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G Model

JECE 263 1–17

Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering


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

1
2 Review

3 Relevance of isotherm models in biosorption of pollutants by agricultural


4 byproducts
5 Q1 S. Rangabhashiyam, N. Anu, M.S. Giri Nandagopal, N. Selvaraju *
6 Department of Chemical Engineering, National Institute of Technology Calicut, Kozhikode 673601, Kerala, India

A R T I C L E I N F O A B S T R A C T

Article history: Industries generating wastewater with elevated concentrations of pollutants (e.g. metals, dyes, phenolic
Received 1 October 2013 compounds, anions, etc.) need specialized treatment 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
Wastewater treatment
biosorbent. This paper presents a state of the art on the review of adsorption isotherm models in an
Pollutants exhaustive manner on the basis of two, three, four and five parameters respectively. Focuses on the
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.
ß 2014 Published by Elsevier Ltd.

7
8 Contents

9 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
10 Biosorption and the characteristic features of the biosorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
11 Adsorption isotherm models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
12 Two parameter isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
13 The Langmuir Isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
14 The Freundlich isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
15 The Temkin isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
16 The Dubinin–Radushkevich isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
17 The Flory–Huggins isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
18 The Elovich isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
19 The Fowler–Guggenheim isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
20 The Kiselev isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
21 The Hill–de Boer model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
22 The Jovanovic isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
23 The Halsey isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
24 The Harkin–Jura isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
25 Three parameter isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
26 The Redlich–Peterson isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
27 The Hill isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
28 The Toth isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
29 The Jossens isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000

* 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 ß 2014 Published by Elsevier Ltd.


http://dx.doi.org/10.1016/j.jece.2014.01.014

Please cite this article in press as: S. Rangabhashiyam, et al., Relevance of isotherm models in biosorption of pollutants by agricultural
byproducts, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.01.014
G Model
JECE 263 1–17

2 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

30 The Fritz–Schlunder isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000


31 The Sips isotherm model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
32 The Koble–Corrigan isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
33 The Khan isotherm model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
34 The Radke–Prausnitz isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
35 The Frumkin isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
36 The Liu isotherm model [87] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
37 Four parameter isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
38 The Weber–van Vliet isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
39 The Fritz–Schlunder isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
40 The Baudu isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
41 Five parameter isotherms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
42 The Fritz–Schlunder isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
43 BET isotherm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
44 Adsorption isotherm models in the assessment of biosorbents for different pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
45 Adsorption isotherm model significance in the biosorbent evaluation for metal removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
46 Adsorption isotherm model significance in the biosorbent evaluation for dye removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
47 Adsorption isotherm model significance in the biosorbent evaluation for phenolic removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
48 Adsorption isotherm model significance in the biosorbent evaluation for anions removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
49 The selection of isotherm model for the adsorption studies [231] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
50 Error function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
51 Average relative error . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
52 Sum of squares of the error . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
53 Determination coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
54 Adjusted determination coefficient. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
55 Error function [179,236] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
56 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
57 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
58 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
59

Nomenclature
KFG Fowler–Guggenheim equilibrium constant
(L/mg)
Ce equilibrium concentration of adsorbate (mg/L)
uFG, uK, uH fractional coverage
qe adsorbate adsorbed per gram of the adsor-
W interaction energy between adsorbed
bent at equilibrium (mg/g)
molecules (kJ/mol)
Q0 monolayer coverage capacity (mg/g)
K1K Kiselev equilibrium constant (L/mg)
KL Langmuir isotherm constant (L/mg)
kn constant of complex formation between
RL separation factor or equilibrium parameter
adsorbed molecules
C0 adsorbate initial concentration (mg/L)
K1H Hill–de Boer constant (L/mg)
Kf Freundlich isotherm constant
K2 energetic constant of the interaction
(mg1(1/n) L1/n g1)
between adsorbed molecules (J/mol)
n adsorption intensity
Kj Jovanovic isotherm constant (L/mg)
AT Temkin isotherm equilibrium binding con-
KH Halsey isotherm constant
stant (L/mg)
nH Halsey equation exponents
bT Temkin isotherm constant
AH Harkins–Jura isotherm parameter
R universal gas constant (8.314 J/mol K)
B2 Harkins–Jura isotherm constant
T absolute temperature (K)
KRP Redlich–Peterson model isotherm constant
B heat of sorption constant (J/mol)
(L/g)
K Dubinin–Radushkevich isotherm constant
aRP Redlich–Peterson model constant (mg/L)g
related to the adsorption energy (mol2/kJ2)
g Redlich–Peterson model exponent
Qm theoretical isotherm saturation capacity
qsH Hill isotherm maximum uptake saturation
(mg/g)
(mg/L)
e Polanyi potential
KD Hill constant
E mean free energy (kJ/mol)
nH Hill cooperativity coefficient of the binding
KFH Flory–Huggins equilibrium constant (L/mg)
interaction
nFH model exponent
KT Toth equilibrium constant
DG8 Gibbs free energy (kJ/mol)
TT Toth model exponent
u degree of surface coverage of adsorbent
H, F, p parameters of the Jossens equation
surface
qmFS Fritz–Schlunder maximum adsorption
KE Elovich equilibrium constant (L/mg)
capacity (mg/g)
qm Elovich maximum adsorption capacity
KFS Fritz–Schlunder equilibrium constant (L/mg)
(mg/g)

Please cite this article in press as: S. Rangabhashiyam, et al., Relevance of isotherm models in biosorption of pollutants by agricultural
byproducts, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.01.014
G Model
JECE 263 1–17

S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 3

[13,14], and dyes [15–17]. A general modelling of the sorption 84


mFS Fritz–Schlunder model exponent isotherms under 4 particular cases (C, L, H and S isotherm 85
qms Sips maximum adsorption capacity (mg/g) respectively) with 4 main shapes of isotherm were commonly 86
KS Sips equilibrium constant (L/mg)ms observed [18]. The adsorption isotherm does not provide 87
mS Sips model exponent automatically any information about the reactions involved in 88
the adsorption phenomenon. Therefore, mechanistic interpreta- 89
a Koble–Corrigan parameter(Ln mg1n/g)
tions must be carefully verified for the appropriate measurements 90
b Koble–Corrigan parameter(L/mg)n
and interpretations of isotherm data [19]. In order to investigate 91
bK Khan isotherm model constant
novel adsorbents in the ideal adsorption system, it is essential to 92
qs theoretical isotherm saturation capacity introduce the most appropriate adsorption equilibrium correlation 93
(mg/g) [20], which is important for reliable prediction of adsorption 94
nK Khan model exponent parameters and for the quantitative comparison of adsorbent 95
qmRPI, qmRPII, Radke–Prausnitz maximum adsorption behaviour under different adsorbent systems or different experi- 96
qmRPIII capacities (mg/g) mental conditions [21,22]. With this perception, equilibrium 97
KRPI, KRPII, Radke–Prausnitz equilibrium constants relationships also known as the adsorption isotherms describes 98
KRPIII how pollutants interact with the adsorbent materials, critical for 99
mRPI, mRPII, optimization of the adsorption mechanism pathways, expression 100
Radke–Prausnitz models exponents
of the surface properties and capacities of adsorbents and effective 101
mRPIII
design of the adsorption systems [23,24]. 102
f interaction coefficient of the Frumkin
equation
Biosorption and the characteristic features of the biosorbents 103
KFF equilibrium constant of Frumkin equation
Kg Liu equilibrium constant (L/mg) Biosorption is a potential alternative technique for the removal 104
nL dimensionless exponent of the Liu equation of organic pollutants like metals, dyes and phenolics from 105
P1, P2, P3, P4 parameters of Weber–van Vliet equation wastewaters. Agricultural byproducts of various origins serve as 106
A, B Fritz–Schlunder parameters the biosorbents are known to bind with the pollutants [25,26]. Use 107
a, b Fritz–Schlunder equation exponents of agricultural, botanical residues in biosorption process suggests 108
qm0 Baudu maximum adsorption capacity (mg/g) the following importance over other unitary operations. (1) The 109
b0 equilibrium constant materials are usually highly economical. (2) There is no need of 110
costly growth media and maintenance of aseptic conditions. (3) 111
x, y Baudu parameters
The process is independent of physiological constraints of living 112
qmFS5 Fritz–Schlunder maximum adsorption
cells. (4) Reversible process, the biosorbent can be subjected for the 113
capacity (mg/g) further recycle. (5) The formation of chemical or biological sludge 114
K1, K2, m1, m2 Fritz–Schlunder parameters is minimized [27]. 115
CBET BET adsorption isotherm relating to the The biomass source of agricultural byproducts includes wood, 116
energy of surface interaction (L/mg) short rotation woody crops, agricultural wastes, short rotation 117
Cs adsorbate monolayer saturation herbaceous species, wood wastes, bagasse, sawdust, biosolids, 118
concentration (mg/L) grass, etc. [28]. Most of the organic materials are produced from 119
the sources of plants, trees and crops. The two major carbohydrates 120
having significant value are cellulose and hemicelluloses [29]. 121
Cellulose, a remarkable pure organic polymer comprised exclu- 122
60 Introduction sively of the units of anhydroglucose and bound together through 123
giant straight chain molecule [30]. These anhydroglucose units are 124
61 The global increase in water pollution has augmented bound together by b-(1,4)-glycosidic linkages. Through intramo- 125
62 awareness among the public and more attention has been focused lecular and intermolecular hydrogen bonds between OH groups 126
63 to combat the problem [1]. The major cause of water pollution is within the same cellulose chain and the surrounding cellulose 127
64 the industrial activities [2]. Conventional methods used for the chains, the chains tend to be arranged parallel and form a 128
65 removal of wastewater pollutants include chemical precipitation, crystalline super molecular structure [31]. Cellulose is insoluble in 129
66 ion exchange, filtration, reverse osmosis, electrochemical treat- most of the solvents and has a low accessibility to acid and 130
67 ment, electrodialysis and adsorption on activated carbon. In enzymatic hydrolysis. Hemicelluloses consist of different mono- 131
68 comparison of all the methods, adsorption plays as the most saccharide units and the polymer chains have short branches and 132
69 versatile and widely used method for the removal of pollutants are amorphous in nature, which makes it partially soluble or 133
70 because of its cost effectiveness, simplicity of design and operation swellable in water. Hemicellulose occurs as much shorter molecule 134
71 and high removal capacity [3,4]. Adsorption has been revealed as chains in comparison with cellulose [32]. Xylose is the most 135
72 the most promising and widely used method for the removal of important sugar component in the hemicelluloses. In hardwood 136
73 both inorganic and organic pollutants from contaminated water xylan, the xylose units act as the backbone linked by means of b- 137
74 [5]. Activated carbon with the properties of higher surface area, (1,4)-glycosidic bonds and branched by a-(1,2)-glycosidic bonds 138
75 good adsorption capacity and fast kinetics is used for the with 4-omethylglucuronic acid groups [31]. In case of the softwood 139
76 adsorption of pollutants from contaminated water. The use of xylan, the acetyl groups fewer distributed in the backbone chain 140
77 activated carbon in adsorption process is based on the surface and has additional branches composed of arabino furanose units 141
78 chemistry and pore structure of porous carbons [6,7]. Activated linked by means of a-(1,3)-glycosidic bonds. Hemicelluloses are 142
79 carbon is expensive and this setback, limits its employment on a highly soluble in alkali gets easily hydrolyzed [33–35]. Lignins are 143
80 large industrial scale application. Therefore cost-effective materi- polymers of aromatic compounds provides structural strength, 144
81 als are needed [8]. Biosorption subjecting agricultural byproducts sealing of water conducting system that links roots with leaves, 145
82 acts as the economic and pragmatic method for the removal of and protect plants against degradation [36]. Lignin a macromole- 146
83 different pollutants like heavy metals [9,10], COD [11,12], phenol cule consists of alkylphenols and has a complex three-dimensional 147

Please cite this article in press as: S. Rangabhashiyam, et al., Relevance of isotherm models in biosorption of pollutants by agricultural
byproducts, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.01.014
G Model
JECE 263 1–17

4 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Fig. 1. The chemical structure of major organic compounds of agricultural byproduct.

148 structure. Lignin is covalently linked with xylans in the case of Two parameter isotherms 186
149 hardwoods and with galactoglucomannans in softwoods [37]. The
150 basic chemical phenylpropane units of lignin are bonded together The Langmuir Isotherm model 187
151 through a set of linkages in such a way to form a very complex This model describes quantitatively about the formation of a 188
152 matrix. This matrix comprises of various functional groups like monolayer adsorbate on the outer surface of the adsorbent and 189
153 hydroxyl, methoxyl and carbonyl imparts a high polarity to the after that no further adsorption takes place. The Langmuir 190
154 lignin macromolecule [31,38]. The basic chemical structures of represents the equilibrium distribution of adsorbate between 191
155 cellulose, hemicelluloses, xylose and lignin were shown in Fig. 1. the solid and liquid phases [45]. The Langmuir adsorption isotherm 192
156 A biosorption process performed through several modes. The the most widely used isotherm for the biosportion of pollutants 193
157 batch and continuous modes of operation are the often employed from a liquid solution based on the following hypotheses. (1) 194
158 modes in order to conduct laboratory scale biosorption processes. Monolayer adsorption. (2) Adsorption takes place at specific 195
159 In most of the industrial applications the continuous mode of homogeneous sites on the adsorbent. (3) Once a pollutant occupies 196
160 operations are employed but for the evaluation of fundamental in a site; no further adsorption can take place in that site. (4) 197
161 information’s like biosorbent efficiency, optimum experimental Adsorption energy is constant and does not depend on the degree 198
162 conditions, biosorption rate and possibility of biosorbent regener- of occupation of an adsorbent’s active centres. (5) The strength of 199
163 ation batch experiments are deployed [26]. the intermolecular attractive forces is believed to fall off rapidly 200
with distance. (6) The adsorbent has a finite capacity for the 201
164 Adsorption isotherm models pollutant. (7) All sites are identical and energetically equivalent. 202
(8) The adsorbent is structurally homogeneous. (9) There is no 203
165 Adsorption isotherm indicates the graphical representation of interaction between molecules adsorbed on neighbouring sites 204
166 the relationship between the amount adsorbed by a unit weight of [41]. Based upon these assumptions, Langmuir represented the 205
167 adsorbent and the amount of adsorbate remaining in a test following equation: 206
168 medium at a constant temperature under equilibrium condition. It
Q 0K LCe
169 gives the information about the distribution of adsorbable solute qe ¼ (1)
1 þ K LCe
170 between the liquid and solid phases at various equilibrium
171 concentrations. The data under the study of adsorption isotherm where Ce is the equilibrium concentration of adsorbate (mg/L), qe 207
208
172 are to be specific for each system and the determination of denotes the adsorbate adsorbed per gram of the adsorbent at 209
173 isotherm are to be carried out for every application [39]. The equilibrium (mg/g), Q0 represents the monolayer coverage 210
174 different types of the equilibrium isotherm models (Langmuir, capacity (mg/g) and KL is the Langmuir isotherm constant (L/mg). 211
175 Freundlich, Temkin, Dubinin–Radushkevich, Flory–Huggins, Elo- The essential features of the Langmuir isotherm may be 212
176 vich, Fowler–Guggenheim, Kiselev, Hill–de Boer, Jovanovic, Halsey, expressed in terms of equilibrium parameter RL, a dimensionless 213
177 Harkin–Jura, Redlich–Peterson, Hill, Toth, Jossens, Fritz–Schlunder, constant, referred to as separation factor or equilibrium parameter 214
178 Sips, Koble–Corrigan, Khan, Radke–Prausnitz, Frumkin, Liu, Weber [46]: 215
179 –van Vliet, Baudu) have been put together on the basis of three
180 fundamental approaches [38,40]. Kinetic consideration [41], 1
RL ¼ (2)
181 thermodynamics [42,43] and potential theory [44]. The availability 1 þ K LC0
182 of the two, three, four and five parameter adsorption isotherm are where C0 is the adsorbate initial concentration (mg/L), KL is the 216
217
183 represented in Fig. 2, those isotherm models can be subjected for constant related to the energy of adsorption (Langmuir constant). 218
184 the investigation of novel biosorbents for the removal of RL value indicates the adsorption nature of unfavourable if RL > 1, 219
185 wastewater pollutants. linear if RL = 1, favourable if 0 < RL < 1 and irreversible if RL = 0. 220

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Adsorption isotherm models

1450parameter isotherm
Two Three parameter isotherm Four parameter isotherm Five parameter isotherm

1452
1. Redlich–Peterson 1. Fritz–Schlunder
1. Langmuir 1. Weber–van Vliet
1453 2. Hill 2. Fritz–Schlunder
2. Freundlich
3. Toth 3. Baudu
3.1454
Temkin
4. Jossens
4. Dubinin–Radushkevich
5. Fritz–Schlunder
1455ry–Huggins
5.Flo
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.

221 The Freundlich isotherm model where AT is the Temkin isotherm equilibrium binding constant (L/ 251
250
222 The Freundlich equilibrium isotherm equation is an empirical mg), bT is the Temkin isotherm constant R is the universal gas 252
223 equation used for the description of multilayer adsorption with constant (8.314 J/mol K), T is the temperature (K), B is the constant 253
224 interaction between adsorbed molecules: related to heat of sorption (J/mol) [52]. The Temkin equation better 254
1=n
holds for the prediction of gas phase equilibria. Nevertheless, in 255
qe ¼ K f Ce (3) case of liquid phase adsorption particularly of heavy metals using 256
biosorbent, this model fall-short in representing the equilibrium 257
226
225 where Kf is the Freundlich isotherm constant (mg1(1/n) L1/n g1), n data. In comparison with the gas phase adsorption, the liquid phase 258
227 represents the adsorption intensity, Ce indicates the equilibrium is a more complex phenomenon since the adsorbed molecules do 259
228 concentration of adsorbate (mg/L), qe is the amount of adsorbate not necessarily organized in a tightly packed structure with 260
229 adsorbed per gram of the adsorbent at equilibrium (mg/g). identical orientation. The solvent molecules and micelles forma- 261
230 The model is applicable to the adsorption on heterogeneous tion from adsorbed molecules add to the complexity of liquid 262
231 surfaces by a uniform energy distribution and reversible adsorp-
phase adsorption. Many factors such as pH, adsorbate solubility in 263
232 tion. The Freundlich equation implies that adsorption energy the solvent, temperature and surface chemistry of the adsorbent 264
233 exponentially decreases on the finishing point of adsorptional
influence the adsorption from liquid phase. The Temkin equation is 265
234 centres of an adsorbent [47]. The Freundlich constants are often not suitable for representation of experimental data of the 266
235 empirical constants depends on many environmental factors.
liquid phase adsorption in complex systems, since the derivation 267
236 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 268
237 non-linearity between solution concentration and adsorption [48].
complex phenomenon in liquid phase adsorption are not taken 269
238 If the value of 1/n is equal to 1, the adsorption is linear [49]. Henry’s into account [53]. 270
239 isotherm or one parameter isotherm is applicable for linear
240 adsorption under the condition when n = 1 in Eq. (3). The Dubinin–Radushkevich isotherm model 271
The Dubinin–Radushkevich isotherm can be applied for the 272
241 The Temkin isotherm model estimation of apparent free energy and the characteristics of 273
242 Temkin equation, the early model proposed to depict adsorp-
adsorption [44,54,55]. The Dubinin–Radushkevich equation de- 274
243 tion of hydrogen on platinum electrodes within acidic solutions. fined by the following equation [56,57]: 275
244 The derivation of the Temkin isotherm based on the assumption
245 that the decline of the heat of sorption as a function of temperature
qe ¼ Q m expðK e2 Þ (6)
246 is linear rather than logarithmic, as implied in the Freundlich
247 equation [50,51]. The model is given by the following equation:
where K is the Dubinin–Radushkevich isotherm constant related to 276
277
RT the adsorption energy (mol2/kJ2), Qm is the theoretical isotherm 278
qe ¼ lnðAT C e Þ (4)
B saturation capacity (mg/g), e is the Polanyi potential, calculated 279
from Eq. (7): 280
249
248 where
 
RT 1
B¼ (5) e ¼ RT ln 1 þ (7)
bT Ce

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282
281 where R is the gas constant (8.314 J/mol K) and T is the Fowler–Guggenheim equation will reduce to the Langmuir 334
283 temperature (K). The mean free energy E (kJ/mol) of sorption equation. 335
284 can be found by using K values represented in Eq. (8).
The Kiselev isotherm model 336
1 The adsorption isotherm [64] in localized monomolecular layer 337
E ¼ pffiffiffiffiffiffiffi (8)
2K expressed by the equation 338

287
286
285 The Dubinin–Radushkevich isotherm model is a temperature uK
288 dependent, when the adsorption data at different temperatures k1K C e ¼ (13)
ð1  uK Þð1 þ kn uK Þ
289 plotted as a function of logarithm of amount adsorbed versus the
290 square of potential energy, all suitable data will lie on the same where k1K is the Kiselev equilibrium constant (L/mg), and kn is the 339
340
291 curve, referred to as the characteristic curve [58–60]. constant of complex formation between adsorbed molecules. 341

292 The Flory–Huggins isotherm model The Hill–de Boer model 342
293 Flory–Huggins isotherm model [61] derives the degree of This model [65,66] describes the mobile adsorption and lateral 343
294 surface coverage characteristics of adsorbate onto adsorbent, interaction among adsorbed molecules 344
295 express the feasibility and spontaneous nature of an adsorption
 
296 process. u indicates the degree of surface coverage of adsorbent uH uH K 2 uH
297 surface, KFH and nFH are the Flory–Huggins equilibrium constant (L/ K 1H C e ¼ exp  (14)
1  uH 1  uH RT
298 mg) and model exponent. The equilibrium constant KFH used to
299 calculate the spontaneity of Gibbs free energy (DG8). The equation where K 1H is the Hill–de Boer constant (L/mg), K2 is the energetic 345
346
300 of the Flory–Huggins isotherm is as follows: constant of the interaction between adsorbed molecules (J/mol). 347
A positive K2 value indicates the attraction between adsorbed 348
u nFH
¼ K FH ð1  u Þ (9) species and a negative value means repulsion. The apparent 349
C0
affinity is increased with loading when there exist the attraction 350
302
301 The degree of surface coverage of adsorbent surface calculated between adsorbed species and it is decreased with loading when 351
303 using the following equation: there is repulsion among the adsorbed species. When there is no 352
interaction between adsorbed molecules (i.e. K2 = 0), the Hill–de 353
Ce Boer equation will be reduced to the Volmer equation. 354
u ¼1 (10)
C0
The Jovanovic isotherm model 355
304
305 An adsorption surface assumption considered in this model [67] 356
306 The Elovich isotherm model is similar to that considered by Langmuir. It corresponds to another 357
307 The equation defining the Elovich model based on the kinetic approximation for monolayer localized adsorption without lateral 358
308 principle with the assumption of adsorption sites increase interactions. This model is similar to that of Langmuir model, 359
309 exponentially with adsorption, which implies a multilayer except that the allowance is made in the former for the surface 360
310 adsorption [62]. The model is expressed by the relation: binding vibrations of an adsorbed species. This model shown by 361
  using the following nonlinear relationship 362
qe q
¼ K E C e exp  e (11)
qm qm
qe ¼ qm ð1  eK j C e Þ (15)
312
311 where KE represents the Elovich equilibrium constant (L/mg), qm is
where Kj is the Jovanovic isotherm constant (L/mg), qm is the 363
364
313 the Elovich maximum adsorption capacity (mg/g).
maximum adsorption capacity in Jovanovic model (mg/g). 365
314 The Fowler–Guggenheim isotherm model
The Halsey isotherm model 366
315 For the derivation of this isotherm equation, takes in account of
Adsorption isotherm equation of this model [68] given as 367
316 the lateral interaction of the adsorbed molecules [63]. The model
follows: 368
317 has the following explicit form:
   
uFG 2uFG W ln K H  ln C e
K FG C e ¼ exp (12) qe ¼ exp (16)
1  uFG RT nH

319
318 where KFG is the Fowler–Guggenheim equilibrium constant (L/mg), where KH represents the Halsey isotherm constant, nH represents 369
370
320 uFG is the fractional coverage, W is the interaction energy between the Halsey equation exponents. 371
321 adsorbed molecules (kJ/mol). Eq. (18) is appropriate for the multilayer adsorption and the 372
322 Fowler–Guggenheim equation is the simplest equations with fitting of the experimental data to this equation confirms to the 373
323 the consent to the lateral interaction. The heat of adsorption varies heteroporous nature of the adsorbent. 374
324 linearly with loading. If the interaction between the adsorbed
325 molecules is attractive (i.e. W is positive), the heat of adsorption The Harkin–Jura isotherm model 375
326 will increase with loading. This is because of the increased The adsorption isotherm equation of this model [69] expressed 376
327 interaction between adsorbed molecules as the loading increases. as follows: 377
328 This means that if the measured heat of adsorption shows an  1=2
329 increase with respect to loading, it indicates the positive lateral AH
qe ¼ (17)
330 interaction between adsorbed molecules. Conversely, if the B2  log C e
331 interaction among adsorbed molecules is repulsive (i.e. W is
332 negative), the heat of adsorption shows a decrease with loading. In where AH is the Harkins–Jura isotherm parameter, B2 is the 378
379
333 the case of no interaction between adsorbed molecules (i.e. W = 0), Harkins–Jura isotherm constant. 380

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381 Three parameter isotherms The Fritz–Schlunder isotherm model 428


The Fritz–Schlunder [80] equation has been represented in the 429
382 The Redlich–Peterson isotherm model following form: 430
383 Redlich and Peterson included the features of both the
qmFS K FS C e
384 Langmuir and Freundlich isotherms into a single equation qe ¼ (24)
385 presented as follows: 1 þ qm CemFS
where qmFS is the Fritz–Schlunder maximum adsorption capacity 431
432
K RP C e (mg/g), KFS is the Fritz–Schlunder equilibrium constant (L/mg), and 433
qe ¼ (18)
1 þ aRP Ceg mFS is the Fritz–Schlunder model exponent. 434

387
386 where KRP is the Redlich–Peterson model isotherm constant (L/g), The Sips isotherm model 435
388 aRP is the Redlich–Peterson model constant (mg/L)g; g is the By identifying the problem of continuing increase in the 436
389 Redlich–Peterson model exponent, should be 0 < g  1. When g = 1 adsorbed amount with an increase in concentration in the 437
390 the Redlich–Peterson equation becomes the Langmuir equation: Freundlich equation, Sips [81] proposed an equation similar in 438
form to the Freundlich equation, but it has a finite limit when the 439
K RP C e concentration is sufficiently high: 440
qe ¼ (19)
1 þ aRP C e
qms K S Cems
qe ¼ (25)
392
391 where g = zero it becomes the Henry’s law [70]. 1 þ K s Cems
where qms is the Sips maximum adsorption capacity (mg/g), KS is 442
441
K RP C e
qe ¼ (20) the Sips equilibrium constant (L/mg)ms, and mS is the Sips model 443
1 þ aRP exponent, limited from 0 to 1. At the low adsorbate concentrations 444
the Sips isotherm model effectively reduces to the Freundlich 445
393
394
isotherm and thus does not obey Henry’s law. And at high 446
395 The Hill isotherm model
adsorbate concentrations, this model predicts a monolayer 447
396 Hill equation [71], from the non-ideal competitive adsorption
sorption capacity characteristic of the Langmuir isotherm [22]. 448
397 [72] model, and postulated to explain about the binding of
398 different species onto homogeneous substrates. The model
The Koble–Corrigan isotherm model 449
399 assumes that adsorption process as a cooperative phenomenon,
Koble–Corrigan model [82] is the three-parameter empirical 450
400 with the ligand binding ability at one site on the macromolecule,
model based on the combination of both the Langmuir and 451
401 may influence the different binding sites on the same macromole-
Freundlich isotherm equations representing in one non-linear 452
402 cule [73].
equation of the equilibrium adsorption data. The model is 453
qsH CenH commonly expressed by Eq. (26): 454
qe ¼ (21)
K D þ CenH aCen
qe ¼ (26)
1 þ bCen
404
403 where qsH is the Hill isotherm maximum uptake saturation (mg/L),
where a (Lnmg1n/g), b (L/mg)n and n are the Koble–Corrigan 456
455
405 KD is the Hill constant, nH is the Hill cooperativity coefficient of the
parameters. 457
406 binding interaction.
This model is generally applied for heterogeneous sorbent 458
surface [83]. 459
407 The Toth isotherm model
408 Toth [74] modified the Langmuir equation in order to reduce
The Khan isotherm model 460
409 the error between experimental data and predicted values of
This model [84] suggests a generalized isotherm for the bi-solute 461
410 equilibrium adsorption data. The significance of the equation is
adsorption from dilute aqueous solution. The correlation repre- 462
411 best suited to multilayer adsorption, which is a special type of
sented in Eq. (27) has a unique characteristic by covering both 463
412 Langmuir isotherm and has very restrictive validity [75]. The Toth
extremes of the Langmuir and Freundlich isotherm. The generalized 464
413 correlation is given for the application to liquid–solid adsorption
equation for pure component adsorption isotherms as follows: 465
414 generally presented as [76–78].
qs bK C e
K T Ce qe ¼ n (27)
qe ¼ (22) ð1 þ bK C e Þ K
1=T T
½AT þ C e T T 
where bK is the Khan isotherm model constant, qs is the theoretical 467
466
416
415 where KT is the Toth equilibrium constant, and TT is the Toth model isotherm saturation capacity (mg/g), nK is the Khan model exponent. 468
417 exponent. When nK is equal to unity, Eq. (27) reduces to the Langmuir 469
isotherm. This equation at large value of Ce reduces to the 470
418 The Jossens isotherm model Freundlich isotherm. 471
419 This model is based on a distribution of the energy of
420 interactions adsorbate–adsorbent on adsorption sites [79]. The The Radke–Prausnitz isotherm model 472
421 model assumes that the activated carbon surface is heterogeneous, The three isotherms [85] of this model can be represented as 473
422 with respect to the interactions which it engages with the qmRPI K RPI C e
423 adsorbate: qe ¼ (28)
ð1 þ K RPI C e ÞmRPI
qe
Ce ¼ expðFqep Þ (23) qmRPII K RPII C e 475
474
H qe ¼ (29)
1 þ K RPII CemRPII
425
424 where H, F and p represent the parameters of the Jossens equation.
qmRPIII K RPIII CemRPIII 477
476
426 H and F depend only on temperature. Eq. (23) can be reduced to qe ¼ (30)
427 Henry’s law at low capacities. 1þ K RPII CemRPIII1

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479
478 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 528
527
480 adsorption capacities (mg/g), KRPI, KRPII and KRPIII are the Radke– b0, qm0, x, and y. 529
481 Prausnitz equilibrium constants, and mRPI, mRPII and mRPIII are the This model gives the transformed the Langmuir equation as 530
482 Radke–Prausnitz models exponents. expressed in Eq. (38) 531
ð1þxþyÞ
483 The Frumkin isotherm model qm0 b0 Ce
qe ¼ ð1þxÞ
with ð1 þ x þ yÞ and ð1 þ xÞ < 1 (38)
484 This is the three-parameter isotherm model [86,87] depicted in 1 þ b0 Ce
485 Eq. (31)
qm0 is the Baudu maximum adsorption capacity (mg/g), b0 is the 532
533
 
 fu equilibrium constant, and x and y are the Baudu parameters. 534
K FF C e ¼ u exp (31)
1u For lower surface coverage, Eq. (38) reduces to the Freundlich 535
486
487 where f is the interaction coefficient of the Frumkin equation, KFF equation, i.e. 536
488 indicates the equilibrium constant of Frumkin equation. ð1þxþyÞ
qm0 b0 Ce
qe ¼ (39)
489 The Liu isotherm model [87] 1 þ b0
490
537
538
Q max  K g CenL Five parameter isotherms 539
Qe ¼ (32)
1 þ K g CenL
The Fritz–Schlunder isotherm model 540
491
492 where Qe is the adsorption capacity (mg/g), Qmax is the maximum
This model represents a broad field of equilibrium data through 541
493 adsorption capacity of the adsorbent (mg/g), Kg is the Liu
the five-parameter empirical expression [80]. 542
494 equilibrium constant (L/mg), Ce is the adsorbate concentration
495 at the equilibrium (mg/L), nL is the dimensionless exponent of the qmFS5 K 1 Cem1
496 Liu equation. qe ¼ with m1 and m2  1 (40)
1 þ K 2 Cem2

497 Four parameter isotherms where qmFS5 is the Fritz–Schlunder maximum adsorption capacity 543
544
(mg/g) and K1, K2, m1, and m2 are the Fritz–Schlunder parameters. 545
498 The Weber–van Vliet isotherm model
499 Weber and van Vliet [88] proposed an empirical relation with BET isotherm 546
500 four parameters isotherm models in order to describe the
501 equilibrium data Brunauer et al. [90] developed an equation for the multilayer 547
adsorption and the expression has been represented as follows: 548
P
ðP2 qe 3 þP4 Þ
C e ¼ P 1 qe (33) qs C BET C e
qe ¼ (41)
502
503 where P1, P2, P3 and P4 are the isotherm parameters of Weber–van ðC s  C e Þ½1 þ ðC BET  1ÞðC e =C s Þ
504 Vliet equation.
In which CBET, BET adsorption isotherm relating to the energy of 549
550
surface interaction (L/mg), Cs, adsorbate monolayer saturation 551
505 The Fritz–Schlunder isotherm model
concentration (mg/L) 552
506 Four-parameter equation of another form of Langmuir–
507 Freundlich type developed empirically by Fritz and Schlunder
Adsorption isotherm models in the assessment of biosorbents 553
508 [80]. The equation of this model expressed as follows: for different pollutants 554
ACea
qe ¼ b
with a and b  1 (34) A functional expression for quantity of adsorption with 555
1 þ BCe
concentration of solute at a constant temperature. Adsorption 556
510
509 where A and B are the Fritz–Schlunder parameters, and a and b are properties and equilibrium data are commonly known as 557
511 the Fritz–Schlunder equation exponents. adsorption isotherms. The adsorption isotherms show the 558
512 At high liquid-phase concentrations of the adsorbate, Eq. (34) pollutants interaction with adsorbent materials and are thus 559
513 reduces to the Freundlich equation as shown in Eq. (35) critical in optimizing for the use of biosorbents [91,92]. In order to 560
optimize the design of an adsorption system to remove pollutant 561
A ab from wastewater, it is important to establish the most appropriate 562
qe ¼ C (35)
B e correlation for the equilibrium curve. An accurate mathematical 563
description of equilibrium adsorption capacity is indispensable for 564
515
514 where A/B and (a  b) present the parameters Kf and 1/n of the
516 Freundlich model. reliable prediction of adsorption parameters and quantitative 565
comparison of adsorption behaviour for different adsorbent 566
517 For a = b = 1, Eq. (34) reduces to the Langmuir equation, with
518 KL = B is the Langmuir adsorption constant (L/mg) related to the systems [22,49,92]. 567
519 energy of adsorption and A = KLQ0.
Adsorption isotherm model significance in the biosorbent evaluation 568
for metal removal 569
520 The Baudu isotherm model
521 The calculation of the Langmuir coefficients, KL and Q0, carried out
Special concern over the heavy metal remediation is due to the 570
522 through the measurement of tangents at the different equilibrium
523 concentrations. Shows that they are not constants in a broad recalcitrant and persistency nature of heavy metals in the 571
environment. The distributions of cellulosic agricultural waste 572
524 concentration range [89]. Their variations written as follows:
materials act as the copious source for significant metal biosorp- 573
K L ¼ b0 Cex (36) tion. The agricultural waste biomass consists of functional groups 574
like phenolic, amido, amino, acetamido, alcoholic, carbonyl, 575
526
525 Q 0 ¼ qm0 Cey (37) sulphydryl groups, etc. have affinity towards heavy metal ions 576

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577 in order to form metal complexes or chelates [93]. The design and comparison with the unmodified orange peel, the biosorption 643
578 analysis of biosorption process entails relevant biosorption capacity increased for modified biomass by 4.2-, 4.6- and 16.5-fold 644
579 equilibrium. At the equilibrium condition, a certain relationship for Pb2+, Cd2+ and Ni2+, respectively [102]. Pecan nutshell (Carya 645
580 exists between adsorbate and adsorbent. Their equilibrium illinoensis) used for the removal of Cu(II), Mn(II) and Pb(II) from 646
581 concentrations are a function of temperature. Initially several aqueous solutions. The effects such as, pH, biosorbent dosage was 647
582 adsorption isotherm models used for gas phase adsorption and considered in the study. Fractionary order kinetic model was 648
583 then those isotherm models were readily adopted to show observed as the best fitted kinetic model. The equilibrium data 649
584 relationship adsorption equilibrium in heavy metals biosorption were fitted to Langmuir, Freundlich, Redlich–Peterson and Sips 650
585 [94]. Biosorption has mainly been considered for heavy metal isotherm models. Sips isotherm model best fitted the equilibrium 651
586 removal in order to detoxify metal-bearing effluents. The process data. The maximum biosorption capacities of pecan nutshell were 652
587 features a high heavy metal selectivity and cost-effectiveness for found as 85.9, 98.0 and 195.9 mg/g for Cu(II), Mn(II) and Pb(II) 653
588 low metal concentrations as compared with ion exchange resins. respectively [103]. 654
589 There is also no hazardous sludge by-product generation in both Chemically modified orange peel subjected for the adsorption 655
590 processes and biosorbents can also be easily regenerated for of environmentally problematic metal ions namely Cd2+, Cu2+ and 656
591 multiple reuses [95]. Pb2+ from aqueous solutions. And the comparison made with the 657
592 Pinhao (Araucaria angustifolia) waste and pinhao loaded with original orange peel. The metals uptake by chemically modified 658
593 Congo red were investigated for the Cu(II) removal from aqueous orange peel shows rapid and the equilibrium time attained within 659
594 solutions. After optimizing the batch adsorption system through 30 min at constant temperature and pH. The mechanism of metal 660
595 statistical design of experiments, the adsorption equilibrium data adsorption by chemically modified orange peel gave good fits for 661
596 fitted to the Langmuir and Freundlich models. The maximum Freundlich and Langmuir models in comparison to the Dubinin– 662
597 adsorption capacity of pinhao waste and pinhao loaded with Congo Radushkevich isotherm model. The modified biosorption data 663
598 red for Cu(II) removal was found as 32.2 mg/g and 68.6 mg/g perfectly fits the Langmuir and Freundlich adsorption isotherms 664
599 respectively [96]. The evaluation of the feasibility of sugarcane models with determination coefficient > 0.95 for all the metal ions 665
600 bagasse carried out for the adsorption of nickel from aqueous Cd2+, Cu2+ and Pb2+ [104]. A lignocellulosic material extracted from 666
601 solution. The biosorption data were fitted to Langmuir, Freundlich rice husk (Oryza sativa) modified by iron coating through 667
602 and Sips isotherm models. The Langmuir model shows better hydrolization of ferric nitrate while adding an alkaline solution 668
603 representation of data, with determination coefficient greater than drop wise into the batch type reactor. The parameters studied 669
604 0.99 [97]. The sugar cane bagasse subjected as a selective solid includes pH, As(V) concentrations, contact times, ionic strength 670
605 phase extractor for Fe(III). Batch experiments were carried out at and adsorbent amounts. Maximum percentage removal of As(V) 671
606 the pH range 1.0–4.0, initial concentration of metal ion (10– ions 94% occurs at pH 4.0. The Langmuir model fitted the 672
607 100 mmol), weight of biosorbent (25, 50, 75, 100, 125 and 150 mg) equilibrium data better than Freundlich model and confirms the 673
608 and shaking time (10, 30, 45, 60, 90, 120 and 150 min). The surface homogeneity of adsorbent [105]. The adsorption of Cu(II) 674
609 equilibrium data better fits with Langmuir model in comparison by carbons prepared from rice husk through pyrolysis and steam 675
610 with the Freundlich model [98]. The yellow passion fruit shell activation were investigated. The Cu(II) adsorption on the rice husk 676
611 (Passiflora edulis Sims. f. flavicarpa Degener) was reported as an carried out with an optimum pH value of 5.0 and an equilibrium 677
612 biosorbent for the removal Cr(III) and Pb(II) from aqueous time of 24 h. The Langmuir isotherm model fits better the 678
613 solutions in batch studies. The effects of contact time and pH experimental data in comparison with the Freundlich isotherm, 679
614 were considered in the biosorption study. The biosorption kinetics Dubinin–Radushkevitch isotherm. The values of E obtained in D–R 680
615 followed the pseudo second order. The maximum removal capacity model found to be greater than 14 kJ/mol, indicating the 681
616 of yellow passion fruit shell were 85.1 and 151.6 mg/g for Cr(III) adsorption process as chemical ion-exchange process [106]. The 682
617 and Pb(II) respectively. The Langmuir isotherm model suitably magnitude of E between 8 and 16 kJ/mol corresponds to a chemical 683
618 fitted for both the metallic ions [99]. ion-exchange process while the value of E < 8 kJ/mol represents as 684
619 The capacity of Polyaniline coated on saw dust as synthetic physical nature process [107]. Coir pith chemically modified by 685
620 adsorbent investigated for the removal of Cd(II) ions from aqueous grafting with acrylic acid for the removal of Cr(VI). The maximum 686
621 solutions by means of batch operation. The optimum pH for Cr(VI) removal (99.99  0.07%) attained under the following 687
622 adsorption of Cd(II) found to be 6. Adsorption was rapid and conditions: 1.3% (w/v) dosage of acrylic acid-grafted coir pith, pH 688
623 occurred within 20 min for a cadmium concentration range of 10– of 2, contact time of 22 h, temperature of 30 8C, particle size of 689
624 40 mg/L. The equilibrium adsorption data for Cd(II) were better <150 mm and an initial Cr(VI) of 1171 mg/l. The adsorption isotherm 690
625 fitted to the Freundlich isotherm model in comparison with the of 2 M acrylic acid-grafted coir pith shows a good fit with the 691
626 Langmuir adsorption isotherm model [100]. Rubber wood (Hevea Langmuir isotherm in comparison with the Freundlich isotherm 692
627 brasiliensis) saw dust modified by the chemical treatment of [108]. 693
628 phosphoric acid and sodium hydroxide with different impregna- The garden grass was subjected for the biosorption of copper(II) 694
629 tion ratios in order to improve adsorption capacity for the removal from water. Copper adsorption depends on important parameters 695
630 of copper. The effects of variables like solution pH, temperature, like the pH, initial copper concentrations, contact time, adsorbent 696
631 adsorbent dose, initial copper concentration, on the removal of doses, temperature and particle sizes. The equilibrium data were 697
632 copper ions have been studied. Adsorption equilibrium data were well fitted by the Langmuir, Sips and Redlich–Peterson isotherm 698
633 fitted to the adsorption isotherm models like Langmuir, Freundlich models. The maximum biosorption of 58.34 mg/g was obtained for 699
634 Dubinin–Radushkevich and Temkin. The equilibrium data were 1 g dose [109]. Rice husk evaluated was evaluated for the 700
635 best represented by the Langmuir and Freundlich isotherms [101]. biosorption of U(VI). Biosorbent used in the form of native, SDS- 701
636 Grafted copolymerization-modified orange peel used for the treated and immobilized. The adsorption study parameters 702
637 biosorption of Pb2+, Cd2+ and Ni2+ ions from aqueous solution. investigated were pH, biosorbent dosage, contact time, initial 703
638 Langmuir and Freundlich isotherm models were applied to U(VI) concentration and temperature. Maximum biosorption 704
639 describe the biosorption. Langmuir model fits the equilibrium capacity for native (29.56 mg/g) and immobilized biomass 705
640 data better than the Freundlich isotherm. The maximum adsorp- (17.59 mg/g) followed with SDS-treated biomass showed maxi- 706
641 tion capacities found through the Langmuir equation, for Pb2+, Cd2+ mum removal of 28.08 mg/g. The Langmuir sorption isotherm 707
642 and Ni2+ ions were 476.1, 293.3 and 162.6 mg/g respectively. In model best fitted best with the U(IV) biosorption equilibrium data 708

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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]

709 [110]. The single and binary biosorption of copper and lead ions Langmuir isotherm and isotherm data of Acid Blue 7 follows 744
710 from aqueous solution carried out using rice straw. The modified Freundlich isotherm models [142]. The potential of lotus leaf for 745
711 extended-Langmuir model with incorporation of solute’s selectiv- the removal of methylene blue from aqueous solution was 746
712 ity factor gave good correlation results against binary adsorption investigated. The experiments performed under various conditions 747
713 data [111]. The biosorbents and the best fitted adsorption isotherm like solution pH, salt ionic strength, temperature, contact time, 748
714 model are shown in Table 1. adsorbent dose and initial methylene blue concentration. In order 749
to describe the adsorption behaviour, isotherm models like the 750
715 Adsorption isotherm model significance in the biosorbent evaluation Langmuir, Freundlich and Koble–Corrigan were employed. In 751
716 for dye removal comparison, the equilibrium data were perfectly represented by 752
Koble–Corrigan isotherm [143]. The study carried out by using 753
717 Dye decolourization now becomes the foremost difficulty for the palm kernel fibre for the removal of methylene blue and crystal 754
718 treatment plants of various industries like textiles, rubber, paper, violet from aqueous solutions. Adsorption studies parameters 755
719 plastics, leather, cosmetic, food, etc. yearly 10–15% of the synthetic includes the different initial dye concentrations (20, 40, 80 and 756
720 textile dyes used is lost to waste streams and of about 20% of these 160 mg/L), contact time, pH (1.0–11.0) and sorbent doses (0.4, 2.0, 757
721 losses enter the environment through effluent generated the 4.0 and 8.0 g/L). Adsorption data were modelled using Langmuir, 758
722 treatment plant [136]. The effluent generated is the most important Freundlich and Temkin adsorption isotherms. Equilibrium data of 759
723 threatening factor to the environment because it affects the biotic the biosorption process fitted very well to the Freundlich model 760
724 and the abiotic systems [137]. Biosorption represents a powerful (determination coefficient = 0.997 and 0.991 for methylene blue 761
725 technique for the dye removal. Biosorption process involves solid and crystal violet, respectively) [144]. Activated and non-activated 762
726 living or non-living biosorbent attracts a component to its surface carbonaceous materials of Brazilian pine-fruit-shell (A. angustifo- 763
727 from the aqueous solution and form an attachment through a lia) were tested for the removal of Procion Red MX 3B dye from 764
728 physical or chemical bond, thereby removing the component from aqueous solutions. Procion Red MX 3B dye uptake was higher at 765
729 the liquid phase [138,139]. Agricultural byproducts hold significant the pH range of 2–3 for non-activated carbonaceous adsorbent and 766
730 potential for the removal of the toxic dye substances from the 2–7 for activated carbonaceous adsorbent. For the adsorption 767
731 effluent discharging into the water bodies [140]. equilibrium data, the Ferror values of the Sips isotherm model were 768
732 Rhodamine 6G removal from aqueous solutions carried out by at least 4.0 lower than the values of Langmuir, Freundlich and 769
733 almond shell (Prunus dulcis) in a batch technique. The investigation Redlich–Peterson isotherm models [145]. The activated carbon 770
734 carried out with the consideration of parameters like pH, contact from bamboo culms wastes were employed for the removal of 771
735 time, Rhodamine 6G concentration, almond shell concentration, Disperse Red 167. The adsorption isotherm data were fitted to nine 772
736 temperature etc. The biosorption pattern of Rhodamine 6G onto non-linear adsorption isotherm models. The Akaike Information 773
737 almond shell well fits with both the Langmuir and Freundlich Criterion analysis was confirmed as the best statistical tool for 774
738 isotherm models. Through the Langmuir model equations biosorp- analyzing the data obtained. Temkin isotherm equation best 775
739 tion capacity of almond shell found to be as 32.6 mg/g [141]. The described the adsorption isotherm data [146]. The Brazilian pine 776
740 adsorption of Acid Black 26, Acid Green 25 and Acid Blue 7 fruit shell (A. angustifolia) was tested as biosorbent for the removal 777
741 investigated on Pine Cone. Equilibrium isotherms were analyzed of non-hydrolyzed reactive red 194 and hydrolyzed reactive red 778
742 using Langmuir, Freundlich and Tempkin adsorption models. The 194 dyes from aqueous solutions. Chemical treatments of Brazilian 779
743 isotherm data of Acid Black 26 and Acid Green 25 follows the pine fruit shell, with chromium, with acid and with acid followed 780

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781 by chromium were carried out in the study. The adsorption data and Halsey isotherm equations respectively. The highest values of 847
782 were fitted to Langmuir, Freundlich, Sips and Redlich–Peterson determination coefficient (0.997) were obtained with Langmuir 848
783 isotherm models. For non-hydrolyzed reactive red 194 reactive dye isotherm model [155]. 849
784 the equilibrium data were best fitted to the Sips isotherm using Meranti (Philippine mahogany) sawdust showed strong scaveng- 850
785 raw and acid treated biosorbent and Redlich–Peterson isotherm ing behaviour towards methylene blue through adsorption from 851
786 using chromium treated pine fruit shell and acid followed by aqueous solution. To analyze the equilibrium data, the isotherm 852
787 chromium treated biosorbents. In the case of hydrolyzed reactive models like Langmuir, Freundlich and Temkin isotherms were used 853
788 red 194 reactive dye, the equilibrium data were best fitted to the at different temperatures. The experimental data fits well with the 854
789 Sips isotherm using raw, acid treated biosorbent and acid followed Langmuir adsorption isotherm, representing the mono layer 855
790 by chromium treated biosorbents and the Redlich–Peterson adsorption of the dye. The monolayer sorption capacity of meranti 856
791 isotherm model for chromium treated biosorbents [147]. Brazilian sawdust for methylene blue found to be 120.48, 117.64, 149.25 and 857
792 pine fruit shells (A. angustifolia) in raw form and as activated 158.73 mg/g at 30, 40, 50 and 60 8C respectively [156]. The study 858
793 carbon were used for the biosorption of remazol black B from examine the potential use of activated carbon prepared from the 859
794 aqueous effluents. The fractionary-order kinetic model best fitted epicarp of Ricinus communis for the removal of malachite green dye 860
795 the experimental data. Adsorption data of both forms of the from simulated wastewater. As the amount of the adsorbent 861
796 biosorbent better fitted the Sips isotherm equation [148]. increased, the percentage of dye removal increased consequently. 862
797 The adsorption of crystal violet dye by grapefruit peel subjected Dye adsorption occurs at the optimum pH of 7.0. The experimental 863
798 as the potential adsorbent in the remediation of dye contaminated data were analyzed by using isotherm models of Langmuir, 864
799 wastewaters. The equilibrium process is well described by the Freundlich, Tempkin and Dubinin–Radushkevich isotherm models. 865
800 Langmuir isotherm model than the Freundlich isotherm model. Adsorption behaviour is well described by a monolayer Langmuir- 866
801 The maximum adsorption capacity found as 254.16 mg/g [149]. type isotherm. The maximum removal of MG was obtained at pH 7 as 867
802 The study carried out on the adsorption of Crystal Violet and 99.04% for adsorbent dose of 1 g 50 m/L and 25 mg/L initial dye 868
803 Rhodamine B by Acacia nilotica leaves. The effect of solution pH, concentration at room temperature [157]. The wheat straw has been 869
804 agitation time and initial dye concentration was evaluated. The modified by etherification to prepare a kind of quaternary 870
805 applicability of Langmuir, Freundlich, Dubinin–Radushkevich, and ammonium straw adsorbents. The adsorption behaviours of the 871
806 Temkin equations was examined. The Langmuir isotherm shows modified straw for methyl orange and acid green 25 were studied in 872
807 the best fit with the experimental data and the maximum both batch and column systems. The maximal methyl orange and 873
808 monolayer capacity found as 33 mg/g for Crystal Violet and acid green 25 uptakes were more than 300 and 950 mg/g. The 874
809 37 mg/g for Rhodamine B respectively [150]. Pine cone studied for Mechanism studies using equilibrium data through Langmuir 875
810 its potential application as an adsorbent in raw form and model, Freundlich model, Sips model, Dubinin–Radushkevich model 876
811 hydrochloric acid modified form to remove anionic dye Congo indicates that the adsorption process as monolayer chemical 877
812 red from aqueous solution. The Congo red adsorption of both form adsorption, therefore well described by the Langmuir isotherm 878
813 of the biosobent increased with initial dye concentration, model [158]. Single-dye equilibrium data fitted well with the 879
814 temperature, contact time, but decreased with increase of solution Langmuir–Freundlich model and the maximum biosorption capaci- 880
815 pH and amount of adsorbent of the system. Equilibrium data were ties were 0.68 mmol/g for methylene blue and 0.50 mmol/g for 881
816 best represented by Freundlich isotherm model among Langmuir rhodamine B. Competitive dynamic biosorption demonstrated the 882
817 and Freundlich adsorption isotherm models. Freundlich constant preference of the modified cone chips for biosorbing methylene blue 883
818 ‘n’ indicates favourable adsorption [151]. The potential of garlic [159]. Table 2 shows the valid adsorption isotherm model for the 884
819 peel evaluated in a batch process for the remove methylene blue biosorbents in dye sequestration. 885
820 from aqueous solution. Experiments were carried out in account of
821 the parameters like contact time, initial concentration (25– Adsorption isotherm model significance in the biosorbent evaluation 886
822 200 mg/L), pH (4–12) and temperature (303, 313 and 323 K). for phenolic removal 887
823 Adsorption isotherms assessed through Langmuir, Freundlich, and
824 Temkin isotherms. The data fits well with the Freundlich isotherm. Phenol is the major organic water pollutants since of its toxicity 888
825 The maximum monolayer adsorption capacities found to be 82.64, effects even at low concentrations. The presence of phenol in natural 889
826 123.45, and 142.86 mg/g at 303, 313, and 323 K, respectively [152]. waters forms substituted compounds during disinfection and 890
827 A chemically modified adsorbent prepared from kenaf fibre oxidation processes [188]. The thousands of known phenolic 891
828 char by HCl treatment, which increased the BET surface area in turn compounds distributed in a high molecular diversity and are 892
829 increased the Methylene blue adsorption. The highest percentage categorized on the basis of carbon atoms and structure [189–191]. 893
830 removal of Methylene blue dye found to be 95 wt% at a Even at low concentrations of phenol, act as an impediment to the 894
831 concentration of 50 mg/L. The equilibrium data analyzed using use or reuse of water. A phenol gives an unpleasant taste, odour to 895
832 the Langmuir, Freundlich and Temkin isotherm models and best drinking water and exerts negative effects on different biological 896
833 represented by the Langmuir isotherm model [153]. Olive pomace processes. Most of the phenolic compounds are suspected to the 897
834 evaluated for the removal of reactive textile dye, RR198. The causative agents for human carcinogens [192]. The all-pervading 898
835 highest dye biosorption capacity occurs at pH 2 and the nature of phenols, their toxicity effects even in trace level and the 899
836 equilibrium time was 40 min with a biosorbent concentration of stricter environmental regulations compulsorily made in develop- 900
837 3.0 g/L. The equilibrium data were analyzed by Langmuir, ing processes for the phenols removal from wastewaters [193]. 901
838 Freundlich and Dubinin–Radushkevich isotherm models and the Phenolic removal through adsorption is regarded as a good option 902
839 isotherm studies indicate that the data fits better with the since it offers several advantages like (a) non-selectivity in 903
840 Langmuir isotherm model [154]. Bagasse pith modified through micropollutants removal at low concentration, (b) efficiency in 904
841 chemical activating agent H3PO4 or KOH followed by carbonization the operational time, (c) convenient handling, (d) economical, 905
842 at 500 8C for the removal of Rhodamine-B. The adsorption ability of availability and reusability, (e) no Sludge formation and (f) being 906
843 Bagasse pith activated by H3PO4 is higher than that of the Bagasse eco-friendly [194,195]. 907
844 pith activated by KOH by approximately 10 folds (198.6 and Carrot dross was subjected to activated carbon preparation, 908
845 21.5 mg/g, respectively). The adsorption was analyzed by using magnetized and used for the p-nitrophenol removal from aqueous 909
846 isotherm models of Langmuir, Freundlich, Temkin, Harkins–Jura, solution. Batch sorption studies carried out at different pH values, 910

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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]

911 solid/liquid ratios, contact times and pollutant initial concentra- solution carried out on granular activated carbon. The effect of 946
912 tions in the presence and absence of ultrasonic irradiation. The parameters like pH, temperature, adsorbent dose and contact time 947
913 magnetic activated carbons of carrot dross in the ultrasound were evaluated. Phenol removal takes place at an optimum pH 8, 948
914 presence fit well the Freundlich isotherm. But in contrast, activated temperature 30 8C and adsorbent dose of 30 g/L, 79.9% of 200 mg/L 949
915 carbon in the presence of ultrasonic irradiation fit well with the phenol. Four multicomponent isotherms were applied to the 950
916 Langmuir model [196]. The adsorption potential of thermally experimental data conducted at an initial concentration range of 951
917 activated carbon from maize cob used for the removal of 2,4- 100–1000 mg/L. Single component isotherms viz. Langmuir and 952
918 dichlorophenol from aqueous solutions. Study carried out to Freundlich were applied to determine the multicomponent 953
919 analyze the effects of contact time, 2,4-dichlorophenol initial isotherm parameters. It was found that phenol adsorption followed 954
920 concentration, pH and temperature. Langmuir isotherm fitted well extended Langmuir isotherm while cyanide adsorption followed 955
921 with experimental data. The adsorption capacity of maize cob extended Freundlich isotherm in multicomponent system. The 956
922 carbon found as 17.94 mg/g for the particle size of 250–500 mm monolayer adsorption capacity of GAC was found to be 269.7 and 957
923 [197]. The adsorption of five phenolic compounds like phenol, 2- 1.95 mg/g for phenol and cyanide, respectively as calculated by 958
924 chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-tri- extended Langmuir isotherm [201]. Isotherms for adsorption of 2,4- 959
925 chlorophenol onto granular activated carbon were subjected under dinitrophenol from water and basal salt medium onto date seeds and 960
926 study through the adsorption equilibrium isotherm. For determin- activated carbon were determined. The experimental data fits the 961
927 ing the best fit isotherm, the equilibrium data analyzed through Freundlich isotherm. 0.5 g of date seeds, with a 125 mL salt medium, 962
928 thirteen adsorption isotherm models. The experimental data fits act the suitable adsorbent for the removal of 2,4-dinitrophenol[202]. 963
929 the adsorption isotherm models in the order of Baudu > Langmuir– Table 3 shows the best fitted adsorption isotherm model for the 964
930 Freundlich > Sips > Fritz–Schlunder > Toth > Fritz–Schlunder > phenolic removal using biosorbents. 965
931 Redlich–Peterson [198]. The adsorption tests carried out for the
932 adsorption of five phenolic compounds like phenol, 2-chlorophenol, Adsorption isotherm model significance in the biosorbent evaluation 966
933 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on for anions removal 967
934 granular activated carbon using the seven adsorption equilibrium
935 isotherm models (Langmuir, Freundlich, Elovich, Temkin, Fowler– Inorganic anions are the main category of aquatic pollutants 968
936 Guggenheim, Kiselev, and Hill–de Boer). Experimental data obtained found in above the normal concentrations in the drinking water 969
937 reveals that the adsorption isotherm models fits the data in the order sources. The pollutants removal from drinking water supplies is a 970
938 of Fowler–Guggenheim > Hill–de Boer > Temkin > Freundlich > rising issue [216,217]. Increased nitrate concentrations in water 971
939 Kiselev > Langmuir isotherms [199]. causes severe health hazard due to reduction of nitrate to nitrite in 972
940 The potential of Dalbergia sissoo sawdust charred at 673 K the gastrointestinal human tract. Nitrite causes methemoglobine- 973
941 evaluated for the removal of phenol from aqueous solution. The mia. Nitrate and nitrite have the potential to form carcinogenic N- 974
942 experimental data for removal from single-contaminant water fits nitroso compounds. At high concentrations of Sulfate causes 975
943 well on the Langmuir adsorption model, showing maximum catharsis, dehydration and gastrointestinal irritation [218]. 976
944 phenol uptake capacity of 344.83 mg phenol/g sawdust at 45 8C Excess fluoride intake causes various diseases such as 977
945 [200]. The co-adsorption of phenol and cyanide from binary osteoporosis, cancer, infertility, brain damage, arthritis, brittle 978

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byproducts, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.01.014
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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]

979 bones, Alzheimer syndrome and thyroid disorder [219,220]. Sum of squares of the error 1008
1009
980 Phosphate direct discharge into surface waters perturbs the
p
X
981 aquatic organisms and affects water quality by depletion of the
ðqe;calc  qe;meas Þ2i (44)
982 dissolved oxygen level. Depletion of the oxygen level leads to i¼1
983 eutrophication in the confined water bodies [220]. Vanadium holds
984 harmful effects on the circulatory system and disturbs the plants This is the most widely used common error function but the 1012
1011
1010
985 metabolism leads to chlorosis and limited growth [221]. Table 4 major drawback is that the isotherm parameters derived using this 1013
986 illustrates the suitable adsorption isotherm model for the anions error function will provide a better fit as the magnitude of the 1014
987 removal using biosorbents. errors and therefore the sum of squares of the error increases – 1015
biasing the fit towards data obtained at the at higher end of the 1016
988 The selection of isotherm model for the adsorption liquid-phase concentration ranges [235]. 1017
989 studies [231]
Determination coefficient 1018
990 The Akaike information criterion is used for the selection of The determination coefficient (R2) is calculated using the 1019
991 appropriate model under the situation of when data fitted by following equation [179,236]: 1020
992 more than one model [232,233]. The general representation of !
Pn P
993 the Akaike information criterion is represented as follows: i ðqi;exp  q̄i;exp Þ2  ni ðqi;exp  qi;model Þ2
R2 ¼ Pn 2
(45)
i ðqi;exp  q̄i;exp Þ
AIC ¼ 2k  2 lnðLÞ (42)
where qe,a,meas is the average of qe,meas. determination coefficient is 1022
1021
994
995 where k is the number of parameters in the model and L is the used to check the validity of the kinetic and isotherm models used 1023
996 maximum value of the likelihood function for the model. in describing the experimental data. 1024

997 Error function Adjusted determination coefficient 1025


A measure of the variability of the linear model is explained by 1026
998 Average relative error the adjusted linear coefficient of determination ðR2Ad j Þ [179,236] 1027
999
represented in Eq. (46) 1028
" #
p
100 X ðqe;cal  qe;meas Þ  
(43) n1
n i¼1 qe;meas R2Ad j ¼ 1  ð1  R2 Þ  (46)
i n p

1002
1001
1000 Average relative error function attempts to reduce the fractional 1029
1030
1003 error distribution across the entire concentration range [234]. Error function [179,236] 1031
1032
1004 Where qe,calc is the calculated adsorbate concentration at vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1005 equilibrium(mg/g), qe,meas measured adsorbate concentration at u  X n
u 1
1006 equilibrium (mg/g), n is the number of data points and p is the F error ¼t  ðqi;exp  qi;model Þ2 (47)
n p i
1007 number of parameter of the isotherm equation.

Please cite this article in press as: S. Rangabhashiyam, et al., Relevance of isotherm models in biosorption of pollutants by agricultural
byproducts, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.01.014
G Model
JECE 263 1–17

14 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

1033
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Please cite this article in press as: S. Rangabhashiyam, et al., Relevance of isotherm models in biosorption of pollutants by agricultural
byproducts, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.01.014
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byproducts, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.01.014
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Please cite this article in press as: S. Rangabhashiyam, et al., Relevance of isotherm models in biosorption of pollutants by agricultural
byproducts, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.01.014
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