Journal of Environmental Chemical Engineering 2 (2014) 398–414

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Review

Relevance of isotherm models in biosorption of pollutants by agricultural

byproducts
S. Rangabhashiyam, N. Anu, M.S. Giri Nandagopal, N. Selvaraju *
Department of Chemical Engineering, National Institute of Technology Calicut, Kozhikode 673601, Kerala, India

ARTICLEINFO AB STR ACT

Article history: Industries generating wastewater with elevated concentrations of pollutants (e.g. metals, dyes, phenolic
Received 1 October 2013 compounds, anions, etc.) need specialized atreatment systems. Adsorption is one of the most extensively
Accepted 13 January 2014 applied techniques for the removal of pollutants from the industrial effluents. The prominent and
emerging trend of subjecting biosorbent in the adsorption technology is mainly because of their natural
Keywords: existence, abundance, renewable, biodegradable and economic features. The adsorption isotherm
Adsorption equations used to describe the experimental data and the thermodynamic assumptions of the models
Isotherms often provide some insight into the sorption mechanism, the surface properties and affinity of the
Biosorbents
biosorbent. This paper presents a state of the art on the review of adsorption isotherm models in an
Wastewater treatment
exhaustive manner on the basis of two, three, four and five parameters respectively. Focuses on the
Pollutants
various sources of agricultural byproducts as biosorbents and describes on the potential applications of
different adsorption isotherm models for the evaluation of the wastewater pollutants biosorption. It is
evident from the literature survey that various adsorption isotherm models have been considered under
study by the researchers but mostly two and three parameter isotherm model were best fitted the
equilibrium data. This paper reviews the adsorption isotherm models on the basis of parameters that can
be applied for exploring a novel biosorbents.
© 2014 Elsevier Ltd. All rights reserved.

Contents

Introduction ...................................................................................................................................................................................................................... 400

Biosorption and the characteristic features of the biosorbents .................................................................................................................................. 400
Adsorption isotherm models ...........................................................................................................................................................................................401
Two parameter isotherms .....................................................................................................................................................................................401
The Langmuir Isotherm model .............................................................................................................................................................. 401
The Freundlich isotherm model ............................................................................................................................................................ 402
The Temkin isotherm model................................................................................................................................................................402
The Dubinin–Radushkevich isotherm model ....................................................................................................................................... 402
The Flory–Huggins isotherm model ..................................................................................................................................................... 403
The Elovich isotherm model................................................................................................................................................................403
The Fowler–Guggenheim isotherm model ........................................................................................................................................... 403
The Kiselev isotherm model ................................................................................................................................................................403
The Hill–de Boer model ........................................................................................................................................................................ 403
The Jovanovic isotherm model ............................................................................................................................................................. 403
The Halsey isotherm model .................................................................................................................................................................403
The Harkin–Jura isotherm model .......................................................................................................................................................... 403
Three parameter isotherms ...................................................................................................................................................................................404
The Redlich–Peterson isotherm model ................................................................................................................................................. 404
The Hill isotherm model ......................................................................................................................................................................404
The Toth isotherm model .....................................................................................................................................................................404
The Jossens isotherm model ................................................................................................................................................................404

* Corresponding author. Tel.: +91 495 2285409; fax: +91 495 2287250.
E-mail addresses: selvaraju@nitc.ac.in, selvaraju.n@gmail.com (N. Selvaraju).

2213-3437/$ – see front matter © 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2014.01.014
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 399

The Fritz–Schlunder isotherm model ................................................................................................................................................... 404

The Sips isotherm model ..................................................................................................................................................................... 404
The Koble–Corrigan isotherm model ................................................................................................................................................... 404
The Khan isotherm model ................................................................................................................................................................... 404
The Radke–Prausnitz isotherm model .................................................................................................................................................. 404
The Frumkin isotherm model ............................................................................................................................................................... 405
The Liu isotherm model [87] ................................................................................................................................................................ 405
Four parameter isotherms .................................................................................................................................................................................... 405
The Weber–van Vliet isotherm model ................................................................................................................................................. 405
The Fritz–Schlunder isotherm model ................................................................................................................................................... 405
The Baudu isotherm model ................................................................................................................................................................. 405
Five parameter isotherms ..................................................................................................................................................................................... 405
The Fritz–Schlunder isotherm model ................................................................................................................................................... 405
BET isotherm ......................................................................................................................................................................................................... 405
Adsorption isotherm models in the assessment of biosorbents for different pollutants .......................................................................................... 405
Adsorption isotherm model significance in the biosorbent evaluation for metal removal .......................................................................... 405
Adsorption isotherm model significance in the biosorbent evaluation for dye removal ............................................................................. 407
Adsorption isotherm model significance in the biosorbent evaluation for phenolic removal ..................................................................... 408
Adsorption isotherm model significance in the biosorbent evaluation for anio ns removal ........................................................................ 409
The selection of isotherm model for the adsorption studies [231]............................................................................................................................. 410
Error function ......................................................................................................................................................................................................... 410
Average relative error .......................................................................................................................................................................... 410
Sum of squares of the error ................................................................................................................................................................. 410
Determination coefficient .................................................................................................................................................................... 410
Adjusted determination coefficient ..................................................................................................................................................... 410
Error function [179,236] ........................................................................................................................................................................ 410
Conclusion ......................................................................................................................................................................................................................... 411
Acknowledgements .......................................................................................................................................................................................................... 411
References .......................................................................................................................................................................................................................... 411

Nomenclature
qm Elovich maximum adsorption capacity
(mg/g)
Ce equilibrium concentration of adsorbate
KFG Fowler–Guggenheim equilibrium constant
(mg/L)
(L/mg)
qe adsorbate adsorbed per gram of the
uFG, uK, uH fractional coverage
adsorbent at equilibrium (mg/g)
W interaction energy between adsorbed
Q0 monolayer coverage capacity (mg/g)
molecules (kJ/mol)
KL Langmuir isotherm constant (L/mg)
K1K Kiselev equilibrium constant (L/mg)
RL separation factor or equilibrium parameter
kn constant of complex formation between
C0 adsorbate initial concentration (mg/L)
adsorbed molecules
Kf Freundlich isotherm constant
K1H Hill–de Boer constant (L/mg)
ðmg1—ð1=nÞ L1=n g—1Þ
K2 energetic constant of the interaction
n adsorption intensity
between adsorbed molecules (J/mol)
AT Temkin isotherm equilibrium binding
Kj Jovanovic isotherm constant (L/mg)
constant (L/mg)
KH Halsey isotherm constant
bT Temkin isotherm constant
nH Halsey equation exponents Harkins–
R universal gas constant (8.314 J/mol K)
AH Jura isotherm parameter Harkins–Jura
T absolute temperature (K)
B2 isotherm constant
B heat of sorption constant (J/mol) Dubinin–
KRP Redlich–Peterson model isotherm constant
K Radushkevich isotherm constant related to
(L/g)
the adsorption energy (mol2/kJ2) theoretical
aRP Redlich–Peterson model constant (mg/L)—g
Qm isotherm saturation capacity (mg/g)
g Redlich–Peterson model exponent
Polanyi potential
q sH Hill isotherm maximum uptake saturation
e mean free energy (kJ/mol)
(mg/L)
E Flory–Huggins equilibrium constant (L/mg)
KD Hill constant
KFH model exponent
nH Hill cooperativity coefficient of the binding
nFH Gibbs free energy (kJ/mol)
interaction
DG8 degree of surface coverage of adsorbent
KT Toth equilibrium constant
u surface
TT Toth model exponent
Elovich equilibrium constant (L/mg)
H, F, p parameters of the Jossens equation
KE
400 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

large industrial scale application. Therefore cost-effective materi-

qmFS Fritz–Schlunder maximum adsorption als are needed [8]. Biosorption subjecting agricultural byproducts
capacity (mg/g) acts as the economic and pragmatic method for the removal of
KFS Fritz–Schlunder equilibrium constant (L/mg) different pollutants like heavy metals [9,10], COD [11,12], phenol
mFS Fritz–Schlunder model exponent [13,14], and dyes [15–17]. A general modelling of the sorption
q ms isotherms under 4 particular cases (C, L, H and S isotherm
Sips maximum adsorption capacity (mg/g)
respectively) with 4 main shapes of isotherm were commonly
KS Sips equilibrium constant ðL=mgÞms
observed [18]. The adsorption isotherm does not provide
mS Sips model exponent automatically any information about the reactions involved in
a Koble–Corrigan parameter(Ln mg1—n/g) the adsorption phenomenon. Therefore, mechanistic interpreta-
b Koble–Corrigan parameter(L/mg)n tions must be carefully verified for the appropriate measurements
bK Khan isotherm model constant and interpretations of isotherm data [19]. In order to investigate
qs theoretical isotherm saturation capacity novel adsorbents in the ideal adsorption system, it is essential to
(mg/g) introduce the most appropriate adsorption equilibrium correlation
nK Khan model exponent Radke– [20], which is important for reliable prediction of adsorption
qmRPI, qmRPII, Prausnitz maximum adsorption parameters and for the quantitative comparison of adsorbent
qmRPIII behaviour under different adsorbent systems or different experi-
capacities (mg/g)
mental conditions [21,22]. With this perception, equilibrium
KRPI, KRPII, Radke–Prausnitz equilibrium constants
relationships also known as the adsorption isotherms describes
KRPIII
how pollutants interact with the adsorbent materials, critical for
mRPI, mRPII, Radke–Prausnitz models exponents optimization of the adsorption mechanism pathways, expression
mRPIII of the surface properties and capacities of adsorbents and effective
f interaction coefficient of the Frumkin design of the adsorption systems [23,24].
equation
KFF equilibrium constant of Frumkin equation Biosorption and the characteristic features of the biosorbents
Kg Liu equilibrium constant (L/mg)
nL dimensionless exponent of the Liu equation Biosorption is a potential alternative technique for the removal
P1, P2, P3, P4 parameters of Weber–van Vliet equation of organic pollutants like metals, dyes and phenolics from
wastewaters. Agricultural byproducts of various origins serve as
A, B Fritz–Schlunder parameters
the biosorbents are known to bind with the pollutants [25,26]. Use
a, b Fritz–Schlunder equation exponents
of agricultural, botanical residues in biosorption process suggests
qm0 Baudu maximum adsorption capacity (mg/g)
the following importance over other unitary operations. (1) The
b0 equilibrium constant materials are usually highly economical. (2) There is no need of
x, y Baudu parameters costly growth media and maintenance of aseptic conditions. (3)
qmFS5 Fritz–Schlunder maximum adsorption The process is independent of physiological constraints of living
capacity (mg/g) cells. (4) Reversible process, the biosorbent can be subjected for the
K1, K2, m1, m2 Fritz–Schlunder parameters further recycle. (5) The formation of chemical or biological sludge
CBET BET adsorption isotherm relating to the is minimized [27].
energy of surface interaction (L/mg) The biomass source of agricultural byproducts includes wood,
adsorbate monolayer saturation short rotation woody crops, agricultural wastes, short rotation
Cs
herbaceous species, wood wastes, bagasse, sawdust, biosolids,
concentration (mg/L)
grass, etc. [28]. Most of the organic materials are produced from
the sources of plants, trees and crops. The two major carbohydrates
having significant value are cellulose and hemicelluloses [29].
Cellulose, a remarkable pure organic polymer comprised exclu-
Introduction sively of the units of anhydroglucose and bound together through
giant straight chain molecule [30]. These anhydroglucose units are
The global increase in water pollution has augmented bound together by b-(1,4)-glycosidic linkages. Through intramo-
awareness among the public and more attention has been focused lecular and intermolecular hydrogen bonds between OH groups
to combat the problem [1]. The major cause of water pollution is within the same cellulose chain and the surrounding cellulose
the industrial activities [2]. Conventional methods used for the chains, the chains tend to be arranged parallel and form a
removal of wastewater pollutants include chemical precipitation, crystalline super molecular structure [31]. Cellulose is insoluble in
ion exchange, filtration, reverse osmosis, electrochemical treat- most of the solvents and has a low accessibility to acid and
ment, electrodialysis and adsorption on activated carbon. In enzymatic hydrolysis. Hemicelluloses consist of different mono-
comparison of all the methods, adsorption plays as the most saccharide units and the polymer chains have short branches and
versatile and widely used method for the removal of pollutants are amorphous in nature, which makes it partially soluble or
because of its cost effectiveness, simplicity of design and operation swellable in water. Hemicellulose occurs as much shorter molecule
and high removal capacity [3,4]. Adsorption has been revealed as chains in comparison with cellulose [32]. Xylose is the most
the most promising and widely used method for the removal of important sugar component in the hemicelluloses. In hardwood
both inorganic and organic pollutants from contaminated water xylan, the xylose units act as the backbone linked by means of b-
[5]. Activated carbon with the properties of higher surface area, (1,4)-glycosidic bonds and branched by a-(1,2)-glycosidic bonds
good adsorption capacity and fast kinetics is used for the with 4-omethylglucuronic acid groups [31]. In case of the softwood
adsorption of pollutants from contaminated water. The use of xylan, the acetyl groups fewer distributed in the backbone chain
activated carbon in adsorption process is based on the surface and has additional branches composed of arabino furanose units
chemistry and pore structure of porous carbons [6,7]. Activated linked by means of a-(1,3)-glycosidic bonds. Hemicelluloses are
carbon is expensive and this setback, limits its employment on a highly soluble in alkali gets easily hydrolyzed [33–35]. Lignins are
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414
Fig. 1. The chemical structure of major organic compounds of agricultural byproduct.
polymers of aromatic compounds provides structural strength,
sealing of water conducting system that links roots with leaves,
and protect plants against degradation [36]. Lignin a macromole-
cule consists of alkylphenols and has a complex three-dimensional
structure. Lignin is covalently linked with xylans in the case of
hardwoods and with galactoglucomannans in softwoods [37]. The
basic chemical phenylpropane units of lignin are bonded together
through a set of linkages in such a way to form a very complex
matrix. This matrix comprises of various functional groups like
hydroxyl, methoxyl and carbonyl imparts a high polarity to the
lignin macromolecule [31,38]. The basic chemical structures of
cellulose, hemicelluloses, xylose and lignin were shown in Fig. 1.
A biosorption process performed through several modes. The
batch and continuous modes of operation are the often employed
modes in order to conduct laboratory scale biosorption processes.
In most of the industrial applications the continuous mode of
operations are employed but for the evaluation of fundamental
information’s like biosorbent efficiency, optimum experimental
conditions, biosorption rate and possibility of biosorbent regener-
ation batch experiments are deployed [26].
Adsorption isotherm models
Adsorption isotherm indicates the graphical representation of
the relationship between the amount adsorbed by a unit weight of
adsorbent and the amount of adsorbate remaining in a test
medium at a constant temperature under equilibrium condition. It
gives the information about the distribution of adsorbable solute
between the liquid and solid phases at various equilibrium
concentrations. The data under the study of adsorption isotherm
are to be specific for each system and the determination of
isotherm are to be carried out for every application [39]. The
different types of the equilibrium isotherm models (Langmuir,
Freundlich, Temkin, Dubinin–Radushkevich, Flory–Huggins, Elo-
vich, Fowler–Guggenheim, Kiselev, Hill–de Boer, Jovanovic, Halsey,
Harkin–Jura, Redlich–Peterson, Hill, Toth, Jossens, Fritz–Schlunder,
Sips, Koble–Corrigan, Khan, Radke–Prausnitz, Frumkin, Liu, We-
ber–van Vliet, Baudu) have been put together on the basis of three
fundamental approaches [38,40]. Kinetic consideration [41],
thermodynamics [42,43] and potential theory [44]. The availability
401
of the two, three, four and five parameter adsorption isotherm are
represented in Fig. 2, those isotherm models can be subjected for
the investigation of novel biosorbents for the removal of
wastewater pollutants.
Two parameter isotherms
The Langmuir Isotherm model
This model describes quantitatively about the formation of a
monolayer adsorbate on the outer surface of the adsorbent and after
that no further adsorption takes place. The Langmuir represents the
equilibrium distribution of adsorbate between the solid and liquid
phases [45]. The Langmuir adsorption isotherm the most widely
used isothermforthe biosportion of pollutantsfroma liquidsolution
based on the following hypotheses. (1) Monolayer adsorption. (2)
Adsorption takes place at specific homogeneous sites on the
adsorbent. (3) Once a pollutant occupies in a site; no further
adsorption can take place in that site. (4) Adsorption energy is
constant and does not depend on the degree of occupation of an
adsorbent’s active centres. (5) The strength of the intermolecular
attractive forces is believed to fall off rapidly with distance. (6) The
adsorbent has a finite capacity for the pollutant. (7) All sites are
identical and energetically equivalent. (8) The adsorbent is
structurally homogeneous. (9) There is no interaction between
molecules adsorbed on neighbouring sites [41]. Based upon these
assumptions, Langmuir represented the following equation:
Q 0K L Ce
qe ¼ (1)
1 þ KLCe
where Ce is the equilibrium concentration of adsorbate (mg/L), qe
denotes the adsorbate adsorbed per gram of the adsorbent at
equilibrium (mg/g), Q0 represents the monolayer coverage
capacity (mg/g) and KL is the Langmuir isotherm constant (L/mg).
The essential features of the Langmuir isotherm may be expressed
in terms of equilibrium parameter RL, a dimensionless constant,
referred to as separation factor or equilibrium parameter
[46]:
1
RL ¼ (2)
1 þ KLC0
402 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

Adsorption isotherm models

1450 parameter isotherm

Two Three parameter isotherm Four parameter isotherm Five parameter isotherm

1452
1. Redlich–Peterson 1. Weber–van Vliet 1. Fritz–Schlunder
1. Langmuir
1453 2. Hill
2. Freundlich 2. Fritz–Schlunder
3. Toth 3. Baudu
3.1454
Temkin
4. Jossens
4. Dubinin–Radushkevich
5. Fritz–Schlunder
1455
5.Flory–Huggins
6. Sips
6. Elovich
7. Koble–Corrigan
7.1456
Fowler–Guggenheim
8. Khan
8.Kiselev
1457 9. Radke–Prausnitz Explore novel biosorbents
9. Hill–de Boer
10. Frumkin
10. Jovanovic
1458
11.Liu
11. Halsey
1459
12. Harkin-Jura

Fig. 2. The significance of adsorption isotherm models in exploring novel biosorbents.

where C0 is the adsorbate initial concentration (mg/L), KL is the where

constant related to the energy of adsorption (Langmuir constant).
RL value indicates the adsorption nature of unfavourable if RL > 1, RT
B¼ bT (5)
linear if RL = 1, favourable if 0 < RL < 1 and irreversible if RL = 0.

The Freundlich isotherm model where AT is the Temkin isotherm equilibrium binding constant
The Freundlich equilibrium isotherm equation is an empirical (L/mg), bT is the Temkin isotherm constant R is the universal gas
equation used for the description of multilayer adsorption with constant (8.314 J/mol K), T is the temperature (K), B is the constant
interaction between adsorbed molecules: related to heat of sorption (J/mol) [52]. The Temkin equation better
holds for the prediction of gas phase equilibria. Nevertheless, in
1=n
qe ¼ K f Ce (3) case of liquid phase adsorption particularly of heavy metals using
biosorbent, this model fall-short in representing the equilibrium
where Kf is the Freundlich isotherm constant ðmg1—ð1=nÞ L1=n g—1Þ, n
data. In comparison with the gas phase adsorption, the liquid phase
represents the adsorption intensity, Ce indicates the equilibrium
is a more complex phenomenon since the adsorbed molecules do
concentration of adsorbate (mg/L), qe is the amount of adsorbate
not necessarily organized in a tightly packed structure with
adsorbed per gram of the adsorbent at equilibrium (mg/g).
identical orientation. The solvent molecules and micelles forma-
The model is applicable to the adsorption on heterogeneous
tion from adsorbed molecules add to the complexity of liquid
surfaces by a uniform energy distribution and reversible adsorp-
phase adsorption. Many factors such as pH, adsorbate solubility in
tion. The Freundlich equation implies that adsorption energy
the solvent, temperature and surface chemistry of the adsorbent
exponentially decreases on the finishing point of adsorptional
influence the adsorption from liquid phase. The Temkin equation is
centres of an adsorbent [47]. The Freundlich constants are
often not suitable for representation of experimental data of the
empirical constants depends on many environmental factors.
liquid phase adsorption in complex systems, since the derivation
The value of 1/n ranges between 0 and 1 indicates the degree of
for the Temkin equation are based of simple assumption and the
non-linearity between solution concentration and adsorption [48].
complex phenomenon in liquid phase adsorption are not taken
If the value of 1/n is equal to 1, the adsorption is linear [49]. Henry’s
into account [53].
isotherm or one parameter isotherm is applicable for linear
adsorption under the condition when n = 1 in Eq. (3).
The Dubinin–Radushkevich isotherm model
The Dubinin–Radushkevich isotherm can be applied for the
The Temkin isotherm model
estimation of apparent free energy and the characteristics of
Temkin equation, the early model proposed to depict adsorp-
adsorption [44,54,55]. The Dubinin–Radushkevich equation de-
tion of hydrogen on platinum electrodes within acidic solutions.
fined by the following equation [56,57]:
The derivation of the Temkin isotherm based on the assumption
that the decline of the heat of sorption as a function of temperature
qe ¼ Q m expð—K e2Þ (6)
is linear rather than logarithmic, as implied in the Freundlich
equation [50,51]. The model is given by the following equation:
where K is the Dubinin–Radushkevich isotherm constant related to
RT the adsorption energy (mol2/kJ2), Qm is the theoretical isotherm
qe ¼ lnðATCe Þ (4)
B saturation capacity (mg/g), e is the Polanyi potential, calculated
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 403

from Eq. (7): interaction among adsorbed molecules is repulsive (i.e. W is

. Σ negative), the heat of adsorption shows a decrease with loading. In
1
e ¼ RT ln 1 þ (7) the case of no interaction between adsorbed molecules (i.e. W = 0),
Ce Fowler–Guggenheim equation will reduce to the Langmuir
where R is the gas constant (8.314 J/mol K) and T is the equation.
temperature (K). The mean free energy E (kJ/mol) of sorption
can be found by using K values represented in Eq. (8). The Kiselev isotherm model
The adsorption isotherm [64] in localized monomolecular layer
1 expressed by the equation
E ¼ pffi ffiffiffiffiffi (8)
2K

The Dubinin–Radushkevich isotherm model is a tempera-

uK (13)
k1 C e ¼
K
ð1 — uK Þð1 þ knuK Þ
ture dependent, when the adsorption data at different tem-
peratures plotted as a function of logarithm of amount adsorbed where k1K is the Kiselev equilibrium constant (L/mg), and kn is the
versus the square of potential energy, all suitable data will lie constant of complex formation between adsorbed molecules.
on the same curve, referred to as the characteristic curve [58–
60]. The Hill–de Boer model
This model [65,66] describes the mobile adsorption and lateral
The Flory–Huggins isotherm model interaction among adsorbed molecules
. Σ
Flory–Huggins isotherm model [61] derives the degree of uH uH K u
K C ¼ exp — 2 H (14)
surface coverage characteristics of adsorbate onto adsorbent,
1 — uH 1 — uH
1H e
express the feasibility and spontaneous nature of an adsorption RT
process. u indicates the degree of surface coverage of adsorbent where K1H is the Hill–de Boer constant (L/mg), K2 is the energetic
surface, KFH and nFH are the Flory–Huggins equilibrium constant constant of the interaction between adsorbed molecules (J/mol).
(L/mg) and model exponent. The equilibrium constant KFH used to
A positive K2 value indicates the attraction between adsorbed
calculate the spontaneity of Gibbs free energy ( DG8). The equation species and a negative value means repulsion. The apparent
of the Flory–Huggins isotherm is as follows: affinity is increased with loading when there exist the attraction
u nFH
between adsorbed species and it is decreased with loading when
¼ KFHð1 — uÞ (9) there is repulsion among the adsorbed species. When there is no
C0
interaction between adsorbed molecules (i.e. K2 = 0), the Hill–de
The degree of surface coverage of adsorbent surface calculated Boer equation will be reduced to the Volmer equation.
using the following equation:
Ce The Jovanovic isotherm model
u ¼1— (10) An adsorption surface assumption considered in this model [67]
C0
is similar to that considered by Langmuir. It corresponds to another
approximation for monolayer localized adsorption without lateral
The Elovich isotherm model interactions. This model is similar to that of Langmuir model,
The equation defining the Elovich model based on the kinetic except that the allowance is made in the former for the surface
principle with the assumption of adsorption sites increase binding vibrations of an adsorbed species. This model shown by
exponentially with adsorption, which implies a multilayer using the following nonlinear relationship
adsorption [62]. The model is expressed by the relation:
. Σ qe ¼ qmð1 — eK jC e Þ (15)
qe q
¼ K EC eexp — e (11)
where Kj is the Jovanovic isotherm constant (L/mg), qm is the
qm qm
maximum adsorption capacity in Jovanovic model (mg/g).
where KE represents the Elovich equilibrium constant (L/mg), qm is
the Elovich maximum adsorption capacity (mg/g). The Halsey isotherm model
Adsorption isotherm equation of this model [68] given as
The Fowler–Guggenheim isotherm model follows:
For the derivation of this isotherm equation, takes in account of
. Σ
the lateral interaction of the adsorbed molecules [63]. The model ln K H — ln C e
qe ¼ exp (16)
has the following explicit form: nH
. Σ
u FG 2uFG W
K C ¼ exp (12) where KH represents the Halsey isotherm constant, nH represents
1 — uFG
FG e
RT the Halsey equation exponents.
Eq. (18) is appropriate for the multilayer adsorption and the
where KFG is the Fowler–Guggenheim equilibrium constant (L/mg),
fitting of the experimental data to this equation confirms to the
uFG is the fractional coverage, W is the interaction energy between
heteroporous nature of the adsorbent.
adsorbed molecules (kJ/mol).
Fowler–Guggenheim equation is the simplest equations with
The Harkin–Jura isotherm model
the consent to the lateral interaction. The heat of adsorption varies
The adsorption isotherm equation of this model [69] expressed
linearly with loading. If the interaction between the adsorbed
as follows:
molecules is attractive (i.e. W is positive), the heat of adsorption
will increase with loading. This is because of the increased . Σ1=2
AH
interaction between adsorbed molecules as the loading increases. qe ¼ (17)
B2 — log Ce
This means that if the measured heat of adsorption shows an
increase with respect to loading, it indicates the positive lateral where AH is the Harkins–Jura isotherm parameter, B2 is the
interaction between adsorbed molecules. Conversely, if the Harkins–Jura isotherm constant.
404 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

Three parameter isotherms The Fritz–Schlunder isotherm model

The Fritz–Schlunder [80] equation has been represented in the
The Redlich–Peterson isotherm model following form:
Redlich and Peterson included the features of both the qmFS KFSCe
q¼ (24)
e
Langmuir and Freundlich isotherms into a single equation 1 þ qm CemFS
presented as follows:
where qmFS is the Fritz–Schlunder maximum adsorption capacity
KR PCe (mg/g), KFS is the Fritz–Schlunder equilibrium constant (L/mg), and
qe ¼ g (18) mFS is the Fritz–Schlunder model exponent.
1 þ aRPCe

where KRP is the Redlich–Peterson model isotherm constant (L/g),
aRP is the Redlich–Peterson model constant (mg/L)—g; g is the
Redlich–Peterson model exponent, should be 0 < g ≤ 1. When g = 1
the Redlich–Peterson equation becomes the Langmuir equation:
KRPCe
q¼
e 1 þ aRPCe
where g = zero it becomes the Henry’s law [70].
KR PCe
qe ¼
1 þ aRP
The Hill isotherm model
Hill equation [71], from the non-ideal competitive adsorption
[72] model, and postulated to explain about the binding of
different species onto homogeneous substrates. The model
assumes that adsorption process as a cooperative phenomenon,
with the ligand binding ability at one site on the macromolecule,
may influence the different binding sites on the same macromole-
cule [73].
q C nH
qe ¼ sH e
KD þ Cne H
where qsH is the Hill isotherm maximum uptake saturation (mg/L),
KD is the Hill constant, nH is the Hill cooperativity coefficient of the
binding interaction.
The Toth isotherm model
Toth [74] modified the Langmuir equation in order to reduce
the error between experimental data and predicted values of
equilibrium adsorption data. The significance of the equation is
best suited to multilayer adsorption, which is a special type of
Langmuir isotherm and has very restrictive validity [75]. The Toth
correlation is given for the application to liquid–solid adsorption
generally presented as [76–78].
The Sips isotherm model
By identifying the problem of continuing increase in the
adsorbed amount with an increase in concentration in the
Freundlich equation, Sips [81] proposed an equation similar in
form to the Freundlich equation, but it has a finite limit when the
concentration is sufficiently high:
(19)
q K C ms
ms S e
qe ¼ ms (25)
1þK C s e
where qms is the Sips maximum adsorption capacity (mg/g), KS is
the Sips equilibrium constant ðL=mgÞms , and mS is the Sips model
(20)
exponent, limited from 0 to 1. At the low adsorbate concentrations
the Sips isotherm model effectively reduces to the Freundlich
isotherm and thus does not obey Henry’s law. And at high
adsorbate concentrations, this model predicts a monolayer
sorption capacity characteristic of the Langmuir isotherm [22].
The Koble–Corrigan isotherm model
Koble–Corrigan model [82] is the three-parameter empirical
model based on the combination of both the Langmuir and
Freundlich isotherm equations representing in one non-linear
equation of the equilibrium adsorption data. The model is
commonly expressed by Eq. (26):
(21)
aCen
qe ¼ (26)
1 þ bCen
where a (Lnmg1—n/g), b (L/mg)n and n are the Koble–Corrigan
parameters.
This model is generally applied for heterogeneous sorbent
surface [83].
The Khan isotherm model
This model [84] suggests a generalized isotherm for the bi-solute
adsorption from dilute aqueous solution. The correlation repre-
sented in Eq. (27) has a unique characteristic by covering both
extremes of the Langmuir and Freundlich isotherm. The generalized
equation for pure component adsorption isotherms as follows:

KT Ce q sb K C e
qe ¼ (27)
q e¼ (22) ð1 þ b KC eÞnK
TT 1=TT
½AT þ C e ]
where bK is the Khan isotherm model constant, qs is the theoretical
where KT is the Toth equilibrium constant, and TT is the Toth model isotherm saturation capacity (mg/g), nK is the Khan model exponent.
exponent. When nK is equal to unity, Eq. (27) reduces to the Langmuir
isotherm. This equation at large value of Ce reduces to the
The Jossens isotherm model Freundlich isotherm.
This model is based on a distribution of the energy of
interactions adsorbate–adsorbent on adsorption sites [79]. The The Radke–Prausnitz isotherm model
model assumes that the activated carbon surface is heterogeneous, The three isotherms [85] of this model can be represented as
with respect to the interactions which it engages with the qm KRPICe
adsorbate: qe ¼ RPI
m (28)
ð1 þ KRPICeÞ RPI
q qm KRPIICe
¼ e expðFq pÞ (23)
Ce H e qe ¼ RPII
m (29)
1 þ KRPIICe RPII
where H, F and p represent the parameters of the Jossens equation. m
qmRPIII KRPIIICe RPIII
H and F depend only on temperature. Eq. (23) can be reduced to qe ¼ m (30)
Henry’s law at low capacities. 1 þ KRPIICe RPIII—1
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 405

where qmRPI, qmRPII and qmRPIII are the Radke–Prausnitz maximum Graphical study of ln KL = f(ln Ce) and ln Q0 = f(ln Ce) gives access to
adsorption capacities (mg/g), KRPI, KRPII and KRPIII are the Radke– b0, qm0, x, and y.
Prausnitz equilibrium constants, and mRPI, mRPII and mRPIII are the This model gives the transformed the Langmuir equation as
Radke–Prausnitz models exponents. expressed in Eq. (38)
ð1þxþyÞ
The Frumkin isotherm model qm0 b0 C e with ð1 þ x þ yÞ and ð1 þ xÞ < 1 (38)
qe¼
This is the three-parameter isotherm model [86,87] depicted in 1 þ b0 C eð1þxÞ
Eq. (31)
qm0 is the Baudu maximum adsorption capacity (mg/g), b0 is the
. Σ — fu
KFFCe u exp¼ (31) equilibrium constant, and x and y are the Baudu parameters.
1—u For lower surface coverage, Eq. (38) reduces to the Freundlich
equation, i.e.
where f is the interaction coefficient of the Frumkin equation, KFF
ð1þxþyÞ
indicates the equilibrium constant of Frumkin equation. qm0 b0 C e
qe ¼ (39)
1 þ b0
The Liu isotherm model [87]

Five parameter isotherms

nL
Qe ¼ Q max · K gC e (32)
1 þ KgCe nL The Fritz–Schlunder isotherm model
This model represents a broad field of equilibrium data through
where Qe is the adsorption capacity (mg/g), Qmax is the maximum the five-parameter empirical expression [80].
adsorption capacity of the adsorbent (mg/g), Kg is the Liu
q K1Cm1
equilibrium constant (L/mg), Ce is the adsorbate concentration q e 1¼þmKFS5 e with m and m ≤ 1 (40)
at the equilibrium (mg/L), n is the dimensionless exponent of the Cm2 1 2
L 2e
Liu equation.
where qmFS5 is the Fritz–Schlunder maximum adsorption capacity
(mg/g) and K1, K2, m1, and m2 are the Fritz–Schlunder parameters.
Four parameter isotherms
BET isotherm
The Weber–van Vliet isotherm model
Weber and van Vliet [88] proposed an empirical relation with
Brunauer et al. [90] developed an equation for the multilayer
four parameters isotherm models in order to describe the
adsorption and the expression has been represented as follows:
equilibrium data
qsCBET C e (41)
ð P3 þP Þ q¼
e
e s e BET e s
P2 q e
Ce ¼ P1q 4
(33) ðC — C Þ½1 þ ðC — 1ÞðC =C Þ]
where P1, P2, P3 and P4 are the isotherm parameters of Weber–van In which CBET, BET adsorption isotherm relating to the energy of
Vliet equation. surface interaction (L/mg), Cs, adsorbate monolayer saturation
concentration (mg/L)
The Fritz–Schlunder isotherm model
Four-parameter equation of another form of Langmuir– Adsorption isotherm models in the assessment of biosorbents
Freundlich type developed empirically by Fritz and Schlunder for different pollutants
[80]. The equation of this model expressed as follows:
ACa A functional expression for quantity of adsorption with
q¼ e
with a and b ≤ 1 (34) concentration of solute at a constant temperature. Adsorption
1 þ BCeb
e
properties and equilibrium data are commonly known as
where A and B are the Fritz–Schlunder parameters, and a and b are adsorption isotherms. The adsorption isotherms show the
the Fritz–Schlunder equation exponents. pollutants interaction with adsorbent materials and are thus
At high liquid-phase concentrations of the adsorbate, Eq. (34) critical in optimizing for the use of biosorbents [91,92]. In order to
reduces to the Freundlich equation as shown in Eq. (35) optimize the design of an adsorption system to remove pollutant
from wastewater, it is important to establish the most appropriate
A
q e¼ e Ca—b (35) correlation for the equilibrium curve. An accurate mathematical
B description of equilibrium adsorption capacity is indispensable for
where A/B and (a — b) present the parameters Kf and 1/n of the reliable prediction of adsorption parameters and quantitative
Freundlich model. comparison of adsorption behaviour for different adsorbent
For a = b = 1, Eq. (34) reduces to the Langmuir equation, with systems [22,49,92].
KL = B is the Langmuir adsorption constant (L/mg) related to the
energy of adsorption and A = KLQ0. Adsorption isotherm model significance in the biosorbent evaluation
for metal removal
The Baudu isotherm model
The calculation of the Langmuir coefficients, KL and Q0, carried out Special concern over the heavy metal remediation is due to the
through the measurement of tangents at the different equilibrium recalcitrant and persistency nature of heavy metals in the
concentrations. Shows that they are not constants in a broad environment. The distributions of cellulosic agricultural waste
concentration range [89]. Their variations written as follows: materials act as the copious source for significant metal biosorp-
tion. The agricultural waste biomass consists of functional groups
KL ¼ b0Cxe (36) like phenolic, amido, amino, acetamido, alcoholic, carbonyl,
sulphydryl groups, etc. have affinity towards heavy metal ions
Q 0 ¼ qm0Cey (37) in order to form metal complexes or chelates [93]. The design and
406 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414
analysis of biosorption process entails relevant biosorption
equilibrium. At the equilibrium condition, a certain relationship
exists between adsorbate and adsorbent. Their equilibrium
concentrations are a function of temperature. Initially several
adsorption isotherm models used for gas phase adsorption and
then those isotherm models were readily adopted to show
relationship adsorption equilibrium in heavy metals biosorption
[94]. Biosorption has mainly been considered for heavy metal
removal in order to detoxify metal-bearing effluents. The process
features a high heavy metal selectivity and cost-effectiveness for
low metal concentrations as compared with ion exchange resins.
There is also no hazardous sludge by-product generation in both
processes and biosorbents can also be easily regenerated for
multiple reuses [95].
Pinhao (Araucaria angustifolia) waste and pinhao loaded with
Congo red were investigated for the Cu(II) removal from aqueous
solutions. After optimizing the batch adsorption system through
statistical design of experiments, the adsorption equilibrium
data fitted to the Langmuir and Freundlich models. The
maximum adsorption capacity of pinhao waste and pinhao
loaded with Congo red for Cu(II) removal was found as 32.2 mg/g
and 68.6 mg/g respectively [96]. The evaluation of the feasibility
of sugarcane bagasse carried out for the adsorption of nickel from
aqueous solution. The biosorption data were fitted to Langmuir,
Freundlich and Sips isotherm models. The Langmuir model
shows better representation of data, with determination coeffi-
cient greater than 0.99 [97]. The sugar cane bagasse subjected as
a selective solid phase extractor for Fe(III). Batch experiments
were carried out at the pH range 1.0–4.0, initial concentration of
metal ion (10–100 mmol), weight of biosorbent (25, 50, 75, 100,
125 and 150 mg) and shaking time (10, 30, 45, 60, 90, 120 and
150 min). The equilibrium data better fits with Langmuir model
in comparison with the Freundlich model [98]. The yellow
passion fruit shell (Passiflora edulis Sims. f. flavicarpa Degener)
was reported as an biosorbent for the removal Cr(III) and Pb(II)
from aqueous solutions in batch studies. The effects of contact
time and pH were considered in the biosorption study. The
biosorption kinetics followed the pseudo second order. The
maximum removal capacity of yellow passion fruit shell were
85.1 and 151.6 mg/g for Cr(III) and Pb(II) respectively. The
Langmuir isotherm model suitably fitted for both the metallic
ions [99].
The capacity of Polyaniline coated on saw dust as synthetic
adsorbent investigated for the removal of Cd(II) ions from aqueous
solutions by means of batch operation. The optimum pH for
adsorption of Cd(II) found to be 6. Adsorption was rapid and
occurred within 20 min for a cadmium concentration range of 10–
40 mg/L. The equilibrium adsorption data for Cd(II) were better
fitted to the Freundlich isotherm model in comparison with the
Langmuir adsorption isotherm model [100]. Rubber wood (Hevea
brasiliensis) saw dust modified by the chemical treatment of
phosphoric acid and sodium hydroxide with different impregna-
tion ratios in order to improve adsorption capacity for the removal
of copper. The effects of variables like solution pH, temperature,
adsorbent dose, initial copper concentration, on the removal of
copper ions have been studied. Adsorption equilibrium data were
fitted to the adsorption isotherm models like Langmuir, Freundlich
Dubinin–Radushkevich and Temkin. The equilibrium data were
best represented by the Langmuir and Freundlich isotherms [101].
Grafted copolymerization-modified orange peel used for the
biosorption of Pb2+, Cd2+ and Ni2+ ions from aqueous solution.
Langmuir and Freundlich isotherm models were applied to
describe the biosorption. Langmuir model fits the equilibrium
data better than the Freundlich isotherm. The maximum adsorp-
tion capacities found through the Langmuir equation, for Pb2+, Cd2+
and Ni2+ ions were 476.1, 293.3 and 162.6 mg/g respectively. In
comparison with the unmodified orange peel, the biosorption
capacity increased for modified biomass by 4.2-, 4.6- and 16.5-fold
for Pb2+, Cd2+ and Ni2+, respectively [102]. Pecan nutshell (Carya
illinoensis) used for the removal of Cu(II), Mn(II) and Pb(II) from
aqueous solutions. The effects such as, pH, biosorbent dosage was
considered in the study. Fractionary order kinetic model was
observed as the best fitted kinetic model. The equilibrium data
were fitted to Langmuir, Freundlich, Redlich–Peterson and Sips
isotherm models. Sips isotherm model best fitted the equilibrium
data. The maximum biosorption capacities of pecan nutshell were
found as 85.9, 98.0 and 195.9 mg/g for Cu(II), Mn(II) and Pb(II)
respectively [103].
Chemically modified orange peel subjected for the adsorption
of environmentally problematic metal ions namely Cd2+, Cu2+ and
Pb2+ from aqueous solutions. And the comparison made with the
original orange peel. The metals uptake by chemically modified
orange peel shows rapid and the equilibrium time attained within
30 min at constant temperature and pH. The mechanism of metal
adsorption by chemically modified orange peel gave good fits for
Freundlich and Langmuir models in comparison to the Dubinin–
Radushkevich isotherm model. The modified biosorption data
perfectly fits the Langmuir and Freundlich adsorption isotherms
models with determination coefficient > 0.95 for all the metal ions
Cd2+, Cu2+ and Pb2+ [104]. A lignocellulosic material extracted from
rice husk (Oryza sativa) modified by iron coating through
hydrolization of ferric nitrate while adding an alkaline solution
drop wise into the batch type reactor. The parameters studied
includes pH, As(V) concentrations, contact times, ionic strength
and adsorbent amounts. Maximum percentage removal of As(V)
ions 94% occurs at pH 4.0. The Langmuir model fitted the
equilibrium data better than Freundlich model and confirms the
surface homogeneity of adsorbent [105]. The adsorption of Cu(II)
by carbons prepared from rice husk through pyrolysis and steam
activation were investigated. The Cu(II) adsorption on the rice husk
carried out with an optimum pH value of 5.0 and an equilibrium
time of 24 h. The Langmuir isotherm model fits better the
experimental data in comparison with the Freundlich isotherm,
Dubinin–Radushkevitch isotherm. The values of E obtained in D–R
model found to be greater than 14 kJ/mol, indicating the
adsorption process as chemical ion-exchange process [106]. The
magnitude of E between 8 and 16 kJ/mol corresponds to a chemical
ion-exchange process while the value of E < 8 kJ/mol represents as
physical nature process [107]. Coir pith chemically modified by
grafting with acrylic acid for the removal of Cr(VI). The maximum
Cr(VI) removal (99.99 T 0.07%) attained under the following
conditions: 1.3% (w/v) dosage of acrylic acid-grafted coir pith, pH
of 2, contact time of 22 h, temperature of 30 8C, particle size of
<150 mm and an initial Cr(VI) of 1171 mg/l. The adsorption isotherm
of 2 M acrylic acid-grafted coir pith shows a good fit with the
Langmuir isotherm in comparison with the Freundlich isotherm
[108].
The garden grass was subjected for the biosorption of copper(II)
from water. Copper adsorption depends on important parameters
like the pH, initial copper concentrations, contact time, adsorbent
doses, temperature and particle sizes. The equilibrium data were
well fitted by the Langmuir, Sips and Redlich–Peterson isotherm
models. The maximum biosorption of 58.34 mg/g was obtained for
1 g dose [109]. Rice husk evaluated was evaluated for the
biosorption of U(VI). Biosorbent used in the form of native, SDS-
treated and immobilized. The adsorption study parameters
investigated were pH, biosorbent dosage, contact time, initial
U(VI) concentration and temperature. Maximum biosorption
capacity for native (29.56 mg/g) and immobilized biomass
(17.59 mg/g) followed with SDS-treated biomass showed maxi-
mum removal of 28.08 mg/g. The Langmuir sorption isotherm
model best fitted best with the U(IV) biosorption equilibrium data
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 407

Table 1
Applicable isotherm models in the metal biosorption.

Biosorbent Metal ion Equilibrium model Reference

Coconut copra meal Cd(II) Freundlich [112]

Carpinus betulus tree leaves Cd(II) Sips [113]
Chestnut shell Cd(II), Cu(II) Sips [114]
Pb(II), Zn(II)
Wheat bran Cu(II) Langmuir [115]
Coffee wastes Cr(VI) Sips [116]
Golden Shower Leaves Ni(II) Freundlich [117]
Grapefruits peels Cd(II) Freundlich [118]
Litter of poplar forests Cu(II) Freundlich [119]
Wheat shell Cu(II) Freundlich [120]
Rice shell Cu(II) Freundlich [120]
Maize husk Pb(II), Zn(II) Freundlich [121]
Cedar sawdust Cu(II) Freundlich [122]
Coir pith Cr(VI) Freundlich [123]
Almond shell Cu(II) Sips [124]
Sugar beet pulp Pb(II), Cd(II) Freundlich [125]
Mango peel waste Cd(II) Langmuir [126]
Peanut hull Cu(II), Pb(II) Langmuir [126]
Pomelo peel Cd(II) Langmuir [127]
Orange peel Cu(II) Langmuir [128]
Tamarind fruit shell U(VI) Sips [129]
Coconut shell, Neem leaves, hyacinth roots, Cu(II) Freundlich and Halsey [130]
rice straw, rice bran, rice husk
Modified Rice Husk Zn(II) Langmuir [131]
Palm oil fruit shells Cu(II) Sips, Redlich–Peterson, Toth, [132]
Radke–Prausnitz, Hill
Ficus carica Cr(VI) Langmuir [133]
Opuntia ficus indica Cd(II),Pb(II) Langmuir [134]
Bamboo leaf powder Hg(II) Freundlich and Temkin [135]

[110]. The single and binary biosorption of copper and lead ions
from aqueous solution carried out using rice straw. The modified
extended-Langmuir model with incorporation of solute’s selectiv-
ity factor gave good correlation results against binary adsorption
data [111]. The biosorbents and the best fitted adsorption isotherm
model are shown in Table 1.
Adsorption isotherm model significance in the biosorbent evaluation
for dye removal
Dye decolourization now becomes the foremost difficulty for the
treatment plants of various industries like textiles, rubber, paper,
plastics, leather, cosmetic, food, etc. yearly 10–15% of the synthetic
textile dyes used is lost to waste streams and of about 20% of these
losses enter the environment through effluent generated the
treatment plant [136]. The effluent generated is the most important
threatening factor to the environment because it affects the biotic
and the abiotic systems [137]. Biosorption represents a powerful
technique for the dye removal. Biosorption process involves solid
living or non-living biosorbent attracts a component to its surface
from the aqueous solution and form an attachment through a
physical or chemical bond, thereby removing the component from
the liquid phase [138,139]. Agricultural byproducts hold significant
potential for the removal of the toxic dye substances from the
effluent discharging into the water bodies [140].
Rhodamine 6G removal from aqueous solutions carried out by
almond shell (Prunus dulcis) in a batch technique. The investigation
carried out with the consideration of parameters like pH, contact
time, Rhodamine 6G concentration, almond shell concentration,
temperature etc. The biosorption pattern of Rhodamine 6G onto
almond shell well fits with both the Langmuir and Freundlich
isotherm models. Through the Langmuir model equations biosorp-
tion capacity of almond shell found to be as 32.6 mg/g [141]. The
adsorption of Acid Black 26, Acid Green 25 and Acid Blue 7
investigated on Pine Cone. Equilibrium isotherms were analyzed
using Langmuir, Freundlich and Tempkin adsorption models. The
isotherm data of Acid Black 26 and Acid Green 25 follows the
Langmuir isotherm and isotherm data of Acid Blue 7 follows
Freundlich isotherm models [142]. The potential of lotus leaf for
the removal of methylene blue from aqueous solution was
investigated. The experiments performed under various conditions
like solution pH, salt ionic strength, temperature, contact time,
adsorbent dose and initial methylene blue concentration. In order
to describe the adsorption behaviour, isotherm models like the
Langmuir, Freundlich and Koble–Corrigan were employed. In
comparison, the equilibrium data were perfectly represented by
Koble–Corrigan isotherm [143]. The study carried out by using
palm kernel fibre for the removal of methylene blue and crystal
violet from aqueous solutions. Adsorption studies parameters
includes the different initial dye concentrations (20, 40, 80 and
160 mg/L), contact time, pH (1.0–11.0) and sorbent doses (0.4, 2.0,
4.0 and 8.0 g/L). Adsorption data were modelled using Langmuir,
Freundlich and Temkin adsorption isotherms. Equilibrium data of
the biosorption process fitted very well to the Freundlich model
(determination coefficient = 0.997 and 0.991 for methylene blue
and crystal violet, respectively) [144]. Activated and non-activated
carbonaceous materials of Brazilian pine-fruit-shell (A. angustifo-
lia) were tested for the removal of Procion Red MX 3B dye from
aqueous solutions. Procion Red MX 3B dye uptake was higher at
the pH range of 2–3 for non-activated carbonaceous adsorbent and
2–7 for activated carbonaceous adsorbent. For the adsorption
equilibrium data, the Ferror values of the Sips isotherm model were
at least 4.0 lower than the values of Langmuir, Freundlich and
Redlich–Peterson isotherm models [145]. The activated carbon
from bamboo culms wastes were employed for the removal of
Disperse Red 167. The adsorption isotherm data were fitted to nine
non-linear adsorption isotherm models. The Akaike Information
Criterion analysis was confirmed as the best statistical tool for
analyzing the data obtained. Temkin isotherm equation best
described the adsorption isotherm data [146]. The Brazilian pine
fruit shell (A. angustifolia) was tested as biosorbent for the removal
of non-hydrolyzed reactive red 194 and hydrolyzed reactive red
194 dyes from aqueous solutions. Chemical treatments of Brazilian
pine fruit shell, with chromium, with acid and with acid followed
408 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414
by chromium were carried out in the study. The adsorption data
were fitted to Langmuir, Freundlich, Sips and Redlich–Peterson
isotherm models. For non-hydrolyzed reactive red 194 reactive dye
the equilibrium data were best fitted to the Sips isotherm using
raw and acid treated biosorbent and Redlich–Peterson isotherm
using chromium treated pine fruit shell and acid followed by
chromium treated biosorbents. In the case of hydrolyzed reactive
red 194 reactive dye, the equilibrium data were best fitted to the
Sips isotherm using raw, acid treated biosorbent and acid followed
by chromium treated biosorbents and the Redlich–Peterson
isotherm model for chromium treated biosorbents [147]. Brazilian
pine fruit shells (A. angustifolia) in raw form and as activated
carbon were used for the biosorption of remazol black B from
aqueous effluents. The fractionary-order kinetic model best fitted
the experimental data. Adsorption data of both forms of the
biosorbent better fitted the Sips isotherm equation [148].
The adsorption of crystal violet dye by grapefruit peel subjected
as the potential adsorbent in the remediation of dye contaminated
wastewaters. The equilibrium process is well described by the
Langmuir isotherm model than the Freundlich isotherm model.
The maximum adsorption capacity found as 254.16 mg/g [149].
The study carried out on the adsorption of Crystal Violet and
Rhodamine B by Acacia nilotica leaves. The effect of solution pH,
agitation time and initial dye concentration was evaluated. The
applicability of Langmuir, Freundlich, Dubinin–Radushkevich, and
Temkin equations was examined. The Langmuir isotherm shows
the best fit with the experimental data and the maximum
monolayer capacity found as 33 mg/g for Crystal Violet and
37 mg/g for Rhodamine B respectively [150]. Pine cone studied for
its potential application as an adsorbent in raw form and
hydrochloric acid modified form to remove anionic dye Congo
red from aqueous solution. The Congo red adsorption of both form
of the biosobent increased with initial dye concentration,
temperature, contact time, but decreased with increase of solution
pH and amount of adsorbent of the system. Equilibrium data were
best represented by Freundlich isotherm model among Langmuir
and Freundlich adsorption isotherm models. Freundlich constant
‘n’ indicates favourable adsorption [151]. The potential of garlic
peel evaluated in a batch process for the remove methylene blue
from aqueous solution. Experiments were carried out in account of
the parameters like contact time, initial concentration (25–
200 mg/L), pH (4–12) and temperature (303, 313 and 323 K).
Adsorption isotherms assessed through Langmuir, Freundlich, and
Temkin isotherms. The data fits well with the Freundlich isotherm.
The maximum monolayer adsorption capacities found to be 82.64,
123.45, and 142.86 mg/g at 303, 313, and 323 K, respectively [152].
A chemically modified adsorbent prepared from kenaf fibre char
by HCl treatment, which increased the BET surface area in turn
increased the Methylene blue adsorption. The highest percentage
removal of Methylene blue dye found to be 95 wt% at a
concentration of 50 mg/L. The equilibrium data analyzed using
the Langmuir, Freundlich and Temkin isotherm models and best
represented by the Langmuir isotherm model [153]. Olive pomace
evaluated for the removal of reactive textile dye, RR198. The
highest dye biosorption capacity occurs at pH 2 and the
equilibrium time was 40 min with a biosorbent concentration of
3.0 g/L. The equilibrium data were analyzed by Langmuir,
Freundlich and Dubinin–Radushkevich isotherm models and the
isotherm studies indicate that the data fits better with the
Langmuir isotherm model [154]. Bagasse pith modified through
chemical activating agent H 3PO4 or KOH followed by carbonization
at 500 8C for the removal of Rhodamine-B. The adsorption ability of
Bagasse pith activated by H 3PO4 is higher than that of the Bagasse
pith activated by KOH by approximately 10 folds (198.6 and
21.5 mg/g, respectively). The adsorption was analyzed by using
isotherm models of Langmuir, Freundlich, Temkin, Harkins–Jura,
and Halsey isotherm equations respectively. The highest values of
determination coefficient (0.997) were obtained with Langmuir
isotherm model [155].
Meranti (Philippine mahogany) sawdust showed strong scav-
enging behaviour towards methylene blue through adsorption
from aqueous solution. To analyze the equilibrium data, the
isotherm models like Langmuir, Freundlich and Temkin isotherms
were used at different temperatures. The experimental data fits
well with the Langmuir adsorption isotherm, representing the
mono layer adsorption of the dye. The monolayer sorption capacity
of meranti sawdust for methylene blue found to be 120.48, 117.64,
149.25 and 158.73 mg/g at 30, 40, 50 and 60 8C respectively [156].
The study examine the potential use of activated carbon prepared
from the epicarp of Ricinus communis for the removal of malachite
green dye from simulated wastewater. As the amount of the
adsorbent increased, the percentage of dye removal increased
consequently. Dye adsorption occurs at the optimum pH of 7.0. The
experimental data were analyzed by using isotherm models of
Langmuir, Freundlich, Tempkin and Dubinin–Radushkevich iso-
therm models. Adsorption behaviour is well described by a
monolayer Langmuir-type isotherm. The maximum removal of MG
was obtained at pH 7 as 99.04% for adsorbent dose of 1 g 50 m/L
and 25 mg/L initial dye concentration at room temperature [157].
The wheat straw has been modified by etherification to prepare a
kind of quaternary ammonium straw adsorbents. The adsorption
behaviours of the modified straw for methyl orange and acid green
25 were studied in both batch and column systems. The maximal
methyl orange and acid green 25 uptakes were more than 300 and
950 mg/g. The Mechanism studies using equilibrium data through
Langmuir model, Freundlich model, Sips model, Dubinin–Radush-
kevich model indicates that the adsorption process as monolayer
chemical adsorption, therefore well described by the Langmuir
isotherm model [158]. Single-dye equilibrium data fitted well with
the Langmuir–Freundlich model and the maximum biosorption
capacities were 0.68 mmol/g for methylene blue and 0.50 mmol/g
for rhodamine B. Competitive dynamic biosorption demonstrated
the preference of the modified cone chips for biosorbing methylene
blue [159]. Table 2 shows the valid adsorption isotherm model for
the biosorbents in dye sequestration.
Adsorption isotherm model significance in the biosorbent evaluation
for phenolic removal
Phenol is the major organic water pollutants since of its toxicity
effects even at low concentrations. The presence of phenol in
natural waters forms substituted compounds during disinfection
and oxidation processes [188]. The thousands of known phenolic
compounds distributed in a high molecular diversity and are
categorized on the basis of carbon atoms and structure [189–191].
Even at low concentrations of phenol, act as an impediment to the
use or reuse of water. A phenol gives an unpleasant taste, odour to
drinking water and exerts negative effects on different biological
processes. Most of the phenolic compounds are suspected to the
causative agents for human carcinogens [192]. The all-pervading
nature of phenols, their toxicity effects even in trace level and the
stricter environmental regulations compulsorily made in develop-
ing processes for the phenols removal from wastewaters [193].
Phenolic removal through adsorption is regarded as a good option
since it offers several advantages like (a) non-selectivity in
micropollutants removal at low concentration, (b) efficiency in
the operational time, (c) convenient handling, (d) economical,
availability and reusability, (e) no Sludge formation and (f) being
eco-friendly [194,195].
Carrot dross was subjected to activated carbon preparation,
magnetized and used for the p-nitrophenol removal from aqueous
solution. Batch sorption studies carried out at different pH values,
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 409

Table 2
Applicable isotherm models in the dye biosorption.

Biosorbent Dye Equilibrium model Reference

Rice husk Indigo carmine Freundlich, Redlich-Peterson [160]

Rice husk a-Picoline Radke–Prausnitz [161]
Wheat straw Methylene blue Langmuir [162]
Yellow passion fruit Methylene blue Sips [163]
Barley straw Acid blue 40 Langmuir [164]
Pine fruit shell Methylene blue Sips [165]
Cupuassu shell Reactive Red 194, Direct Blue 53 Sips [166]
Wood shaving Egacid orange Langmuir–Freundlich [167]
Canola stalks Acid Orange 7, Remazol Black 5 Langmuir [168]
Jujuba seeds Congo red Langmuir [169]
Coir pith Acid Yellow 99 Langmuir–Freundlich [170]
Olive-waste cakes Lanaset Grey G Langmuir [171]
Sesame hull Methylene blue Langmuir [172]
Pyracantha coccinea berries Methylene blue Langmuir [173]
Olive-waste cakes BlackDycem TTO Langmuir [174]
Swede rape straw Methylene blue Langmuir [175]
Jatropha curcas pods Remazol Brilliant Blue R Langmuir [6]
Cypress cone chips Methylene blue, Rhodamine B Langmuir–Freundlich [159]
Aminoethanethiol modified cellulose Reactive red dye RB Langmuir [176]
Wheat straw Methylene blue Langmuir [177]
Sugarcane bagasse Brilliant Red 2BE Sips [178]
Jatropha curcas shell Reactive Red 120 Liu [179]
Oil palm empty fruit bunch Phenol red Freundlich [180]
Oil palm empty fruit bunch Methylene blue Langmuir [180]
Pine cone Acid Red 114, Acid Yellow 117 Temkin [181]
Pine cone Acid Black 80, Acid Black 1, Acid Blue 113 Langmuir [181]
Pinefruit shell Reactive orange 16 Sips [182]
Pine cone Methyl orange Jovanovic [183]
Cashew nut shell Congo red Redlich–Peterson, Toth Koble–Corrigan model, Sips [184]
Mangifera indica seeds Victazol Orange 3R Liu [185]
Mustard husk Alizarin Red S Freundlich [186]
Cocoa pod husk Methylene blue Freundlich [187]

solid/liquid ratios, contact times and pollutant initial concentra-
tions in the presence and absence of ultrasonic irradiation. The
magnetic activated carbons of carrot dross in the ultrasound
presence fit well the Freundlich isotherm. But in contrast, activated
carbon in the presence of ultrasonic irradiation fit well with the
Langmuir model [196]. The adsorption potential of thermally
activated carbon from maize cob used for the removal of 2,4-
dichlorophenol from aqueous solutions. Study carried out to
analyze the effects of contact time, 2,4-dichlorophenol initial
concentration, pH and temperature. Langmuir isotherm fitted well
with experimental data. The adsorption capacity of maize cob
carbon found as 17.94 mg/g for the particle size of 250–500 mm
[197]. The adsorption of five phenolic compounds like phenol, 2-
chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-tri-
chlorophenol onto granular activated carbon were subjected under
study through the adsorption equilibrium isotherm. For determin-
ing the best fit isotherm, the equilibrium data analyzed through
thirteen adsorption isotherm models. The experimental data fits
the adsorption isotherm models in the order of Baudu > Langmuir–
Freundlich > Sips > Fritz–Schlunder > Toth > Fritz–Schlunder >
Redlich–Peterson [198]. The adsorption tests carried out for the
adsorption of five phenolic compounds like phenol, 2-chlorophe-
nol, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophe-
nol on granular activated carbon using the seven adsorption
equilibrium isotherm models (Langmuir, Freundlich, Elovich,
Temkin, Fowler–Guggenheim, Kiselev, and Hill–de Boer). Experi-
mental data obtained reveals that the adsorption isotherm models
fits the data in the order of Fowler–Guggenheim > Hill–de Boer >
Temkin > Freundlich > Kiselev > Langmuir isotherms [199].
The potential of Dalbergia sissoo sawdust charred at 673 K
evaluated for the removal of phenol from aqueous solution. The
experimental data for removal from single-contaminant water fits
well on the Langmuir adsorption model, showing maximum phenol
uptake capacity of 344.83 mg phenol/g sawdust at 45 8C [200]. The
co-adsorption of phenol and cyanide from binary solution carried
out on granular activated carbon. The effect of parameters like pH,
temperature, adsorbent dose and contact time were evaluated.
Phenol removal takes place at an optimum pH 8, temperature 30 8C
and adsorbent dose of 30 g/L, 79.9% of 200 mg/L phenol. Four
multicomponent isotherms were applied to the experimental data
conducted at an initial concentration range of 100–1000 mg/L.
Single component isotherms viz. Langmuir and Freundlich were
applied to determine the multicomponent isotherm parameters. It
was found that phenol adsorption followed extended Langmuir
isotherm while cyanide adsorption followed extended Freundlich
isotherm in multicomponent system. The monolayer adsorption
capacity of GAC was found to be 269.7 and 1.95 mg/g for phenol and
cyanide, respectively as calculated by extended Langmuir isotherm
[201]. Isotherms for adsorption of 2,4-dinitrophenol from water and
basal salt medium onto date seeds and activated carbon were
determined. The experimental data fits the Freundlich isotherm.
0.5 g of date seeds, with a 125 mL salt medium, act the suitable
adsorbent for the removal of 2,4-dinitrophenol [202]. Table 3 shows
the best fitted adsorption isotherm model for the phenolic removal
using biosorbents.
Adsorption isotherm model significance in the biosorbent evaluation
for anions removal
Inorganic anions are the main category of aquatic pollutants
found in above the normal concentrations in the drinking water
sources. The pollutants removal from drinking water supplies is a
rising issue [216,217]. Increased nitrate concentrations in water
causes severe health hazard due to reduction of nitrate to nitrite in
the gastrointestinal human tract. Nitrite causes methemoglobine-
mia. Nitrate and nitrite have the potential to form carcinogenic N-
nitroso compounds. At high concentrations of Sulfate causes
catharsis, dehydration and gastrointestinal irritation [218].
Excess fluoride intake causes various diseases such as
osteoporosis, cancer, infertility, brain damage, arthritis, brittle
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 411

Table 3
Applicable isotherm models in the phenol biosorption.

Biosorbent Phenolic pollutants Equilibrium model Reference

Mansonia sawdust 4-Nitrophenol Langmuir [203]

Rice husk p-Chlorophenol, p-Nitrophenol Redlich–Peterson [204]
Coconut husk 2,4,6-Trichlorophenol Langmuir [205]
Coconut shell Phenol Freundlich [206]
Banana peel Phenolic compounds Freundlich, Langmuir [207]
Palm seed coat o-Cresol Freundlich [208]
Palm pith 2,4-Dichlorophenol Tempkin [209]
Coconut shell Parachlorophenol, 2,4,6-trichlorophenol Freundlich [210]
Avocado kernel seeds Phenol Langmuir [211]
Olive pomace Phenols Freundlich, Langmuir [212]
Almond shell residues Pentachlorophenol Freundlich [213]
Coconut shell a-Picoline, b-picoline, and g-picoline Langmuir [214]
Coir pith 2-chlorophenol Freundlich [215]

Table 4
Applicable isotherm models in the anion biosorption.

Biosorbent Anions Equilibrium model Reference

Orange waste Phosphorus Langmuir [222]

Sugarcane bagasse Nitrate Langmuir [223]
Rice hull Nitrate Langmuir [223]
Coir pith Sulfate Langmuir, Freundlich [224]
Coir pith Thiocyanate Langmuir, Freundlich and Dubinin–Radushkevich [225]
Wheat straw Nitrate Freundlich [226]
Mustard straw Nitrate Langmuir [227]
Beet residue Nitrate Langmuir [228]
Orange juice residue Fluoride Langmuir [229]
Coconut shell fibres Nitrate, sulfate and phosphate Langmuir, Sips, and Redlich–Peterson [230]

bones, Alzheimer syndrome and thyroid disorder [219,220]. Sum of squares of the error
Phosphate direct discharge into surface waters perturbs the
aquatic organisms and affects water quality by depletion of the X
p ðqe calc — qe meas Þ2 (44)
dissolved oxygen level. Depletion of the oxygen level leads to
; ; i
eutrophication in the confined water bodies [220]. Vanadium holds i¼1
harmful effects on the circulatory system and disturbs the plants
This is the most widely used common error function but the
metabolism leads to chlorosis and limited growth [221]. Table 4
major drawback is that the isotherm parameters derived using this
illustrates the suitable adsorption isotherm model for the anions
error function will provide a better fit as the magnitude of the
removal using biosorbents.
errors and therefore the sum of squares of the error increases –
biasing the fit towards data obtained at the at higher end of the
The selection of isotherm model for the adsorption studies
liquid-phase concentration ranges [235].
[231]

Determination coefficient
The Akaike information criterion is used for the selection of
The determination coefficient (R2) is calculated using the
appropriate model under the situation of when data fitted by more
following equation [179,236]:
than one model [232,233]. The general representation of the !
Pn P
Akaike information criterion is represented as follows: ðq — q̄i exp Þ2 — n ðqi exp — qi model Þ2
2 i i exp
; ; i ; ;
R ¼ Pn (45)
AIC ¼ 2k — 2 lnðLÞ (42) ðqi exp
;
— q̄i exp
;
Þ2
i

where k is the number of parameters in the model and L is the where qe,a,meas is the average of qe,meas. determination coefficient is
maximum value of the likelihood function for the model. used to check the validity of the kinetic and isotherm models used
in describing the experimental data.
Error function
Adjusted determination coefficient
Average relative error A measure of the variability of the linear model is explained by
the adjusted linear coefficient of determination ðR2 Þ [179,236]
Ad j
" #
represented in Eq. (46)
100 X ðqe;cal — qe;meas Þ
p
. Σ
R
i
n—p
n (43) 2
qe;meas (46)
i¼1 Ad j n—1
¼ 1 — ð1 — R2Þ·

Average relative error function attempts to reduce the

fractional error distribution across the entire concentration range Error function [179,236]
[234].
Where qe,calc is the calculated adsorbate concentration at vffiffiffiffiffiffiffiffiffi ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ffi
equilibrium(mg/g), qe,meas measured adsorbate concentration at u. 1 Σ X n
2
equilibrium (mg/g), n is the number of data points and p is the Ferror ¼ t · ðqi;exp — qi;modelÞ (47)
n—p
number of parameter of the isotherm equation. i
410 n — p 2 (2014) 398–414
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering
i
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414
where qi,model is each value of q predicted by the fitted model, qi,exp
is each value of q measured experimentally, q¯i;exp is the average of q
[15]
experimentally measured, n is the number of experiments
performed, and p is the number of parameters of the fitted model
Conclusion
In this review the adsorption isotherm models have been
discussed in an elaborate manner on the basis of two, three, four
and five parameters respectively. The study reveals that the two
and three parameter isotherm models finds majority in the
assessment of adsorption equilibrium data of the most of the
biosorbents reviewed. Despite a number of papers published by
considering the various adsorption isotherm models, Langmuir
and Freundlich isotherms have the best fit in case of two-
parameter isotherm model followed with the Sips and Liu in case of
three parameter isotherm model for evaluating biosorbents. But
still there is a need to extend the research by subjecting the
equilibrium data through different parameters isotherm models
for biosorbent evaluation. Further the application of the different
isotherm models to be extended from the batch study to the
commercial scale for the betterment of biosorbent utilization in an
effective manner.
Acknowledgements
The authors acknowledge sincere thanks for the financial
assistance from Department of Science and Technology, India
(Grant No. SERC/ET-0356/2012). The authors thank the Editor,
reviewers for their valuable comments and suggestions which
improved the quality of the paper.
References
[1] Y. Wu, J. He, L. Yang, Evaluating adsorption and biodegradation mechanisms
during the removal of microcystin–RR by periphyton, Environ. Sci. Technol. 44
(2010) 6319–6324.
[2] M. Yang, A current global view of environmental and occupational cancers, J.
Environ. Sci. Health Part. C 29 (2011) 223–249.
[3] A. Bhatnagar, M. Sillanpaa, Utilization of agro-industrial and municipal waste
materials as potential adsorbents for water treatment – a review, Chem. Eng. J.
157 (2010) 277–296.
[4] A. Bhatnagar, E. Kumar, M. Sillanpaa, Fluoride removal from water by adsorption
– a review, Chem. Eng. J. 171 (2011) 811–840.
[5] J.F. Gao, Q. Zhang, K. Su, J.H. Wang, Competitive biosorption of Yellow 2G and
reactive Brilliant Red K-2G onto inactive aerobic granules: simultaneous deter-
mination of two dyes by firstorder derivative spectrophotometry and isotherm
studies, Bioresour. Technol. 101 (2010) 5793–5801.
[6] P. Sathishkumar, M. Arulkumar, T. Palvannan, Utilization of agro-industrial
waste Jatropha curcas pods as an activated carbon for the adsorption of reactive
dye Remazol Brilliant Blue R (RBBR), J. Clean. Prod. 22 (2012) 67–75.
[7] A. Bhatnagar, W. Hogland, M. Marques, M. Sillanpaa, An overview of the
modification methods of activated carbon for its water treatment applications
– a review, Chem. Eng. J. 219 (2013) 499–511.
[8] S.-F. Lo, S.-Y. Wang, M.-J. Tsai, L.-D. Lin, Adsorption capacity and removal
efficiency of heavy metal ions by Moso and Ma bamboo activated carbons,
Chem. Eng. Res. Des. 90 (2012) 1397–1406.
[9] M.E. Argun, S. Dursun, C. Ozdemir, M. Karatas, Heavy metal adsorption by
modified oak sawdust: thermodynamics and kinetics, J. Hazard. Mater. 141
(2007) 77–85.
[10] M.K. Aroua, S.P.P. Leong, L.Y. Teo, C.Y. Yin, W.M.A.W. Daud, Real-time determi-
nation of kinetics of adsorption of lead(II) onto palm shell-based activated
carbon using ion selective electrode, J. Bioresour. Technol. 99 (2008) 5786–5792.
[11] M.H. El-Naas, S. Al-Zuhair, M.A. Alhaija, Reduction of COD in refinery wastewater
through adsorption on date-pit activated carbon, J. Hazard. Mater. 173 (2010) 750–
757.
[12] A. Ahmad, B. Hameed, Reduction of COD and color of dyeing effluent from a
cotton textile mill by adsorption onto bamboo-based activated carbon, J. Hazard.
Mater. 172 (2009) 1538–1543.
[13] N.H. Phan, S. Rio, C. Faur, L. Le Coq, P. Le Cloirec, T.H. Nguyen, Production of
fibrous activated carbons from natural cellulose (jute, coconut) fibers for water
treatment applications, Carbon 44 (2006) 2569–2577.
[14] N. El Hannafi, M.A. Boumakhla, T. Berrama, Z. Bendjama, Elimination of phenol
by adsorption on activated carbon prepared from the peach cores: modelling and
optimization, Desalination 223 (2008) 264–268.
411
M.D.G. de Luna, E.D. Flores, D.A.D. Genuino, C.M. Futalan, M.-W. Wan, Adsorption
of Eriochrome Black T (EBT) dye using activated carbon prepared from waste rice
hulls – optimization, isotherm and kinetic studies, J. Taiwan Inst. Chem. Eng. 44
(2013) 646–653.
[16] M. El-Halwany, Study of adsorption isotherms and kinetic models for Methylene
Blue adsorption on activated carbon developed from Egyptian rice hull (part II),
Desalination 250 (2010) 208–213.
[17] M. Halwany, P. Sathishkumar, T. Palvannan, Optimization of orange G dye
adsorption by activated carbon of Thespesia populnea pods using response
surface methodology, J. Hazard. Mater. 186 (2011) 827–834.
[18] C.H. Giles, D. Smith, A. Huitson, A general treatment and classification of the solute
adsorption isotherm. I. Theoretical, J. Colloid Interface Sci. 47 (1974) 755–765.
[19] G. Limousin, J.P. Gaudet, L. Charlet, S. Szenknect, V. Barthes, M. Krimissa, Sorption
isotherms: a review on physical bases, modeling, and measurement, Appl.
Geochem. 22 (2007) 249–275.
[20] V.V. Srivastava, M.M. Swamy, I.D. Mall, B. Prasad, I.M. Mishra, Adsorptive
removal of phenol by bagasse fly ash and activated carbon: equilibrium, kinetics
and thermodynamics, Colloids. Surf. A 272 (2006) 89–104.
[21] F. Gimbert, N. Morin-Crini, F. Renault, P.M. Badot, G. Crini, Adsorption isotherm
models for dye removal by cationized starch-based material in a single compo-
nent system: error analysis, J. Hazard. Mater. 157 (2008) 34–46.
[22] Y.S. Ho, J.F. Porter, G. Mckay, Equilibrium isotherm studies for the sorption of
divalent metal ions onto peat: copper, nickel and lead single component sys-
tems, Water Air Soil Pollut. 141 (2002) 1–33.
[23] M.I. El-Khaiary, Least-squares regression of adsorption equilibrium data: com-
paring the options, J. Hazard. Mater. 158 (2008) 73–87.
[24] G. Thompson, J. Swain, M. Kay, C.F. Forster, The treatment of pulp and paper mill
effluent: a review, Bioresour. Technol. 77 (2001) 275–286.
[25] Z. Aksu, Application of biosorption for the removal of organic pollutants: a
review, Process Biochem. 40 (2005) 997–1026.
[26] K. Vijayaraghavan, Y.-S. Yun, Bacterial biosorbents and biosorption, Biotechnol.
Adv. 26 (2008) 266–291.
[27] J.M. Modak, K.A. Natarajan, Biosorption of metals using non-living biomass – a
review, Miner. Metal. Process. 12 (1995) 189–196.
[28] A. Demirbas, Recent advances in biomass conversion technologies, Energy Educ.
Sci. Technol. 6 (2000) 19–40.
[29] A. Demirbas, Biomass resources for energy and chemical industry, Energy Educ.
Sci. Technol. 5 (2000) 21–45.
[30] A. Demirbas, Mechanisms of liquefaction and pyrolysis reactions of biomass,
Energy Convers. Manage. 41 (2000) 633–646.
[31] A. Hashem, R.A. Akasha, A. Ghith, D.A. Hussein, Adsorbent based on agricultural
wastes for heavy metal and dye removal: a review, Energy Educ. Sci. Technol. 19
(2007) 69–86.
[32] O. Theander, in: R.P. Overand, T.A. Mile, L.K. Mudge (Eds.), Fundamentals of
Thermochemical Biomass Conversion, Elsevier Applied Science Publisher, New
York, 1985.
[33] T.E. Timell, Recent progress in the chemistry of wood hemicelluloses, Wood Sci.
Technol. 1 (1967) 45–70.
[34] H.F.J. Wenzl, F.E. Brauns, D.A. Brauns, The Chemical Technology of Wood,
Academic Press, New York, 1970.
[35] I.S. Goldstein, Organic Chemical from Biomass, CRC Press, Boca Raton, FL, 1981.
[36] W.G. Glasser, S. Sarkanen (Eds.), Lignin: Properties and Materials, American
Chemical Society, Washington, DC, 1989.
[37] K.V. SarkanenF, C.H. Ludwig, Lignins: Occurrence, Formation, Structure and
Reactions, John Wiley & Sons, Inc., New York, 1971.
[38] A. Demirbas, M.M. Kucuk, Delignification of Ailanthus altissimo and Spruce
orientalis with glycerol or alkaline glycerol at atmospheric pressure, Cellulose
Chem. Technol. 27 (1993) 679–686.
[39] N. Chilton, N. Jack, N. Losso, E. Wayne, R. Marshall, Freundlich adsorption
isotherm of agricultural by product based powered activated carbon in geosmin
water system, Bioresour. Technol. 85 (2) (2002) 131–135.
[40] A. Malek, S. Farooq, Comparison of isotherm models for hydrocarbon adsorption
on activated carbon, AIChE J. 42 (11) (1996) 3191–3201.
[41] I. Langmuir, The constitution and fundamental properties of solids and liquids, J.
Am. Chem. Soc. 38 (11) (1916) 2221–2295.
[42] J.H. De Boer, The Dynamical Character of Adsorption, second ed., Oxford
University Press, London, 1968.
[43] A.L. Myers, J.M. Prausnitz, Thermodynamics of mixed gas adsorption, AIChE J. 11
(1) (1965) 121–129.
[44] M.M. Dubinin, The potential theory of adsorption of gases and vapors for
adsorbents with energetically non-uniform surface, Chem. Rev. 60 (1960) 235–
266.
[45] T.H. Vermeulan, K.R. Vermeulan, L.C. Hall, Pore- and solid-diffusion kinetics in
fixed-bed adsorption under constant-pattern conditions, Ind. Eng. Chem. Fun-
dam. 5 (1966) 212–223.
[46] T.N. Webber, R.K. Chakravarti, Pore and solid diffusion models for fixed bed
adsorbers, J. Am. Inst. Chem. Eng. 20 (1974) 228–238.
[47] H.M.F. Freundlich, About the adsorption in solution, Z. Phys. Chem. 57 (1906)
385–471.
[48] R.E. Treybal, Mass Transfer Operations, McGraw-Hill, New York, 1987.
[49] B. Al-Duri, in: G. McKay (Ed.), Use of Adsorbents for the Removal of Pollutants
from Wastewaters, CRC Press, 1996, pp. 133–173.
[50] S. Basha, Z.V.P. Murthy, B. Jha, Sorption of Hg(II) from aqueous solutions onto
Carica papaya: application of isotherms, Ind. Eng. Chem. Res. 47 (2008) 980–986.
[51] M. Isik, Biosorption of Ni(II) from aqueous solutions by living and non-living
ureolytic mixed culture, Colloids. Surf. B 62 (2008) 97–104.
412 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

Y. Liu, Y.-J. Liu, Biosorption isotherms, kinetics and thermodynamics – review,

[52] M.I. Tempkin, V. Pyzhev, Kinetics of ammonia synthesis on promoted iron
Sep. Purif. Technol. 61 (2008) 229–242.
catalyst, Acta PhysChim. USSR 12 (1940) 327–356.
[88] B.M. Van Vliet, W.J. Weber, H. Hozumi, Modeling and prediction of specific
[53] B. Kiran, A. Kaushik, Chromium binding capacity of Lyngbya putealis exopoly-
compound adsorption by activated carbon and synthetic adsorbents, Water Res.
saccharides, Biochem. Eng. J. 38 (2008) 47–54.
14 (1980) 1719–1817.
[54] M.M. Dubinin, Modern state of the theory of volume filling of micropore
[89] M. Baudu, Study of interactions solute-activated carbon fibers. Application and
adsorbents during adsorption of gases and steams on carbon adsorbents, Zh.
regeneration, (Ph.D. thesis), University’s Reindeer I, 1990.
Fiz. Khim. 39 (1965) 1305–1317.
[90] S. Bruanuer, P.H. Emmett, E. Teller, Adsorption of gases in multimolecular layers,
[55] L.V. Radushkevich, Potential theory of sorption and structure of carbons, Zh. Fiz.
J. Am. Chem. Soc. 60 (1938) 309–316.
Khim. 23 (1949) 1410–1420.
[91] G. McKay, Use of Adsorbents for the Removal of Pollutants from Wastewaters,
[56] M.M. Dubininand, L.V. Radushkevich, Equation of the characteristic curve of
CRC Press, Boca Raton, FL, 1996.
activated charcoal, Chem. Zentr. 1 (1947) 875.
[92] C. Tien, Adsorption Calculations and Modeling, Butterworth-Heinemann Series
[57] S.J. Gregg, K.S.W. Sing, Adsorption, Surface Area and Porosity, 2nd ed., Academic
in Chemical Engineering, Butterworth-Heinemann, Boston, 1994.
Press, London, UK, 1982.
[93] D. Sud, G. Mahajan, M.P. Kaur, Agricultural waste material as potential adsorbent
[58] S.M. Hasany, M.H. Chaudhary, Sorption potential of Haro river sand for the
for sequestering heavy metal ions from aqueous solutions – a review, Bioresour.
removal of antimony from acidic aqueous solution, Appl. Radiat. Isotopes 47
Technol. 99 (2008) 6017–6027.
(1996) 467–471.
[94] J. Febrianto, A.N. Kosasih, J. Sunarso, Y.-H. Ju, N. Indraswati, S. Ismadji, Equilib-
[59] A. Benhammou, A. Yaacoubi, L. Nibou, B. Tanouti, Adsorption of metal ions onto
rium and kinetic studies in adsorption of heavy metals using biosorbent: a
Moroccan stevensite: kinetic and isotherm studies, J. Colloid Interface Sci. 282
summary of recent studies, J. Hazard. Mater. 162 (2009) 616–645.
(2005) 320–326.
[95] B. Volesky, Detoxification of metal-bearing effluents: biosorption for the next
[60] J.P. Hobson, Physical adsorption isotherms extending from ultrahigh vacuum to
century, Hydrometallurgy 59 (2001) 203–216.
vapor pressure, J. Phys. Chem. 73 (1969) 2720–2727.
[96] E.C. Lima, B. Royer, J.C.P. Vaghetti, J.L. Brasil, N.M. Simon, A.A. Dos Santos Jr., F.A.
[61] M. Horsfall, A.I. Spiff, Equilibrium sorption study of Al 3+, Co2+ and Ag2+ in
Pavan, S.L.P. Dias, E.V. Benvenutti, E.A. da Silva, Adsorption of Cu(II) on Araucaria
aqueous solutions by fluted pumpkin (Telfairia occidentalis HOOK) waste bio-
angustifolia wastes: determination of the optimal conditions by statistic design
mass, Acta Chim. Slov. 52 (2005) 174–181.
of experiments, J. Hazard. Mater. 140 (2007) 211–220.
[62] S.Y. Elovich, O.G. Larinov, Theory of adsorption from solutions of non electrolytes
[97] I. Aloma, M.A. Martın-Lara, I.L. Rodrıguez, G. Blazquez, M. Calero, Removal of
on solid (I) equation adsorption from solutions and the analysis of its simplest
nickel(II) ions from aqueous solutions by biosorption on sugarcane bagasse, J.
form, (II) verification of the equation of adsorption isotherm from solutions, Izv.
Taiwan Inst. Chem. Eng. 43 (2012) 275–281.
Akad. Nauk. USSR, Otd. Khim. Nauk 2 (1962) 209–216.
[98] E.M. Soliman, S.A. Ahmed, A.A. Fadl, Reactivity of sugar cane bagasse as a natural
[63] R.H. Fowler, E.A. Guggenheim, Statistical Thermodynamics, Cambridge Univer- solid phase extractor for selective removal of Fe(III) and heavy-metal ions from
sity Press, London, 1939, pp. 431–450.
natural water samples, Arab. J. Chem. 4 (2011) 63–70.
[64] A.V. Kiselev, Vapor adsorption in the formation of adsorbate molecule complexes [99] R.A. Jacques, E.C. Lima, S.L.P. Dias, A.C. Mazzocato, F.A. Pavan, Yellow passion-
on the surface, Kolloid Zhur. 20 (1958) 338–348.
fruit shell as biosorbent to remove Cr(III) and Pb(II) from aqueous solution, Sep.
[65] T.L. Hill, Localized and mobile adsorption and adsorption, J. Chem. Phys. 14
Purif. Technol. 57 (2007) 193–198.
(1946) 441.
[100] M.S. Mansour, M.E. Ossman, H.A. Farag, Removal of Cd(II) ion from waste water
[66] J.H. de Boer, The Dynamical Character of Adsorption, Oxford University Press, by adsorption onto polyaniline coated on sawdust, Desalination 272 (2011)
Oxford, 1953. 301–305.
[67] D.S. Jovanovic, Physical adsorption of gases. I: isotherms for monolayer and [101] M. Helen Kalavathy, L.R. Miranda, Comparison of copper adsorption from
multilayer adsorption, Colloid Polym. Sci. 235 (1969) 1203–1214. aqueous solution using modified and unmodified Hevea brasiliensis saw dust,
[68] G. Halsey, Physical adsorption on non-uniform surfaces, J. Chem. Phys. 16 (1948) Desalination 255 (2010) 165–174.
931–937. [102] N. Feng, X. Guo, S. Liang, Y. Zhu, J. Liu, Biosorption of heavy metals from aqueous
[69] W.D. Harkins, E.J. Jura, The decrease of free surface energy as a basis for the solutions by chemically modified orange peel, J. Hazard. Mater. 185 (2011) 49–
development of equations for adsorption isotherms; and the existence of two 54.
condensed phases in films on solids, J. Chem. Phys. 12 (1944) 112–113. [103] J.C.P. Vaghetti, E.C. Lima, B. Royer, B.M. da Cunha, N.F. Cardoso, J.L. Brasil, S.L.P.
[70] O. Redlich, D.L. Peterson, A useful adsorption isotherm, J. Phys. Chem. 63 (1959) 1024. Dias, Pecan nutshell as biosorbent to remove Cu(II), Mn(II) and Pb(II) from
[71] A.V. Hill, The possible effects of the aggregation of the molecules of haemoglobin
aqueous solutions, J. Hazard Mater. 162 (2009) 270–280.
on its dissociation curves, J. Physiol. (Lond.) 40 (1910) 4–7.
[104] M.R. Lasheen, N.S. Ammar, H.S. Ibrahim, Adsorption/desorption of Cd(II), Cu(II)
[72] L.K. Koopal, W.H. Van Riemsdijk, J.C.M. de Wit, M.F. Benedetti, Analytical
and Pb(II) using chemically modified orange peel: equilibrium and kinetic
isotherm equation for multicomponent adsorption to heterogeneous surfaces,
studies, Solid State Sci. 14 (2012) 202–210.
J. Colloid Interface Sci. 166 (1994) 51–60.
[105] E. Pehlivan, T.H. Tran, W.K.I. Oue´ draogo, C. Schmidt, D. Zachmann, M. Bahadir,
[73] D. Ringot, B. Lerzy, K. Chaplain, J.P. Bonhoure, E. Auclair, Y. Larondelle, In vitro
Removal of As(V) from aqueous solutions by iron coated rice husk, Fuel. Process.
biosorption of ochratoxin A on the yeast industry by-products: comparison of
Technol. 106 (2013) 511–517.
isotherm models, Bioresour. Technol. 98 (2007) 1812–1821.
[106] J. Zhang, H. Fu, X. Lv, J. Tang, X. Xu, Removal of Cu(II) from aqueous solution using
[74] J. Toth, Calculation of the BET-compatible surface area from any type I isotherms
the rice husk carbons prepared by the physical activation process, Biomass
measured above the critical temperature, J. Colloid Interface Sci. 225 (2000) 378–
Bioenergy 35 (2011) 464–472.
383.
[107] C.S. Zhu, L.P. Wang, W.B. Chen, Removal of Cu(II) from aqueous solution by
[75] A.R. Khan, R. Ataullah, A. Al-Haddad, Equilibrium adsorption studies of some
agricultural by-product: peanut hull, J. Hazard Mater. 168 (2009) 739–746.
aromatic pollutants from dilute aqueous solutions on activated carbon at
[108] P. Suksabye, P. Thiravetyan, Cr(VI) adsorption from electroplating plating waste-
different temperatures, J. Colloid Interface Sci. 194 (1997) 154–165.
water by chemically modified coir pith, J. Environ. Manage. 102 (2012) 1–8.
[76] A.P. Terzyk, J. Chatlas, P.A. Gauden, G. Rychlicki, P. Kowalczyk, Developing the
[109] M.A. Hossain, H.H. Ngo, W.S. Guo, T. Setiadi, Adsorption and desorption of
solution analogue of the Toth adsorption equation, J. Colloid Interface Sci. 206
copper(II) ions onto garden grass, Bioresour. Technol. 121 (2012) 386–395.
(2003) 473–476.
[110] A. Kausar, H.N. Bhatti, G. MacKinnon, Equilibrium, kinetic and thermodynamic
[77] S. Debnath, U.C. Ghosh, Kinetics, isotherm and thermodynamics for Cr(III) and
studies on the removal of U(VI) by low cost agricultural waste, Colloids Surf. B.
Cr(VI) adsorption from aqueous solutions by crystalline hydrous titanium oxide,
Biointerfaces 111 (2013) 124–133.
J. Chem. Thermodyn. 40 (2008) 67–77.
[111] F.E. Soetaredjo, A. Kurniawan, O.L. Ki, S. Ismadji, Incorporation of selectivity
[78] M. Sathishkumar, K. Vijayaraghavan, A.R. Binupriya, A.M. Stephan, J.G. Choi, S.E.
factor in modeling binary component adsorption isotherms for heavy metals-
Yun, Porogen effect on characteristics of banana pith carbon and sorption of
biomass system, Chem. Eng. J. 219 (2013) 137–148.
dichlorophenols, J. Colloid Interface. Sci. 320 (2008) 22–29.
[112] Y. Ho, A.E. Ofomaja, Biosorption thermodynamics of cadmium on coconut copra
[79] L. Jossens, J.M. Prausnitz, E.U. Fritz, A.L. Myers, Thermodynamics of multi-solute
meal as biosorbent, Biochem. Eng J. 30 (2006) 117–123.
adsorption from dilute aqueous solutions, Chem. Eng. Sci. 33 (1978) 1097–1106.
[113] J. Zolgharnein, N. Asanjarani, T. Shariatmanesh, Taguchi L16 orthogonal array
[80] W. Fritz, E.U. Schlunder, Simultaneous adsorption equilibria of organic solutes in
optimization for Cd(II) removal using Carpinus betulus tree leaves: adsorption
dilute aqueous solution on activated carbon, Chem. Eng. Sci. 29 (1974) 1279–
characterization, Int. Biodeterior. Biodegrad. 85 (2013) 66–77.
1282.
[114] G. Vazquez, M. Olga Mosquera, S. Freire, G. Antorrena, J. Gonzalez-Alvarez,
[81] R. Sips, On the structure of a catalyst surface, J. Chem. Phys. 16 (1948) 490–495.
Alkaline pre-treatment of waste chestnut shell from a food industry to enhance
[82] R.A. Koble, T.E. Corrigan, Adsorption isotherm for pure hydrocarbons, Ind. Eng.
cadmium, copper, lead and zinc ions removal, Chem. Eng. J. 184 (2012) 147–155.
Chem. Res. 44 (1952) 383–387.
[115] X.S. Wang, Z.Z. Li, C. Sun, A comparative study of removal of Cu(II) from aqueous
[83] R. Han, J. Zhang, P. Han, Y. Wang, Z. Zhao, M. Tang, Study of equilibrium, kinetic
solutions by locally low-cost materials: marine macroalgae and agricultural by-
and thermodynamic parameters about methylene blue adsorption onto natural
products, Desalination 235 (2009) 146–159.
zeolite, Chem. Eng. J. 145 (2009) 496–504.
[116] D. Pujol, M. Bartroli, N. Fiol, F. de la Torre, I. Villaescusa, J. Poch, Modelling
[84] A.R. Khan, I.R. Al-Waheab, A. Al-Haddad, A generalized equation for adsorption
synergistic sorption of Cr(VI), Cu(II) and Ni(II) onto exhausted coffee wastes
isotherms for multi-component organic pollutants in dilute aqueous solution,
from binary mixtures Cr(VI)–Cu(II) and Cr(VI)–Ni(II), Chem. Eng. J. 230 (2013)
Environ. Technol. 17 (1996) 13–23.
396–405.
[85] C.J. Radke, J.M. Prausnitz, Adsorption of organic solutions from dilute aqueous
[117] M.A. Hanif, R. Nadeem, H.N. Bhatti, N.R. Ahmad, T.M. Ansari, Ni(II) biosorption by
solution on activated carbon, Ind. Eng. Chem. Fundam. 11 (1972) 445–451.
Cassia fistula (Golden Shower) biomass, J. Hazard. Mater. B139 (2007) 345–355.
[86] T. Grchev, M. Cvetkovska, T. Stafilov, J.W. Schultze, Adsorption of polyacrylamide
[118] S. Schiewer, S.B. Patil, Pectin-rich fruit wastes as biosorbents for heavy metal
on gold and iron from acidic aqueous solutions, Electrochim. Acta 36 (1991)
removal: equilibrium and kinetics, Bioresour. Technol. 99 (2008) 1896–1903.
1315–1323.

[87]
 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 413

A. Leena Prasad, T. Santhi, Adsorption of hazardous cationic dyes from aqueous

[119] M. Dundar, C. Nuhoglu, Y. Nuhoglu, Biosorption of Cu(II) ions onto the litter of
solution onto Acacia nilotica leaves as an eco friendly adsorbent, Sustain. Envi-
natural trembling poplar forest, J. Hazard. Mater. 151 (2008) 86–95.
ron. Res. 22 (2012) 113–122.
[120] H. Aydin, Y. Bulut, C. Yerlikaya, Removal of copper(II) from aqueous solution by
[151] S. Dawood, T. Kanti Sen, Removal of anionic dye Congo red from aqueous
adsorption onto low-cost adsorbents, J. Environ. Manage. 87 (2008) 37–45.
solution by raw pine and acid-treated pine cone powder as adsorbent: equilib-
[121] J.C. Igwe, A.A. Abia, Equilibrium sorption isotherm studies of Cd(II), Pb(II) and
rium, thermodynamic, kinetics, mechanism and process design, Water Res. 46
Zn(II) ions detoxification from waste water using unmodified and EDTA modi-
(2012) 1933–1946.
fied maize husk, Electron. J. Biotechnol. 10 (2007) 536–548.
[152] B.H. Hameed, A.A. Ahmad, Batch adsorption of methylene blue from aqueous
[122] R. Djeribi, O. Hamdaoui, Sorption of copper(II) from aqueous solutions by cedar
solution by garlic peel, an agricultural waste biomass, J. Hazard. Mater. 164
sawdust and crushed brick, Desalination 225 (2008) 95–112.
(2009) 870–875.
[123] K.M.S.S. Sumathi, R.M. Naidu, Use of low-cost biological wastes and vermiculite
[153] D.K. Mahmoud, M.A.M. Salleh, W.A.W.A. Karim, A. Idris, Z.Z. Abidin, Batch
for removal of chromium from tannery effluent, Bioresour. Technol. 96 (3)
adsorption of basic dye using acid treated kenaf fibre char: equilibrium, kinetic
(2005) 309–316. and thermodynamic studies, Chem. Eng. J. 181–182 (2012) 449–457.
[124] A. Ronda, M.A. Martin-Lara, E. Dionisio, G. Blazquez, M. Calero, Effect of lead in [154] T. Akar, I. Tosun, Z. Kaynak, E. Ozkara, O. Yeni, E.N. Sahin, S.T. Akar, An attractive
biosorption of copper by almond shell, J. Taiwan Inst. Chem. Eng. 44 (2013) 466– agro-industrial by-product in environmental cleanup: dye biosorption potential
473. of untreated olive pomace, J. Hazard. Mater. 166 (2009) 1217–1225.
[125] E. Pehlivan, B.H. Yanik, G. Ahmetli, M. Pehlivan, Equilibrium isotherm studies for
[155] H.M.H. Gad, A.A. El-Sayed, Activated carbon from agricultural by-products for the
the uptake of cadmium and lead ions onto sugar beet pulp, Bioresour. Technol.
removal of Rhodamine-B from aqueous solution, J. Hazard. Mater. 168 (2009)
99 (2008) 3520–3527.
1070–1081.
[126] M. Iqbal, A. Saeed, S.I. Zafar, FTIR spectrophotometry, kinetics and adsorption
[156] A. Ahmad, M. Rafatullah, O. Sulaiman, M.H. Ibrahim, R. Hashim, Scavenging
isotherms modeling, ion exchange, and EDX analysis for understanding the
behaviour of meranti sawdust in the removal of methylene blue from aqueous
mechanism of Cd2+ and Pb2+ removal by mango peel waste, J. Hazard. Mater. 164
solution, J. Hazard. Mater. 170 (2009) 357–365.
(2009) 161–171.
[157] T. Santhi, S. Manonmani, T. Smitha, Removal of malachite green from aqueous
[127] F.D. Oliveira, J.H. Paula, O.M. Freitas, S.A. Figueiredo, Copper and lead removal by
solution by activated carbon prepared from the epicarp of Ricinus communis by
peanut hulls: equilibrium and kinetic studies, Desalination 248 (2009) 931–940.
adsorption, J. Hazard. Mater. 179 (2010) 178–186.
[128] S. Liang, X. Guo, N. Feng, Q. Tian, Isotherms, kinetics and thermodynamic studies
[158] W. Zhang, H. Li, X. Kan, L. Dong, H. Yan, Z. Jiang, H. Yang, A. Li, R. Cheng,
of adsorption of Cu2+ from aqueous solutions by Mg2+/K+ type orange peel
Adsorption of anionic dyes from aqueous solutions using chemically modified
adsorbents, J. Hazard. Mater. 174 (2010) 756–762.
straw, Bioresour. Technol. 117 (2012) 40–47.
[129] T.S. Anirudhan, P.G. Radhakrishnan, Kinetics, thermodynamics and surface
[159] M.E. Fernandez, G.V. Nunell, P.R. Bonelli, A.L. Cukierman, Batch and dynamic
heterogeneity assessment of uranium(VI) adsorption onto cation exchange resin
biosorption of basic dyes from binary solutions by alkaline-treated cypress cone
derived from a lignocellulosic residue, Appl. Surf. Sci. 255 (2009) 4983–4991.
chips, Bioresour. Technol. 106 (2012) 55–62.
[130] B. Singha, S. Kumar Das, Adsorptive removal of Cu(II) from aqueous solution and
[160] U.R. Lakshmi, V.C. Srivastva, I.D. Mall, D.H. Lataye, Rice husk ash as an effective
industrial effluent using natural/agricultural wastes, Colloids. Surf. B 107 (2013)
adsorbent: evaluation of adsorptive characteristics for indigo Carmine dye, J.
97–106.
Environ. Manage. 90 (2009) 710–720.
[131] A.O. Dada, A.P. Olalekan, A.M. Olatunya, O. Dada, Langmuir, Freundlich, Temkin
[161] D.H. Lataye, I.M. Mishra, I.D. Mall, Adsorption of a-picoline onto rice husk ash
and Dubinin–Radushkevich isotherms studies of equilibrium sorption of Zn 2+
and granular activated carbon from aqueous solution: equilibrium and thermo-
unto phosphoric acid modified rice husk, IOSR J. Appl. Chem. 3 (2012) 38–45.
dynamic study, Chem. Eng. J. 147 (2009) 139–149.
[132] M.A. Hossain, H.H. Ngo, W.S. Guo, T.V. Nguyen, Palm oil fruit shells as biosorbent
[162] R. Gong, S. Zhu, D. Zhanga, J. Chen, S. Ni, R. Guan, Adsorption behavior of cationic
for copper removal from water and wastewater: experiments and sorption
dyes on citric acid esterifying wheat straw: kinetic and thermodynamic profile,
models, Bioresour. Technol. 113 (2012) 97–101.
Desalination 230 (2008) 220–228.
[133] V.K. Gupta, D. Pathania, S. Agarwal, S. Sharma, Removal of Cr(VI) onto Ficus carica
[163] F.A. Pavan, E.C. Lima, S.L.P. Dias, A.C. Mazzocata, Methylene blue biosorption
biosorbent from water, Environ. Sci. Pollut. Res. 20 (2013) 2632–2644.
from aqueous solutions by yellow passion fruit waste, J. Hazard. Mater. 150
[134] N. Barka, M. Abdennouri, M. El Makhfouk, S. Qourzal, Biosorption characteristics
(2008) 703–712.
of cadmium and lead onto eco-friendly dried cactus (Opuntia ficus indica)
[164] B.C. Oei, S. Ibrahim, S. Wang, H.A. Ang, Surfactant modified barley straw for
cladodes, J. Environ. Chem. Eng. 1 (2013) 144–149.
removal of acid and reactive dyes from aqueous solution, Bioresour. Technol.
[135] D. Kumar Mondal, B. Kumar Nandi, M.K. Purkait, Removal of mercury(II) from
100 (2009) 4292–4295.
aqueous solution using bamboo leaf powder: equilibrium, thermodynamic and
[165] B. Royer, N.F. Cardoso, E.C. Lima, J.C.P. Vaghetti, N.M. Simon, T. Calvete, R.C.
kinetic studies, J. Environ. Chem. Eng. 1 (2013) 891–898.
Veses, Applications of Brazilian pine-fruit shell in natural and carbonized forms
[136] N. Sharma, D.P. Tiwari, S.K. Singh, Decolourisation of synthetic dyes by agricul-
as adsorbents to removal of methylene blue from aqueous solutions – kinetic
tural waste – a review, Int. J. Sci. Eng. Res. 3 (2012) 1–10.
and equilibrium study, J. Hazard. Mater. 164 (2009) 1213–1222.
[137] S. Rangabhashiyam, N. Anu, N. Selvaraju, The significance of fungal Laccase in
[166] N.F. Cardoso, E.C. Lima, I.S. Pinto, C.V. Amavisca, B. Royer, R.B. Pinto, W.S. Alencar,
textile dye degradation – a review, Res. J. Chem. Environ. 17 (2013) 88–95.
S.F.P. Pereira, Application of cupuassu shell as biosorbent for the removal of
[138] E. Demirbas, M. Kobya, M.T. Sulak, Adsorption kinetics of a basic dye from
textile dyes from aqueous solution, J. Environ. Manage. 92 (2011) 1237–1247.
aqueous solutions onto apricot stone activated carbon, Bioresour. Technol. 99
[167] P. Janos, S. Coskun, V. Pilarova, J. Rejnek, Removal of basic (Methylene blue) and
(2008) 5368–5373.
acid (Egacid Orange) dyes from water by sorption on chemically treated wood
[139] N. Ahalya, T.V. Ramachandra, R.D. Kanamadi, Biosorption of heavy metals, Res. J.
shavings, Bioresour. Technol. 100 (2008) 1450–1453.
Chem. Environ. 7 (2003) 71–78.
[168] Y. Hamzeh, A. Ashori, E. Azadeh, A. Abdulkhani, Removal of Acid Orange 7 and
[140] S. Rangabhashiyam, N. Anu, N. Selvaraju, Sequestration of dye from textile
Remazol Black 5 reactive dyes from aqueous solutions using a novel biosorbent,
industry wastewater using agricultural waste products as adsorbents, J. Environ.
Mater. Sci. Eng. C 32 (2012) 1394–1400.
Chem. Eng. 1 (2013) 629–641.
[169] M.C. Somasekhara Reddy, L. Sivaramakrishna, A. Varada Reddy, The use of an
[141] B. Senturk, D. Ozdes, C. Duran, Biosorption of Rhodamine 6G from aqueous
agricultural waste material, Jujuba seeds for the removal of anionic dye (Congo red)
solutions onto almond shell (Prunus dulcis) as a low cost biosorbent, Desalina-
from aqueous medium, J. Hazard. Mater. 203–204 (2012) 118–127.
tion 252 (2010) 81–87.
[170] Md. Motiar, Khan R. Manju Ray, Arun K. Guha, Mechanistic studies on the
[142] N.M. Mahmoodi, B. Hayati, M. Arami, C. Lan, Adsorption of textile dyes on pine
binding of Acid Yellow 99 on coir pith, Bioresour. Technol. 102 (2011) 2394–
cone from colored wastewater: kinetic, equilibrium and thermodynamic stud-
2399.
ies, Desalination 268 (2011) 117–125.
[171] R. Baccar, P. Blanquez, J. Bouzid, M. Feki, M. Sarra, Equilibrium, thermodynamic
[143] X. Han, W. Wang, X. Ma, Adsorption characteristics of methylene blue onto low
and kinetic studies on adsorption of commercial dye by activated carbon derived
cost biomass material lotus leaf, Chem. Eng. J. 171 (2011) 1–8.
from olive-waste cakes, Chem. Eng. J. 165 (2010) 457–464.
[144] G.O. El-Sayed, Removal of methylene blue and crystal violet from aqueous
[172] Y. Feng, F. Yang, Y. Wang, L. Ma, Y. Wu, P.G. Kerr, L. Yang, Basic dye adsorption
solutions by palm kernel fiber, Desalination 272 (2011) 225–232.
onto an agro-based waste material – Sesame hull (Sesamum indicum L.), Bior-
[145] T. Calvete, E.C. Lima, N.F. Cardoso, S.L.P. Dias, F.A. Pavan, Application of carbon esour. Technol. 102 (2011) 10280–10285.
adsorbents prepared from the Brazilian pine-fruit-shell for the removal of
[173] T. Akar, B. Anilan, A. Gorgulu, S.T. Akar, Assessment of cationic dye biosorption
Procion Red MX 3B from aqueous solution – kinetic, equilibrium, and thermo-
characteristics of untreated and non-conventional biomass: Pyracantha coccinea
dynamic studies, Chem. Eng. J. 155 (2009) 627–636. berries, J. Hazard. Mater. 168 (2009) 1302–1309.
[146] L. Wang, Application of activated carbon derived from ‘waste’ bamboo culms for
[174] R. Baccar, P. Blanquez, J. Bouzid, M. Feki, H. Attiya, M. Sarra, Modeling of
the adsorption of azo disperse dye: kinetic, equilibrium and thermodynamic
adsorption isotherms and kinetics of a tannery dye onto an activated carbon
studies, J. Environ. Manage. 102 (2012) 79–87.
prepared from an agricultural by-product, Fuel. Process. Technol. 106 (2013)
[147] E.C. Lima, B. Royer, J.C.P. Vaghetti, N.M. Simon, B.M. da Cunha, F.A. Pavan, E.V.
408–415.
Benvenutti, R. Cataluna-Veses, C. Airoldi, Application of Brazilian pine-fruit shell
[175] Y. Feng, H. Zhou, G. Liu, J. Qiao, J. Wang, H. Lu, L. Yang, Y. Wu, Methylene blue
as a biosorbent to removal of reactive red 194 textile dye from aqueous solution
adsorption onto swede rape straw (Brassica napus L.) modified by tartaric acid:
kinetics and equilibrium study, J. Hazard. Mater. 155 (2008) 536–550.
equilibrium, kinetic and adsorption mechanisms, Bioresour. Technol. 125 (2012)
[148] N.F. Cardoso, R.B. Pinto, E.C. Lima, T. Calvete, C.V. Amavisca, B. Royer, M.L. Cunha,
138–144.
T.H.M. Fernandes, I.S. Pinto, Removal of remazol black B textile dye from
[176] L.S. Silva, L.C.B. Lima, F.C. Silva, J.M.E. Matos, M.R.M.C. Santos, L.S. Santos Junior,
aqueous solution by adsorption, Desalination 269 (2011) 92–103.
K.S. Sousa, E.C. da Silva Filho, Dye anionic sorption in aqueous solution onto a
[149] A. Saeed, M. Sharif, M. Iqbal, Application potential of grapefruit peel as dye
cellulose surface chemically modified with aminoethanethiol, Chem. Eng. J. 218
sorbent: kinetics, equilibrium and mechanism of crystal violet adsorption, J.
(2013) 89–98.
Hazard. Mater. 179 (2010) 564–572.

[150]
414 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

B.H. Hameed, I.A.W. Tan, A.L. Ahmad, Adsorption isotherm, kinetic modeling and
[177] W. Zhang, H. Yan, H. Li, Z. Jiang, L. Dong, X. Kan, H. Yang, A. Li, R. Cheng, Removal
mechanism of 2,4,6-trichlorophenol on coconut husk-based activated carbon,
of dyes from aqueous solutions by straw based adsorbents: batch and column
Chem. Eng. J. 144 (2008) 235–244.
studies, Chem. Eng. J. 168 (2011) 1120–1127.
[206] R. Peel, A. Benedec, Attainment of equilibrium in activated carbon isotherm
[178] L.G. da Silva, R. Ruggiero, P.de M. Gontijo, R.B. Pinto, B. Royer, E.C. Lima, T.H.M.
studies, Environ. Sci. Technol. 14 (1980) 66–71.
Fernandes, T. Calvete, Adsorption of Brilliant Red 2BE dye from water solutions
[207] M. Achak, A. Hafidi, N. Ouazzani, S. Sayadi, L. Mandi, Low cost biosorbent
by a chemically modified sugarcane bagasse lignin, Chem. Eng. J. 168 (2011) 620–
‘‘banana peel’’ for the removal of phenolic compounds from olive mill
628.
wastewater: kinetic and equilibrium studies, J. Hazard. Mater. 166 (2009) 117–
[179] L.D.T. Prola, E. Acayanka, E.C. Lima, C.S. Umpierres, J.C.P. Vaghetti, W.O. Santos, S.
125.
Laminsi, P.T. Djifon, Comparison of Jatropha curcas shells in natural form and
[208] S. Rengaraj, R. Sivabalan, B. Arabindoo, V. Murugesan, Adsorption kinetics of o-
treated by non-thermal plasma as biosorbents for removal of Reactive Red 120
cresol on activated carbon from palm seed coat, Ind. J. Chem. Technol. 7 (2000)
textile dye from aqueous solution, Ind. Crop. Prod. 46 (2013) 328–340.
127–131.
[180] M.S. Sajab, C.H. Chia, S. Zakaria, P.S. Khiew, Cationic and anionic modifications of
[209] M. Sathishkumar, A.R. Binupriya, D. Kavitha, S.E. Yun, Kinetic and isothermal
oil palm empty fruit bunch fibers for the removal of dyes from aqueous
studies on liquid-phase adsorption of 2,4-dichlorophenol by palm pith carbon,
solutions, Bioresour. Technol. 128 (2013) 571–577.
Bioresour. Technol. 98 (2007) 866–873.
[181] M. Hadi, M.R. Samarghandi, G. McKay, Equilibrium two-parameter isotherms of
[210] M. Radhika, K. Palanivelu, Adsorptive removal of chlorophenols from aqueous
acid dyes sorption by activated carbons: study of residual errors, Chem. Eng. J. 160
solution by low cost adsorbent – kinetics and isotherm analysis, J. Hazard. Mater.
(2010) 408–416.
B138 (2006) 116–124.
[182] T. Calvete, E.C. Lima, N.F. Cardoso, J.C.P. Vaghetti, S.L.P. Dias, F.A. Pavan, Appli-
[211] L.A. Rodrigues, M.L.C. Pinto da Silva, M.O. Alvarez-Mendes, A. dos Reis Coutinho,
cation of carbon adsorbents prepared from Brazilian-pine fruit shell for the
G.P. Thim, Phenol removal from aqueous solution by activated carbon produced
removal of reactive orange 16 from aqueous solution: kinetic, equilibrium and
from avocado kernel seeds, Chem. Eng. J. 174 (2011) 49–57.
thermodynamic studies, J. Environ. Manage. 91 (2010) 1695–1706.
[212] A.S. Stasinakis, I. Elia, A.V. Petalas, C.P. Halvadakis, Removal of total phenols from
[183] M.R. Samarghandi, M. Hadi, S. Moayedi, F. Barjasteh Askari, Two-parameter
olive-mill wastewater using an agricultural by-product, olive pomace, J. Hazard.
isotherms of methyl orange sorption by pinecone derived activated carbon, Iran
Mater. 160 (2008) 408–413.
J. Environ. Health. Sci. Eng. 6 (2009) 285–294.
[213] B.N. Estevinho, N. Ratola, A. Alves, L. Santos, Pentachlorophenol removal from
[184] P. Senthil Kumar, S. Ramalingam, C. Senthamarai, M. Niranjana, P. Vijayalakshmi,
aqueous matrices by sorption with almond shell residues, J. Hazard. Mater. B137
S. Sivanesan, Adsorption of dye from aqueous solution by cashew nut shell:
(2006) 1175–1181.
studies on equilibrium isotherm, kinetics and thermodynamics of interactions,
[214] D. Mohan, K.P. Singh, S. Sinha, D. Gosh, Removal of pyridine derivatives from
Desalination 261 (2010) 52–60.
aqueous solution by activated carbons developed from agricultural waste
[185] W.S. Alencar, E. Acayanka, E.C. Lima, B. Royer, F.E. de Souza, J. Lameira, C.N. Alves,
materials, Carbon 43 (2005) 1680–1693.
Application of Mangifera indica (mango) seeds as a biosorbent for removal of
[215] C. Namasivayam, D. Kavitha, Adsorptive removal of 2-chlorophenol by low-cost
Victazol Orange 3R dye from aqueous solution and study of the biosorption
coir pith carbon, J. Hazard. Mater. 98 (2003) 257–274.
mechanism, Chem. Eng. J. 209 (2012) 577–588.
[216] A. Bhatnagar, V.J.P. Vilar, C.M.S. Botelho, R.A.R. Boaventura, Coconut-based
[186] R.K. Gautam, A. Mudhoo, M.C. Chattopadhyaya, Kinetic, equilibrium, thermody-
biosorbents for water treatment – a review of the recent literature, Adv. Colloid
namic studies and spectroscopic analysis of Alizarin Red S removal by mustard
Interface Sci. 160 (2010) 1–15.
husk, J. Environ. Chem. Eng. 1 (2013) 1283–1291.
[217] J. DeZuane, Handbook of Drinking Water Quality, 2nd ed., John Wiley & Sons,
[187] F.l. Pua, M.S. Sajab, C.H. Chia, S. Zakaria, I.A. Rahman, M.S. Salit, Alkaline-treated
New York, 1997.
cocoa pod husk as adsorbent for removing methylene blue from aqueous
[218] WHO, Guidelines for Drinking Water Quality, 2nd ed., vol. 1, World Health
solutions, J. Environ. Chem. Eng. 1 (2013) 460–465.
Organization, Geneva, 1993, pp. 45–55.
[188] G. Busca, S. Berardinelli, C. Resini, L. Arrighi, Technologies for the removal of
[219] N.J. Chinoy, Effects of fluoride on physiology of animals and human beings,
phenol from fluid streams: a short review of recent developments, J. Hazard.
Indian J. Environ. Toxicol. 1 (1991) 17–32.
Mater. 160 (2008) 265–288.
[220] P.T.C. Harrison, Fluoride in water: a UK perspective, J. Fluorine Chem. 126 (2005)
[189] J.B. Harbourne, Methods in Plant Biochemistry. 1. Plant Phenolics, Academic
1448–1456.
Press, London, 1989.
[221] A. Kabata-Pendias, H. Pendias, Biochemistry of Trace Elements, PWN, Warsaw,
[190] W. Vermerris, R. Nicholson, Families of Phenolic Compounds and Means of
Poland, 1993.
Classification. Phenolic Compound Biochemistry, Springer, Netherlands, 2006.
[222] B.K. Biswas, K. Inoue, K.N. Ghimire, H. Harada, K. Ohto, H. Kawakita, Removal and
[191] A. Crozier, M.N. Clifford, H. Ashihara, Plant Secondary Metabolites: Occurrence,
recovery of phosphorus from water by means of adsorption onto orange waste
Structure and Role in the Human Diet, Blackwell Publisher Ltd., Singapore, 2006.
gel loaded with zirconium, Bioresour. Technol. 99 (2008) 8685–8690.
[192] K. Abburi, Adsorption of phenol and p-chlorophenol from their single and
[223] U.S. Orlando, A.U. Baes, W. Nishijima, M. Okada, A new procedure to produce
bisolute aqueous solutions on Amberlite XAD-16 resin, J. Hazard. Mater. B
lignocellulosic anion exchangers from agricultural waste materials, Bioresour.
105 (2003) 143–156.
Technol. 83 (2002) 195–198.
[193] F.A. Banat, B. Al-Bashir, S. Al-Asheh, O. Hayajneh, Adsorption of phenol by
[224] C. Namasivayam, D. Sangeetha, Application of coconut coir pith for the removal
bentonite, Environ. Pollut. 107 (2000) 391–398.
of sulfate and other anions from water, Desalination 219 (2008) 1–13.
[194] K. Mohanty, D. Das, M.N. Biswas, Adsorption of phenol from aqueous solutions
[225] C. Namasivayam, M.V. Sureshkumar, Modelling thiocyanate adsorption onto
using activated carbons prepared from Tectona grandis sawdust by ZnCl2 acti-
surfactant-modified coir pith, an agricultural solid waste, Process Saf. Environ.
vation, Chem. Eng. J. 115 (2005) 121–131.
85 (2007) 521–525.
[195] S.-H. Lin, R.-S. Juang, Adsorption of phenol and its derivatives from water using
[226] Y. Wang, B.-Y. Gao, W.-W. Yue, Q.-Y. Yue, Preparation and utilization of wheat
synthetic resins and low-cost natural adsorbents: a review, J. Environ. Manage.
straw anionic sorbent for the removal of nitrate from aqueous solution, J.
90 (2009) 1336–1349.
Environ. Sci. 19 (2007) 1305–1310.
[196] T.R. Bastami, M.H. Entezari, Activated carbon from carrot dross combined with
[227] P.C. Mishra, R.K. Patel, Use of agricultural waste for the removal of nitrate
magnetite nanoparticles for the efficient removal of p-nitrophenol from aqueous
nitrogen from aqueous medium, J. Environ. Manage. 90 (2009) 519–522.
solution, Chem. Eng. J. 210 (2012) 510–519.
[228] M. Karimi, M.H. Entezari, M. Chamsaz, Sorption studies of nitrate ion by a
[197] M. Sathishkumar, A.R. Binupriya, D. Kavitha, R. Selvakumar, R. Jayabalan, J.G.
modified beet residue in the presence and absence of ultrasound, Ultra. Sono-
Choi, S.E. Yun, Adsorption potential of maize cob carbon for 2,4-dichlorophenol
chem. 17 (2010) 711–717.
removal from aqueous solutions: equilibrium, kinetics and thermodynamics
[229] H. Paudyal, B. Pangeni, K. Inoue, H. Kawakita, K. Ohto, K.N. Ghimire, H. Harada, S.
modeling, Chem. Eng. J. 147 (2009) 265–271.
Alam, Adsorptive removal of trace concentration of fluoride ion from water by
[198] O. Hamdaoui, E. Naffrechoux, Modeling of adsorption isotherms of phenol and
using dried orange juice residue, Chem. Eng. J. 223 (2013) 844–853.
chlorophenols onto granular activated carbon. Part II. Models with more than
[230] A.C.A. de Lima, R.F. Nascimento, F.F. de Sousa, J.M. Filho, A.C. Oliveira, Modified
two parameters, J. Hazard. Mater. 147 (2007) 401–411.
coconut shell fibers: a green and economical sorbent for the removal of anions
[199] O. Hamdaoui, E. Naffrechoux, Modeling of adsorption isotherms of phenol and
from aqueous solutions, Chem. Eng. J. 185–186 (2012) 274–284.
chlorophenols onto granular activated carbon. Part I. Two-parameter models
[231] O.M. Akpa, E.I. Unuabonah, Small-sample corrected akaike information criteri-
and equations allowing determination of thermodynamic parameters, J. Hazard.
on: an appropriate statistical tool for ranking of adsorption isotherm models,
Mater. 147 (2007) 381–394.
Desalination 272 (2011) 20–26.
[200] S. Mubarik, A. Saeed, Z. Mehmood, M. Iqbal, Phenol adsorption by charred
[232] H. Akaike, A new look at the statistical model identification, IEEE Trans. Autom.
sawdust of sheesham (Indian rosewood; Dalbergia sissoo) from single, binary
Control. 19 (1974) 716–723.
and ternary contaminated solutions, J. Taiwan. Inst. Chem. Eng. 43 (2012) 926–
[233] E. Gayawan, S.B. Adebayo, R.A. Ipinyomi, B.A. Oyejola, Modeling fertility curves
933.
in Africa, Demogr. Res. 22 (2010) 211–236.
[201] B. Agarwal, C. Balomajumder, P.K. Thakur, Simultaneous co-adsorptive removal
[234] A. Kapoor, R.T. Yang, Surface-diffusion on energetically heterogeneous surfaces,
of phenol and cyanide from binary solution using granular activated carbon,
AIChE J. 35 (1989) 1735–1738.
Chem. Eng. J. 228 (2013) 655–664.
[235] V.S. Mane, I.D. Mall, V.C. Srivastava, Kinetic and equilibrium isotherm studies for
[202] N.Z. Al-Mutairi, 2,4-Dinitrophenol adsorption by date seeds: effect of physico-
the adsorptive removal of Brilliant Green dye from aqueous solution by rice husk
chemical environment and regeneration study, Desalination 250 (2010) 892–901.
ash, J. Environ. Manage. 84 (2007) 390–400.
[203] A.E. Ofomaja, E.I. Unuabonah, Kinetics and time-dependent Langmuir modeling
[236] F.M. Machado, C.P. Bergmann, T.H.M. Fernandes, E.C. Lima, B. Royer, T. Calvete,
of 4-nitrophenol adsorption onto Mansonia sawdust, J. Taiwan Inst. Chem. Eng.
S.B. Fagan, Adsorption of Reactive Red M-2BE dye from water solutions by multi-
44 (2013) 566–576.
walled carbon nanotubes and activated carbon, J. Hazard. Mater. 192 (2011)
[204] M. Ahmaruzzaman, D.K. Sharma, Adsorption of phenols from wastewater, J.
1122–1131.
Colloid Interface Sci. 287 (2005) 14–24.

[205]