, and initial metal ion
concentrations. Adsorption isotherms were well tted by Langmuir model. Maximum adsorption capacities of MMSCB 3 and 5 for
Cu2+, Cd2+, and Pb2+ were found to be 59.5 and 69.4, 86.2 and 106.4,
158.7 and 222.2 mg g1, respectively.
Activated carbon from agro-waste
Sorption of Cu(II) and Ni(II) ions from aqueous solutions using
calcium oxide activated date (Phoenix dactylifera) stone carbon
have been performed by Danish et al. [199]. The results revealed
that calcium oxide activated date stone has a honeycomb like
surface morphology with large mesoporous surface area
(645.5 cm3 g1) for adsorption and removal of copper and nickel
was followed the pseudo-second-order kinetics and Langmuir
model of isotherms. The trend of adsorption amount of Cu(II) and
Ni(II) was appeared same at the equilibrium, and both ions
adsorption increased as the initial metal ion concentration
increased. The greater electronegativity of Cu(II) have been given
the reason to enhance the binding capacity of copper toward the
negatively charged adsorbent surface, which resulted in a slightly
higher adsorption capacity for Cu(II) than Ni(II).
Lalhruaitluanga et al. [218] have performed the removal of
Pb(II) adsorption from aqueous solutions by raw and activated
charcoals of M. baccifera Roxburgh (bamboo). They have conducted
batch experiments for under varying range of pH (2.06.0), contact
time (15360 min) and metal ion concentrations (5090 mg L1).
The optimum conditions for Pb(II) biosorption were almost same
for M. baccifera raw charcoal and M. baccifera activated charcoal pH
5.0, contact time 120 min. The Langmuir and Freundlich adsorption capacity of Pb(II) onto M. baccifera raw charcoal and M.
baccifera activated charcoal were 10.66 mg g1 and 7.730 mg g1,
and 53.76 mg g1 and 46.32 mg g1, respectively. However, the
activated biosorbents of M. baccifera was found to be more suitable
Fig. 5. Effect of oxidation on the surface charges of coconut shell carbon (CSC); nitric
acid treated coconut shell carbon (CSCN); hydrogen peroxide treated coconut shell
carbon (CSCH); and ammonia persulfate treated coconut shell carbon (CSCA) [190].
than raw biosorbent of M. baccifera for the development of an

efcient adsorbent for the removal of Pb(II) from aqueous
solutions.
Vasu et al. [190] have synthesized the activated carbon by
carbonizing the coconut shells in a mufe furnace at a temperature
of 400 8C for 1 h. Then, the obtained carbon was oxidized with
concentrated nitric acid, hydrogen peroxide and ammonium
persulfate. The purpose of the oxidizing agent modication of
the carbon surface was to enhance the density of the surface
functional groups (Fig. 5). The pHzpc for coconut shell carbon (CSC),
nitric acid treated coconut shell carbon (CSCN), hydrogen peroxide
treated coconut shell carbon (CSCH), and ammonia persulfate
treated coconut shell carbon (CSCA) were 7.45, 6.72, 6.76, and 6.40,
respectively. Several authors have been used hen egg shell as
adsorbent for heavy metal sequestration or as activating agent for
carbon surface [219]. However, the adsorption capacity of raw hen
egg shell was very low. The hen egg shells had been applied as an
activating agent for commercial carbon via modication of their
surface chemistry [219].
A vast array of functional groups such as carboxylates, phenolic
and aliphatic hydroxyls, and carbonyl groups in biomaterials have
the ability to adsorb metal ions. To enhance the heavy metal ion
adsorption of biomass, the biomaterial was chemically modied by
introducing different complexing groups such as aminoalkyl [220],
2,2-diaminoethyl, and amidoxime [221], or an ionic moiety such as
phosphate [222], thiolate [223], carboxy [224], and carboxymethyl
[225,226].
New activated biosorbents
Adsorption of Pb(II) and Cu(II) onto diethylenetriaminebacterial cellulose (EABC) was performed by Shen et al. [227].
EABC was synthesized by amination with diethylenetriamine on
bacterial cellulose. The amount of adsorption of Pb(II) and Cu(II)
onto EABC was maximum in acidic medium at pH 4.5. This was
due to the protonation of the amino groups at the acidic conditions.
But when the pH was >4.5 the adsorption capacity declined
simultaneously. The results showed that the adsorption rate was
well tted by pseudo-second-order rate model, and adsorption
isotherm was well described by the Langmuir model. In this
experiment the adsorption uptake of metal ions was good but it
takes a too longer contact time. For keeping in mind the practical
252
applications of synthesized biomaterial the same authors have

performed desorption experiments and regeneration of adsorbent
by using 0.1 M EDTA and HCl solutions. The desorption efciency
of EDTA was quite high (99%) in comparison of HCl (90%) solution.
Konjac glucomannan (KGM) is a neutral polysaccharide which
consists of mannose and glucose in a molar ratio of 1.6:1 with a b1,4-linkage, derived from the tubers of Amorphophallus konjac
[228]. On the other hand, its dissolution is very high in water
showing increased water absorbency [229]. This limitation
prevents the KGM for being used as adsorbent in separation
science. Niu et al. [230] chemically modied the KGM by
crosslinking agent to overcome this problem and functionalized
with carboxymethyl groups for removal heavy metal ions from
aqueous solutions. Because of low degree of substitution of
carboxymethyl groups on crosslinked KGM, the removal capacity
of crosslinked carboxymethyl KGM biomaterial for heavy metal
ions was not high. Liu et al. [231] synthesized carboxylic acid
functionalized deacetylated konjac glucomannan by free radical
graft copolymerization of methyl acrylate (MA) and methylmethacrylate (MMA) onto the backbone of deacetylated konjac
glucomannan with subsequent chemical activation of the ester
groups in the side chains of the resulting graft copolymer by
sodium hydroxide. The KGM showed a high adsorption capacity for
Cu2+ and Pb2+ ions. The maximum adsorption capacity onto
carboxylic acid functionalized deacetylated konjac glucomannan
was found to 64.5 mg g1 and 191.3 mg g1 for Cu2+ and Pb2+ ions,
respectively. The adsorption isotherm data was well described by
Langmuir model and the kinetic data were tted well to pseudosecond-order rate model.
Hydroxyapatite/chitosan (HApC) composite was synthesized
by precipitation method for the adsorptive removal of Pb2+, Co2+
and Ni2+ by hydroxyapatite/chitosan composite from aqueous
solution [232]. They have investigated the effect of various
physicochemical parameters such as pH, adsorbent dose, contact
time, initial metal ion concentration and temperature on
adsorption of metal ions onto HApC composite. The adsorption
process followed pseudo-second order kinetics and intraparticle diffusion model. The Langmuir constant for Pb2+, Co2+
and Ni2+ removal onto HApC was 12.04, 10.63 and 8.54 mg L1,
respectively. Equilibrium data were tted well in the Langmuir
and Freundlich isotherm models. The effect of different
concentration of Pb2+, Co2+ and Ni2+ on the adsorption had
been investigated at 303 K, Pb2+, Co2+ and Ni2+ adsorption
capacities of HApC were given as a function of equilibrium
concentration. It was clear that Pb2+, Co2+ and Ni2+ adsorption
capacities of HApC increased with increase of equilibrium
concentration. The Increase in adsorption capacity with increase
in equilibrium metal ion concentration for different metal ions
was in the order Pb2+ > Co2+ > Ni2+.
Recovery of metals, regeneration and desorption of biosorbents
In favor of material cycling and safe post-treatment of metal
loaded biosorbent, it is necessary to remove and recover metals
from the metal-loaded biomass that has been used in the
treatment of metal-contaminated wastewater. The metals
adsorbed on the surface of biosorbents can be recovered by
desorption with adequate eluents. Recent research on recovery of
metals from metal-loaded biosorbents using chemical reagents
and regeneration of the biosorbents are summarized in Table 7.
Heavy metals and metalloids can be effectively removed from
metal-laden biosorbents using dilute acids (e.g., HCl, HNO3, and
H2SO4). Even though HCl has a very high capacity to desorb metals,
several studies have shown that it would also decrease metal
adsorption abilities of the regenerated biosorbents because of
hydrolysis of the polysaccharides on the biomass surface as metal
binding sites [233,234]. EDTA can be used as an eluent of metal

cations, although it is less effective as compared with dilute acids.
El-Said et al. [138] have conducted batch desorption experiments and the desorption efciencies were compared, a series of
250 mL Erlenmeyer asks containing 50 mL of aqueous solution of
HCl, H2SO4, HNO3, and CH3COOH of known concentration was
contacted with metal-loaded Rice husk ash (0.5 g) at 25 1 8C. The
mixtures were agitated at 100 rpm for 5 h in the orbital shaker. Then
after, the mixture was centrifuged and the supernatant was analyzed
for metal ions released into the solvent. Desorption of Zn(II) and
Se(IV) using of mineral acids, HCl, H2SO4, and HNO3 compared with
CH3COOH acid showed maximum desorption efciency of 27% for
Zn(II) and 10% for Se(IV). On the other hand, mineral acids, HCl, H2SO4,
and HNO3 showed almost equal and higher recovery efciency 27%
for Zn(II). However, CH3COOH proved to be the best for recovery of
Se(IV).
Regeneration and reuse of a seaweed-based biosorbent in single
and multi-metal systems have been performed by Bakir et al. [235].
The regeneration of the biosorbent using an acid wash resulted in
the release of high metal concentrations during multiple desorption cycles. For desorption experiments, 0.1 M HCl was selected
due to its high metal desorption properties and its lower cost of
operation [236240], the metal loaded biomass was exposed to a
continuous feed of a 0.1 M HCl solution at 25 mL min1 for
180 min. Maximum desorption efciencies of 183%, 122% and 91%
were achieved for Zn(II), Ni(II) and Al(III), respectively, for
subsequent metal loading cycles, signicantly exceeding the
desorption rates observed for conventional sorbents. The regeneration of the sorbent was accomplished with very little loss in metal
removal efciency for both single and multi-metal systems. Values
of 92%, 96% and 94% removal efciency were achieved for Zn(II),
Ni(II) and Al(III), respectively, for the 5th sorption cycle in single
metal aqueous solutions. A slight decrease was observed for the
same metals in multi-metal systems with maximum removal
efciencies of 85%, 82% and 82% for Zn(II), Ni(II) and Al(III),
respectively.
Bernardo et al. [241] have studied the sorption and desorption
of Cr(III) by agro-waste biosorbents such as sorghum straw, oats
straw, and agave bagasse. Biosorption capacity for Cr(III) uptake
were conducted in batch experiments at pH 3 and 4, at 25 8C and
35 8C. The Cr(III) loaded biosorbents were added to 100 mL of
HNO3 (1.0 N or 0.1 N), NaOH (1.0 N or 0.1 N) or EDTA (0.1 M or
0.05 M) solutions at different concentrations and temperatures
(25 8C, 35 8C, and 55 8C). These eluents were selected aiming at an
ion exchange process, between H+ and Na+ with Cr(III) species, or
complexation (EDTA-Cr (III)). The partially saturated agro-waste
materials were efciently regenerated by an EDTA solution at 55 8C
without apparent modications on the biosorbents. The higher
chromium desorption with 1.0 M EDTA obtained at 55 8C
suggested that the interaction Cr(III)-EDTA involved a chelate
formation and an increase in temperature facilitated the chemical
interaction between EDTA and Cr(III). In addition, the initial weight
lost of acid-washed materials due to the regeneration with 0.1 M
EDTA was much lower (09%) than what was obtained when 1.0 N
HNO3 or 1.0 N NaOH was used as eluent. This fact suggested that
EDTA solutions produced fewer structural modications in the
biosorbents than the acid or the alkaline solutions. Acid and
alkaline solutions attacked the carboxyl groups conversely to EDTA
solutions. In addition, alkaline and acid regeneration produced
hydrolysis of the agro-waste materials conrmed by the initial
weight lost, and the biosorbents color change. Therefore, based on
the chromium desorbed and the initial weight lost, EDTA was the
best option to regenerate the chromium-loaded agro-waste
materials.
Das et al. [81] have studied the removal of Zn(II) by untreated
and anionic surfactant treated dead biomass of isolated yeast
Table 7
Recovery of heavy metals and metalloids from metal-loaded biosorbents reported recently.
Biosorbent material
Biosorbent type
Eluent
Number of
adsorption
desorption
cycles
Elution
mode
Elution
time (h)
Recovery (%)
Remarks
References
Cd
Streptomyces clavuligerus
Bacteria
1 M Na2SO4 (pH about 10)
Filtration
>95
[248]
Bakers yeast
Fungi (yeast)
Plants
0.1 M HCl
0.1 M HCl
>6
>3
Batch
Batch
1
1
95
98.5
Pyrolyzed coffee residue
Plants
Distilled water
Batch
0.5
88.091.9
Bakers yeast
Gloeocapsa gelatinosa
Fungi (yeast)
Bacteria
0.1 M HCl
0.01 M EDTA
>6
Batch
Batch
1
0.25 3
95
49.7
Plants
0.1 M HCl
>3
Batch
90.5
Sargassum sp.
Algae
0.05 M HNO3; 0.10 M HNO3;

0.05 M HCl; 0.10 M HCl;
0.05 M Na2EDTA; 0.10 M Na2EDTA
Batch
>95
Cr
Oedogonium hatei
Algae
0.1 M NaOH
Batch
75
Cr
Mucor hiemalis
Fungi
0.1 N NaOH
Batch
1.5
99
50-fold increase in Cd conc. in eluate as compared with

the original Cd solution. The regenerated material had a
higher maximum adsorption capacity than the original
one
Ground and passed through 90 mm screen, then treated
with 0.1 M NaOH; optimal pH for adsorption: near
neutral
Pyrolyzed at 500 8C; mixed with clay as a binder
(pyrolyzed coffee residue:clay = 80:20 [in weight]);
glanular (10 mm in length, 4 mm in diameter)
Lyophilized cells with capsular polysaccharide (CPS);
recovery of metal was repeated 3 times
Ground and passed through 90 mm screen, then treated
with 0.1 M NaOH; optimal pH for adsorption: near
neutral
High value of the conditional formation constant of the
complex Pb(II)EDTA (K0 f = 3.85 1011 at pH = 5.0),
which favors the desorption of lead, >95 lead ions was
recovered by Na2EDTA
Raw biomass of Oedogonium hatei was treated with
0.1 M HCl and then stirred the mixture at 200 rpm for
8.0 h, centrifuged, washed with the physiological saline
solution and dried in an oven at 60 8C.
Desorption data showed that nearly 99% of the Cr(VI)
adsorbed on M. hiemalis was desorbed using 0.1 N
NaOH.
Pb
[155]
[161]
[249]
[155]
[164]
[161]
[168]
[169]
[15]
Metal
253
254
species viz. Candida rugosa and Candida laurentii in both batch and
column mode. The maximum removal was 65.4% and 54.8% of Zn at
pH 6.0 in presence of 90 mg L1 Zn(II) at 30 8C in batch system for C.
rugosa and C. laurentii. Remarkable increase in Zn(II) removal was
noted using dead yeast biomass treated with anionic surfactant
sodium dodecyl sulfate (SDS). The experimental data were
analyzed using two, three and four parameter isotherm models.
Freundlich isotherm model was well tted for the adsorption of
Zn(II) from aqueous system. Four cycles of desorption and sorption
was performed to study the reusability of the biosorbent. A
decreased breakthrough time and exhaustion time were observed
as the regeneration cycles progressed. The elution efciency and
percentage removal of Zn(II) were found to decrease in the
successive cycles. This behavior is primarily due to continuous
usage of the biosorbent.
Outlooks and discussion
Several advantages in using low cost biosorbents for removal
and recovery of heavy metals from aqueous solutions are discussed
below together with the main drawbacks.
The metal ions removal rates from aqueous solution by
biosorption are generally faster than those by other metabolically
mediated processes. This property of biosorption would make it
the most effective in treatment of voluminous water bodies
containing low concentrations of metals, such as the nal
wastewater treatment process to meet regulation standards of
metals before being discharged to the environment.
The costs for formulating biosorbents and operating the
treatment systems are generally low, especially waste bacteria
and fungi from various fermentation industries, agricultural
byproducts, and the biomass that exists abundantly such as exotic
weeds can be utilized as cheap raw materials of biosorbents. It is
not necessary to feed any substrates or energy for propagation of
the raw biomass of biosorbents if these microbial wastes and
abundant biomass are to be utilized. They are, however, often
required to receive some modications before introduction into
the real wastewater treatment systems, and they will take
additional costs according to the reagents and equipments used
for the modications.
A special attention should be paid on reuse aspects. It is
generally easy to recover metals from metal-loaded biosorbents
and regenerate the biosorbents for further adsorptiondesorption
cycles. Dilute acid and alkaline solutions, salt solutions, and
chelating agents such as ethylenediaminetetraacetic acid (EDTA)
solution are reported to be effective in eluting metals from the
metal-laden biosorbents. Desorption of the adsorbed metals with
suitable acid or base results in the regeneration of biosorbents and
the recovery of precious metals.
Performances of biosorbents can be improved through various
kinds of physical and chemical pretreatments. The main purposes
of modication of raw biosorbent materials are to (a) shape and
impart mechanical strength and resistance to chemical and
microbial degradation, and (b) improve biosorption selectivity
for target metals. Pretreatments of raw biomass by physical or
chemical methods have been also found to improve the metal
adsorption performances of the biosorbents, although this is not
always the case.
Biosorption treatment can be operated at a wide range of scales.
A packed bed column reactor conguration is considered to be the
most effective mode of the biosorption process, and this system
can be scaled up to the treatment of a large volume of acid mine
drainage and industrial wastewater and scaled down to the
removal of As from contaminated well water.
Biosorbents are basically biodegradable, and the exhausted
biosorbents that consist mainly of degradable organic matter could
be converted into energy fuels through fermentation processes,

thermal energy by combustion, or composts as fertilizer, if the
complete (if not, sufcient) removal of adsorbed metals from the
biosorbents is secured.
There is a little knowledge about the comparison studies of
biosorbents for the removal of heavy metals from industrial
efuents. Several parameters (batch, column, reactor, etc.) used for
the removal of heavy metals inuence the sorption processes, on
the other hand the comparison of sorption performance depends
not only the parameters related to the experimental conditions and
the efuent. Therefore, a direct comparison of data obtained using
different biosorbents is difcult because of inconsistencies in the
data presentation [242,243].
There is a lack of data concerning the reproducibility of the
adsorption properties and the equilibrium data, commonly known
as adsorption isotherms. In view of industrial developments of the
various kinds of sorbents described in the literature, the physical
and chemical stability of the materials and the reproducibility of
the sorption properties are of utmost importance. Unfortunately,
there is little information on this subject. The design and efcient
operation of adsorption processes also requires equilibrium
adsorption data for use in kinetic and mass transfer models
[244]. These models play an important role in predictive modeling
for analysis and design of adsorption systems. Additional work on
this subject can boost up the zeal of the biosorption of heavy
metals.
Biosorption of metal ions is strongly affected by the properties
of the water to be treated, such as pH, ionic strength, coexisting
ions, and suspended solids. Optimal pH for biosorption of metal
cations is generally around neutral, and their adsorbed amounts
would decrease as solution pH is lowered because of diminishing
of negatively charged sites on the biosorbents due to protonation.
On the other hand, acidic pH favors biosorption of metal anions.
Mine drainage and industrial wastewater usually contain more
than one heavy metal species, and these metal ions would compete
with each other for the binding sites on biosorbents. Not only
heavy metals but also Ca and Mg present in hard water and Al and
Fe in most of industrial efuents and mine drainage may strongly
obstruct biosorption of the target heavy metals [245]. Thus, metal
adsorption performance of biosorbents should be carefully
evaluated in not only a single-metal solution system but also
multi-metal solution systems prior to their practical applications
[246]. This evaluation would clarify at the same time the selectivity
of the biosorbents in metal binding. The adsorption of metal
cations on biosorbents would be also inhibited by inorganic and
organic anions present in the solution due to complexation with
the metal cations.
Concluding notes
In the development of new separation and purication
technologies, such as removal of heavy metals, biosorption can
play a key enabling role. A breakthrough in sorbents development
is needed to solve the critical problem of removal and recovery of
metal ions. However, to remove the poisoning of the metal ions
from aqueous solutions, there is need for the further development
of newer biosorbents of highest removal capacity.
In this review, a wide range of non-conventional low-cost
adsorbents has been presented. Inexpensive, locally available and
effective materials could be used in place of commercial activated
carbon for the removal of heavy metals from industrial efuents.
Undoubtedly biosorbents offer a lot of promising benets for
commercial purposes in the future. In particular, from the recent
literature reviewed, agriculture-based sorbents have demonstrated outstanding removal capabilities for certain metal ions in
comparison to activated carbon. However, despite a number of
papers published on biosorbents, there is as yet little information

containing a full study of comparison between sorbents, and there
is also a big gap in study of multi-metal system. Although much has
been accomplished in the area of low-cost sorbents, much work is
necessary (i) to predict the performance of the adsorption
processes for heavy metal removal from real industrial efuents
under a range of operating conditions, (ii) to better understand
adsorption mechanisms, and (iii) to demonstrate the use of
inexpensive biosorbents at industrial scale.
Acknowledgements
R.K. Gautam is thankful to University Grants Commission, New
Delhi for the award of Junior Research Fellowship (JRF). The
authors equally acknowledge the support and provision of the
necessary facilities by University of Allahabad, Allahabad, India.
The support and encouragement of Prof. V.S. Tripathi from the
Department of Chemistry, University of Allahabad is also
appreciated. We are thankful to the three anonymous reviewers
for giving their kind criticism and comments which fueled the zeal
of the manuscript.
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Journal of Environmental Chemical Engineering 2 (2014) 239259

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

Biomass-derived biosorbents for metal ions sequestration: Adsorbent

* Corresponding author. Tel.: +91 9307663844; fax: +91 532 2541786.

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

Cr, Ni, Zn, Cu

Liquid efuents from plating processes

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

Large amount of sludge containing metals

High initial capital cost

High initial capital cost

Magnetic separation and

Wide variety of target pollutants

Recently, magnetic nanoparticles have been investigated for

this review will help provide a better understanding and

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

Has Henry law and nite

Langmuir equation relates the coverage of molecules on a solid

Does not have Henry law

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

study the biosorption kinetics of heavy metals and quantify the

The equation applicable to experimental results generally differs

another reaction of another order becomes predominant

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

useful model stems from the fact that it is a pseudo-kinetic

energy (DG), enthalpy (DH), and entropy (DS) were determined

where C and Csi is the liquid phase concentration of sorbate in

Biomass and biosorption of metal ions

Gibbs free energy (DG), change in enthalpy (DH), and change

Of the many types of biosorbents (i.e. fungi, bacteria, yeasts,

where D and dp is the intraparticle diffusion coefcient and mean

Thus, a plot of ln KL versus 1/T should be a straight line. DH and DS

Immobilized beads of a tropical tree fruit native to India

Phragmites australis shoot

Spirodela polyrhiza (L.) Schleiden biomass

Penicillium oxalicum var. Armeniaca

0.1, 0.2, 0.3

Phragmites australis shoot

Treated with 10 M NaOH under boiling; ground and passed through

Ground and passed through 0.51 mm screen

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

Spirodela polyrhiza (L.) Schleiden biomass

The huge biomass generated from Spirodela polyrhiza can be

Phragmites australis shoot

Rice husk ash

Phomopsis sp. (lab cultured)

Phragmites australis shoot

Acrylic acid functionalized

Biomass based material

Modied with polyethylenimine and crosslinked with

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

afnity of CH3HgCl > C2H5HgCl > Hg2+, with the maximum

Organometallic compounds biosorption

Various factors such as specic surface area, pore-size

R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239259

Increases acidic functional groups on activated

May decrease BET surface area and pore volume

Enhances in-built catalytic oxidation capability

May, in some cases, decrease the uptake of

of activated carbons have been visited in this review. Table 5 lists

physical and chemical attributes to enhance their afnities toward