Separation & Purification Reviews

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Chemically Modified Polysaccharides for

Hexavalent Chromium Adsorption

Martín Esteban González-López , Cesar Mario Laureano-Anzaldo , Aida

Alejandra Pérez-Fonseca , Martín Arellano & Jorge Ramón Robledo-Ortíz

To cite this article: Martín Esteban González-López , Cesar Mario Laureano-Anzaldo , Aida
Alejandra Pérez-Fonseca , Martín Arellano & Jorge Ramón Robledo-Ortíz (2020): Chemically
Modified Polysaccharides for Hexavalent Chromium Adsorption, Separation & Purification Reviews,
DOI: 10.1080/15422119.2020.1783311

To link to this article: https://doi.org/10.1080/15422119.2020.1783311

Published online: 28 Jun 2020.

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SEPARATION & PURIFICATION REVIEWS
https://doi.org/10.1080/15422119.2020.1783311

Review

Chemically Modified Polysaccharides for Hexavalent Chromium Adsorption

Martín Esteban González-López a, Cesar Mario Laureano-Anzaldo a
, Aida Alejandra Pérez-Fonseca a
,
Martín Arellano a, and Jorge Ramón Robledo-Ortíz b
a
Departamento de Ingeniería Química, CUCEI, Universidad De Guadalajara, Jalisco, México; bDepartamento de Madera, Celulosa y Papel, CUCEI,
Universidad de Guadalajara, Zapopan, Jalisco, México

ABSTRACT ARTICLE HISTORY

Over the last decades, adsorption has emerged as a potential separation process for the removal of Received 30 July 2019
heavy metals that are extensively released in effluents from different industries. Among heavy metals, Revised 9 June 2020
Cr(VI) is relevant due to its high toxicity, and its required concentration limit between 50 and 100 µg/L in Accepted 10 June 2020
water for human consumption. Several adsorbents, including silica, zeolites, clays, and carbon, are KEYWORDS
expensive for this application. This literature review proposed the use of novel adsorbents based on Polysaccharides; hexavalent
polysaccharides, mainly chitosan and cellulose, generalizing the effect of pH, equilibrium, kinetics, chromium; adsorption;
thermodynamics, and mechanism on the adsorption efficiency. It is shown that chitosan and cellulose chitosan; cellulose
exhibit a competitive Cr(VI) adsorption capacity reaching up to 625 and 358 mg/g, respectively. Also,
a general review of sorbent reusability and continuous-flow adsorption is provided as they are critical for
the highly extensive operation where maximum continuous-flow removals of 350 and 93 mg/g are
reported for chitosan and cellulose. The use of polysaccharides as sorbents in batch and semi-
continuous systems is an area of great interest and an opportunity to direct the efforts to provide state-
of-the-art sorbents and technology for the removal of hexavalent chromium from polluted water
streams.

INTRODUCTION countries: South Africa, India, Kazakhstan, Zimbabwe,

Finland, Brazil, and Turkey.[4] Industrial usages of Cr(VI)
In recent years, it was realized that the presence of heavy metals in
release more than 170,000 tons annually into the
water streams was a threat not only for the environment but for
environment.[5] These chromium compounds are extensively
human health as well. Heavy metals are highly carcinogenic and
used in wood preservation, tanning, electroplating, dyes,
accumulate in organisms. Stricter environmental regulations for
mining, pigments, paint industries, among others.[6] In 2006,
industrial effluents and discharges were issued worldwide. Several
the Occupational Safety and Health Administration of the US
toxic species could be found in water streams, such as Hg, Cd, Pb,
Department of Labor estimated that more than 558 thousand
Cu, Ni, As, and Cr. Among chromium species, Cr(III) is necessary
US workers were exposed to Cr(VI).
in biological systems for the metabolism of glucose, lipids, and
All redox reactions that transform Cr(III) to Cr(VI) are
proteins, whereas Cr(VI) is highly toxic due to its ability to diffuse
mediated by constituents that are either naturally present in
through cell membranes in the form of CrO4−2 or HCrO4− ions.
the environment or generated by anthropogenic activities.
The other toxic aforementioned divalent metal cations do not
Thus, Cr(VI) can be naturally present in potable water due
have this ability. The US Environmental Protection Agency
to the oxidation of Cr(III) to Cr(VI) that occurs in oxygenated
(EPA) set the hexavalent chromium maximum tolerable concen­
groundwater. Chromium oxidation is a matter of great con­
tration limit to 100 µg/L. Higher concentrations may trigger liver,
cern because even if treatment methods entirely remove
lung, and kidney damages in long-term exposures. Moreover,
Cr(VI), it could potentially re-form in the distribution system
Cr(VI) causes skin and stomach irritation in short-term expo­
at significant levels when these oxidants are in contact with
sures. Chromium is commonly present in effluents from mining,
soluble Cr(III) or surfaces that contain it.[7]
leather tanning, and electroplating industries, and it is generated
The primary route of human exposure is inhalation. It is
by different sources, such as dyes, metal alloys, and metal corro­
well known that inhaled Cr(VI) is a human carcinogen. In
sion inhibitors.[1–3]
1989, the International Agency for Research on Cancer con­
cluded that there is sufficient evidence in humans for nasal,
sinus and lungs Cr(VI) carcinogenicity as encountered in
HEXAVALENT CHROMIUM: SOURCES, HEALTH
chromate production, chromate pigments, and chromium
IMPLICATIONS, AND REGULATION
plating industries. Health effects of Cr(VI) through ingestion,
Worldwide chromium production is concentrated in a few mainly from drinking water, have been reviewed by the EPA.
regions. Approximately 44 million metric tons are produced Also, the genotoxicity of Cr(VI) has been well described using
per year, and 94% of the total amount is produced in seven a variety of bacterial and mammalian cell cultures in vivo.[8]

CONTACT Jorge Ramón Robledo-Ortíz jorge.robledo@academicos.udg.mx Zapopan, Jalisco 45510, México

Copyright © Taylor & Francis Group, LLC
2 M. E. GONZÁLEZ-LÓPEZ ET AL.

The mechanism of action is based on the similarity of Table 1. Methods for Heavy Metals Removal.
chromate anion with phosphate transporters. Once Cr(VI) is Method Advantages Disadvantages
absorbed into the cell, it is reduced to Cr(III) by low- Adsorption Low initial cost, ease of A chemical modification is
molecular-weight amino acids, such as glutathione and operation, high stability necessary in order to
improve its removal
cysteine. The intracellularly reduced Cr(III) binds directly to Membrane Membrane filtration High operational cost,
DNA and causes DNA-protein cross-linkages, leading to filtration[12] systems can remove membrane fouling,
chromium at a wide complex process
mutagenesis, cell proliferation, and tumor formation.[5] range of operational
Cr(VI) soil pollution alters the structure of soil microbial conditions, less space
communities and enters the food chain causing severe health requirement
Ion exchange[13] High efficiency, low Concentration of solution
problems associated with skin and nasal irritation, ulceration, maintenance must be monitored,
eardrum perforation, and lung carcinoma. There is informa­ solution encouraged to
tion that indicates a direct relationship between chromium maximize efficiency, high
operational cost
inhalation and cardiovascular diseases, and many studies Electrochemical Absence of chemical High cost of electricity,
related to chromium metabolism showed that ingested chro­ coagulation[14] usage, easy to operate, initial investment is high
mium was found in the liver, kidney, and blood.[9] small residence time
Precipitation[15] Low cost, high efficiency Sludge generation, high
The significant health issue induced by environmental and utilization of chemicals
[16]
human exposure to Cr(VI) is universally considered. Reverse osmosis High efficiency Expensive to operate
Environmental regulations are becoming stricter worldwide. Phytoremediation[17] High efficiency High residence times, lack
of knowledge regarding
However, the admissible limit values for chromium in drink­ metal uptake
ing water vary with regulatory agencies. It is 50 µg/L with the Photocatalytic Continuous process Several hundred millivolts
reduction[18] of overpotential are often
World Health Organization, the German Industrial Standard, required due to ohmic,
the Office of Environmental Health Hazard Assessment, the kinetic and mass transfer
Occupational Safety and Health Administration, and the losses
Official Mexican Norm. In comparison, this limit is twice
higher, 100 µg/L, with the Canadian Committee on
Drinking Water and the US Environmental Protection dependent since it affects solid/liquid interfaces, swelling of
Agency.[10,11] It is important to note that these values serve the sorbent, and ion mobility. Besides, thermodynamics deter­
as a reference to minimize the risk of public exposure to mines the spontaneity, randomness, and endothermicity or
chromium sources, and the design of a Cr(VI) separation exothermicity of the process.[22]
method must be considered to achieve these permissible
values in treated effluents.
Conventional Carbonaceous Adsorbents
ADSORPTION The main characteristic required in any given sorbent is
a high adsorption capacity. Thus, the sorbent should have
For the separation of heavy metals from contaminated waters, specific characteristics, e.g., a large surface area, high porosity,
many methods have been tested in the last decades, such as and suitable pore size and volume. Moreover, it should be
reverse osmosis, coagulation, flocculation, ion exchange, and selective, cost-effective, easy to regenerate, and environmen­
the use of membranes or bacteria. However, many of these tally friendly in order to be suitable for high-scale operation.­
methods present a high consumption of reagents, low ener­ [22]
Carbonaceous structures, namely: activated carbon or
getic efficiency, selectivity, and high cost (Table 1).[12–18] In carbon nanostructures, fill up the requirements, hence they
contrast, the ease of adsorption operation, its affordability and are common materials used for adsorption applications.
efficiency make this process feasible and cost-effective for the
removal of metal ions as long as low cost and highly efficient
adsorbents are developed.[1,10,11]
Activated Carbon
Adsorption is a complex phenomenon in which the separa­
tion or sequestration of the adsorbate takes place from an Activated carbon is one of the most used adsorbents due to its
aqueous/gaseous polluted phase onto a solid phase, the adsor­ high porosity and large surface area between 500 and
bent. Adsorption can be decomposed in the following main 1500 m2/g, which increases its efficiency along with the exten­
steps: 1) pollutants, either ions or molecules, diffuse through sively available functional groups.[23,24] However, the main
the solution onto the sorbent surface, 2) they diffuse through drawback of this sorbent is its high cost.[20,21,25] In this
the sorbent pores and 3) adsorption occurs via chemical sense, the interest of researchers in the use of agricultural
linkage, chelation, complexation, ion exchange, electrostatic and natural wastes for the production of activated carbons
attraction, among others.[19] Increasing the amount of sorbent or biochars has grown due to their characteristics as renew­
increases the number of active sites leading to higher removal able sources and low-cost. The preparation of biochars was
efficiencies, but could decrease the adsorption capacity if studied by Altun and Kar,[26] who carried out the co-pyrolysis
a large number of adsorption sites remain unoccupied. of walnut shells and tar sand to obtain a sorbent with a Cr(VI)
Moreover, adsorption is highly dependent on the pH since it removal capacity of 50 mg/g. Moreover, Kumar et al.[27]
governs the metal ion speciation, the degree of ionization, and synthesized carbon spheres from glucose monohydrate and
the surface charge of the sorbent.[19–21] It is also temperature- found an uptake capacity of 117 mg/g through exothermic

and spontaneous adsorption, which was confirmed by
thermodynamics.
Several efforts have been made to enhance heavy metals
adsorption using biochars by increasing their specific surface
area. Doke and Khan[28] obtained an activated carbon from
wood apple shell with a specific surface area of 1900 m2/g,
which yielded a maximum chromium uptake capacity of
151 mg/g. The importance of a high specific surface area lies
in the type of diffusion that governs the process.[29] The
adsorption could be governed by either external film, intra­
particle or pore diffusion, or both.[20] Moreover, chemical
activators or catalysts could be used for the enhancement of
the carbonization during sorbent preparation. Kumar and
Jena[30] prepared activated carbon from fox nutshell by che­
mical activation with ZnCl2. The average pore diameter was
0.65 nm, which yield a Cr(VI) capacity of 44 mg/g. The use of
catalysts provides a higher specific area for the adsorbent, this
was also observed by Norouzi et al.,[31] who carbonized
a waste product, and the activation was driven using NaOH.
In this case, the specific surface area was 2025 m2/g, which
enhanced the uptake capacity to 283 mg/g.
Carbon Nanostructures: Nanotubes, Nanofibers, and
Graphene
Carbonaceous nanostructures, carbon nanotubes (CNTs),
nanofibers (CNFs), and graphene have received particular
interest by researchers in the last decade.[32] Graphene is an
allotropic form of carbon composed by a mono-atomic planar
structure of carbon atoms with sp2 hybridization that was first
isolated by Novoselov et al.[33] In this sense, another impor­
tant carbon allotrope is carbon nanotubes, which were first
discovered by Iijima[34] and consist of hollow graphitic con­
centric layers, specifically formed by graphene layers rolled up
onto single-walled or multi-walled carbon nanotubes
(MWCNTs).[35,36] Despite the high cost of these nanostruc­
tures, their interest for adsorption processes lies in its extre­
mely high surface area, pore diameter, uniform shape, high
thermal stability, and ease of functionalization.[36,37]
Moreover, MWCNTs are hydrophobic due to their intrinsic
characteristics; therefore, they form large aggregates with low
dispersion in aqueous and organic solutions due to strong
Van der Waals interactions.[35] This drawback requires the
development of functionalization strategies to introduce func­
tional groups that enhance their dispersion in polar solvents,
and more importantly, that allow adsorbing higher amounts
of pollutants with a lower mass of sorbent.[38] Thus, for
effective removal, MWCNTs have been modified by simple
oxidation introducing hydrophilic functional groups: hydro­
xyl, carbonyl, and carboxyl groups. These groups enhance
adsorption, giving place to graphene oxide or oxidized carbon
nanotubes.[32]
However, many other chemical modifications have been
carried out in the last years to enhance carbonaceous adsorp­
tion capacity. For instance, Mohamed et al.[39] produced
nanofiber composites using polyacrylonitrile and amino-
functionalized nanoparticles of CNTs and TiO2 using electro­
spinning. The Cr(VI) adsorption experiments showed an
adsorption capacity of 500 mg/g. Further functionalization
SEPARATION & PURIFICATION REVIEWS 3
of carbon nanostructures was also employed to increase affi­
nity toward heavy metals uptake. Fatehi et al.,[40] coated
amino-functionalized carbon with magnetite by co-
precipitation, improving the removal efficiency up to 80%
due to the large surface area and binding capacity of the
magnetite nanoparticles. It is worth to mention that besides
amino groups, carbon nitride is also a well-known material
that has attracted attention due to the incorporation of nitro­
gen atoms in the carbon nanostructure that enhance the
mechanical, conducting, field-emission, and energy-storage
properties of the sorbent. For instance, mesoporous carbon
nitride was reported as an effective sorbent for Cr(VI)
removal by Chen et al.[41] due to pyridine functional groups
giving a Cr(VI) adsorption of 48 mg/g.
Huang et al.[42] tested magnetic multi-wall carbon nano­
tubes (MMWCNTs). Their adsorption experiments found
that elevated temperatures, up to 70°C or 343 K, dilated the
pore volume and surface area, facilitating the Cr(VI) ions
crossing of the external surface and penetrating easily into
the pore, leading to a moderate adsorption value of 16 mg/g.
Another novel approach for CNT functionalization was car­
ried out by Taghizadeh and Hassanpour.[43] They prepared
a novel ion-imprinted polymer (IIP) on the surface of
MMWCNTs, with a capacity of 56 mg/g and notable reusa­
bility of five cycles without exhibiting a significant reduction
in adsorption capacity.
Within the family of nano-carbons, graphene is notable
due to its extensive surface area.[44] However, graphene pos­
sesses poor solubility, and functionalization is required to
introduce functional groups suitable for Cr(VI) adsorption.­
[45]
Thus, the most commonly used graphene structures are
graphene oxide (GO) and reduced graphene oxide (RGO)
since they contain functional groups such as hydroxyl, car­
boxyl, and carbonyl groups.[46] Zhang et al.[45] synthesized
a RGO/NiO composite and found an excellent removal capa­
city of 198 mg/g.
As discussed above, carbon-based sorbents present high
adsorption capacities. However, it is necessary to carry out
a cost-benefit analysis to provide a complete insight on its use
on a high-scale operation process in perspective with the
novel, alternative, economical and environmental-friendly
sorbents. In this sense, Table 2 presents a summary of the
adsorption capacity of some carbonaceous structures.[45–51]
Alternative Organic Adsorbents: Polysaccharides
Many papers are found in the literature reporting the use of
alternative materials as sorbents for heavy metals removal. In
particular, several review articles have been published in the
last decade regarding pollutant adsorption using polysacchar­
ides. Notably, the use of chitosan as sorbent has been
reviewed for the removal of As(V), Hg(II), or in general for
various metal ion species.[52–55] Zhang et al.[22] prepared
a review on modified chitosan sorbents for different heavy
metal removal focusing on a systematic approach using
response surface methodology and highlighting the effect of
process variables, such as pH, temperature, adsorbent dose,
contact time and interfering ions. Also, insights were given in
terms of adsorption mechanism, while very few dynamic
4 M. E. GONZÁLEZ-LÓPEZ ET AL.

Table 2. Structural Representation and Adsorption Capacity of Carbon-based the literature related to continuous-flow adsorption in com­
Adsorbents.
parison with the extensive static adsorption studies.
Adsorption Therefore, this work aims to discuss novel polysaccharides-
Material Structure Adsorbent** capacity (mg/g) Ref.
[31] based adsorbents developed in the last ten years and to com­
Activated Date press cake* 283
carbon Wood apple 152 [28] pare its feasibility against commonly used carbon sorbents.
shell* Also, to generalize the effect of process parameters on the
[27]
Carbon spheres 117
Fe3O4 doped 80 [40] adsorption and its nature, e.g., pH, equilibrium, kinetics,
carbon thermodynamics, and mechanism, for which models used to
[26]
Walnut shells* 50 describe adsorption phenomena are discussed with
[41]
Mesoporous 48
carbon nitride a theoretical approach. More importantly, the sorbent reusa­
[30]
Fox nutshell* 46
[39]
bility and continuous-flow adsorption are discussed, both
Carbon PAN-CNT/TiO2- 714
nanotubes NH2
critical parameters for highly extensive operations of the
AA-CNT 264 [47] adsorption process.
[48]
IL-oxi-MW-CNT 86
[43]
MMW-CNT-IIP 56
[49]
MNP/MW-CNT 42
[42]
MW-CNT 16
[50]
Theoretical Background
Graphene GO/PEI 436
[44]
TEPA/ 408 The mechanism of heavy metal adsorption onto biosorbents is
Polypyrrole/GO
aerogel
a complex process that could involve physisorption, chemi­
GO/HBP/NH2/ 301 [46]
sorption, complexation, ion-exchange, among others.[53]
TEPA Therefore, the study of adsorption often involves the use of
[51]
Fe3O4/Graphene 281
RGO/NiO 198 [45] models to describe the adsorption in terms of equilibrium,
*Activated carbon obtained from the indicated biomass. kinetics, and thermodynamics in an attempt to elucidate the
**Abbreviations: AA, Activated alumina; AC, Activated carbon; CNT, Carbon mechanism carried out in the adsorption process, as well as
nanotubes; IL, Ionic liquid; IIP, Ion imprinted; MNP, Magnetic nanoparticle; the prediction of breakthrough curves in the semi-continuous
MW, Multiwall; MMW, Magnetic multiwall; PAN, Polyacrylonitrile; GO,
Graphene oxide; PEI, Polyethyleneimine; HBP, Hyper-branched polymer; flow process. The following paragraphs summarize the most
TEPA, Tetraethylenepentamine; RGO, Reduced graphene oxide. commonly used equations to describe adsorption systems.

adsorption studies were discussed. More specifically, regard­
ing Cr(VI), Owlad et al.[24] discussed the most widely used
techniques for chromium removal with a particular focus on
adsorption. These authors provided information of sorbents
based on agricultural wastes and its modification as well as
chitosan, pointing out the necessity to crosslink chitosan to
make it more stable even though the adsorption capacity was
reduced since crosslinking agents occupy active adsorption
sites.
Moreover, cellulose and its modified forms were also
described as efficient sorbents. For example, raw and cellu­
lose-based sorbents were reviewed by Hubbe et al.,[56] who
provided a full compilation of previous review papers about
pollutant removal. Also, a mathematical overview of the com­
monly discussed isotherm models was included in this work.
Finally, Hokkanen et al.[57] compiled reports on modified
cellulose-based sorbents for the removal of pollutants such
as metals, dyes, and inorganic anions. They highlighted the
direct modification of cellulose through a variety of chemis­
tries to increase its binding sites and the uptake of pollutants.
Moreover, the absence of reports on column, full-scale studies
as well as real contaminated effluents was mentioned.
It is worth mentioning that in the review papers above­
mentioned, the fixed-bed column adsorption studies were
briefly discussed. Despite adsorption experiments are often
carried out in batch systems to characterize the sorbent and
the adsorption dynamics, the fixed-bed column adsorption
experiments are a subject of great importance, since they
provide useful information required for high-scale applica­
tions. Thus, it is interesting that fewer reports are found in
Adsorption Equilibrium
The adsorption equilibrium could be defined as the distribu­
tion between adsorbate molecules at the solid-liquid interface
and the bulk concentration.[20] Thus, the interaction between
adsorbate and adsorbent is an indication of the sorbent capa­
city, and it becomes a function of the concentration of adsor­
bate at the interface. This relationship is commonly referred
to as adsorption isotherm and represents the equilibrium at
a fixed temperature, which is extensively studied to assess the
maximum adsorption capacity of any given sorbent.[56] For
this purpose, many mathematical models have been proposed.
These empirical models include two-parameters: the number
of binding sites and the adsorbate concentration. They are the
Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin
models. Three-parameter models, like Redlich-Peterson and
Sips isotherms and other multilayer physisorption models add
variations. The adsorption equations, either on their linear­
ized or non-linear forms, are given in the following
paragraphs.
Langmuir
Probably the most used model is the Langmuir isotherm. This
equation suggests that adsorption occurs within a limited
number of homogeneous binding sites, each of which is
independent of other adjacent sites and can adsorb one mole­
cule, neglecting the interaction between adsorbed molecules,
i.e., monolayer adsorption.[58]
qmax KL Ce
qe ¼ (1)
1 þ KL Ce

where Ce (mg/L) is the concentration of solute in the liquid
phase at the equilibrium, qmax (mg/g) is the maximum mass
of the solute adsorbed within the monolayer, and KL (L/mg) is
the Langmuir dissociation constant related to the adsorption
energy, i.e., the affinity of the sorbent for the adsorbate.
Therefore, it is expected to observe high values qmax and KL
for optimal sorbents. Moreover, the dimensionless separation
parameter RL is related to the affinity between sorbent and
adsorbate, namely the effectiveness of the adsorption, and it is
defined as follows:
1
RL ¼ (2)
1 þ KL C0
where C0 is the initial solute concentration. This separation
parameter is interpreted as follows: if RL > 1, the adsorption is
not favorable since KL is negative. The adsorption is linear
when KL = 0 and RL = 1. If 0 < RL < 1, the KL magnitude is an
indication of favorable adsorption. Finally, if RL = 0, the
adsorption is irreversible.[15]
Freundlich
The main difference between the Freundlich and Langmuir
isotherms is that Freundlich assumes a multilayer adsorption,
i.e., the adsorption occurs through heterogeneous active sites,
and interactions between adsorbed molecules are possible.[59]
The heterogeneity of binding sites suggests that stronger sites
are occupied in the early stages of the adsorption, whereas the
binding energy, or strength, decreases as sites become occu­
pied. It is considered to be a non-linear empirical equation
described as follows:
qe ¼ KF Ce n (3)
where KF (mg1-n/g Ln) and n (dimensionless) are the Freundlich
constants that indicate adsorption capacity and intensity,
respectively. If the value of n lies between 1–10, the adsorption
is favorable. Moreover, the surface energy is known to increase
(n < 1) or decrease (n > 1) with the surface density, and
particularly the surface sites are equivalent at n = 1.
Sips
The Sips model combines Langmuir and Freundlich character­
istics in a single three-parameter equation. It considers that the
equilibrium is described by Freundlich isotherm at low concen­
trations but follows a Langmuir isotherm at higher
concentrations.[60] The following equation represents this
behavior:
qmax ðKs Ce Þns
qe ¼ (4)
1 þ ðKs Ce Þns
where Ks (L/mg) is the Sips equilibrium constant, whereas ns
is the exponent of the model. By analyzing the limits of the
function, it is clear that at low adsorbate concentrations, the
Sips model approaches to the Freundlich behavior (heteroge­
neous adsorption is also assumed if ns � 1). Naturally, at
high concentrations, or for values of ns close to 1, it resembles
the Langmuir model describing monolayer adsorption.
SEPARATION & PURIFICATION REVIEWS 5
Redlich-Peterson
The Redlich-Peterson isotherm is another hybrid isotherm,
which also includes features of Freundlich and Langmuir
isotherms.[61] This model has a linear dependence on concen­
tration in the numerator and exponential dependence on
concentration in the denominator. Thus, the Redlich-
Peterson adsorption model can be used over a broad range
of concentrations. The Langmuir equation is well confirmed
for low concentrations and the Freundlich adsorption pro­
vides good fitting for moderate concentrations. The Redlich-
Peterson isotherm combines both being represented as:
ACe
qe ¼ (5)
1 þ BCe g
In which A (L/mg) and B (Lg/mgg) are simply adsorption
constants, whereas g is an indication of the efficiency of the
adsorption, which value lies between 0 and 1. If g = 1, the
Redlich-Peterson model simply becomes the Langmuir iso­
therm, besides, when g = 0, the model approaches the
Freundlich model at high concentration.
The abovementioned isotherms represent the most com­
monly used models for describing the equilibrium of adsorp­
tion of many sorbents. Interestingly, both Redlich-Peterson
and Sips isotherms provide information of both Langmuir
and Freundlich isotherms through three-parameter equations.
A third extra exponent parameter is present in each equation.
Thus, for a better understanding of the effect of these para­
meters, plots for these isotherms with different exponent
values of g (for Redlich-Peterson isotherm) and ns (for Sips
isotherm) are displayed in Figure 1.
Dubinin-Radushkevich
The Dubinin-Radushkevich (D-R) is an empirical equation
usually applied to describe the adsorption mechanism according
to a Gaussian energy distribution within heterogeneous sites
and describes multilayer adsorption governed by a pore-filling
mechanism.[62] The D-R model describes an adsorption site
close to the surface and evaluates the sorption free energy to
provide information about the adsorption nature, either physi­
cal or chemical, and the magnitude of mean adsorption energy,
EDR. It informs on the type of adsorption process, i.e., the
magnitude of EDR indicates whether the adsorption its domi­
nated by ion-exchange, electrostatic attraction or chelation.[63]
The following equation describes the D-R isotherm:
βe ε2
qe ¼ qmax e (6)
in this model, the maximum capacity qmax (mmol/g), the
adsorption free energy βe (mol2 kJ2) and the Polanyi potential
(ε) are related, the latter is calculated by:
� �
1
ε ¼ RT ln 1 þ (7)
Ce
Moreover, by assuming heterogeneous adsorption and
describing all energetically equivalent sites by the Langmuir
isotherm, the mean adsorption energy (EDR) could be calcu­
lated. From this parameter, it is possible to estimate if the
adsorption process is governed by chemisorption (8 < EDR <
16 kJ/mol) or physisorption (EDR < 8 kJ/mol):
6 M. E. GONZÁLEZ-LÓPEZ ET AL.
Figure 1. Comparison between Langmuir, Freundlich, Sips and Redlich-Peterson isotherms. g is the Redlich-Peterson parameter (eq. 5). The lower right inset is an
enlargement of the low pollutant concentration region with four different nS Sips exponents (eq. 4).
1 for this model. The following equation gives the non-linear
EDR ¼ pffiffiffiffiffiffiffiffiffiffi
2βe
Elovich
The Elovich isotherm is based on a kinetic principle assuming
an exponential increase of the adsorption sites implying mul­
tilayer adsorption.[64] The non-linear form of this equation is:
qe qe
¼ KE Ce e qmax
qmax
where KE is the Elovich constant (L/mg).
Temkin
The characteristic of the isotherm proposed by Temkin and
Pyzhev[65] is the consideration of the interactions between
adsorbed molecules. Temkin assumes that the heat of adsorp­
tion decreases linearly rather than logarithmically as the sur­
face becomes covered with adsorbate molecules since
repulsion between these molecules takes place. The following
equation describes the model:
RT
qe ¼ lnðATe Ce Þ
bTe
from this equation, the heat constant bTe (J/mol) describes the
heat of adsorption, whereas the maximum binding energy is
described by the equilibrium binding constant ATe (L/g).
Halsey
Another multilayer adsorption model is the Halsey isotherm.­
[66]
This model describes adsorption over a multilayer at
a relatively large distance from the surface. It is essential to
notice that this model has a similar form to the Freundlich
isotherm. Thus, multilayer adsorption is the main assumption
(8)
form of the Halsey isotherm:
KH
qe ¼ (11)
Ce 1=nH
where KH (Ln/g mgn−1) and nH are the Halsey constants.
Koble-Corrigan Isotherm
Similar to Sips and Redlich-Peterson isotherms, the Koble-
(9) Corrigan isotherm includes characteristics of both Langmuir
and Freundlich model in a single three-parameter equation.­
[67]
Therefore, it resembles the Freundlich isotherm at high
concentrations. The non-linear form of this model is given by:
Ak Ce p
qe ¼ (12)
1 þ Bk Ce p
where Ak (Ln/g mgn−1) and Bk (Ln/mgn) are the Koble-
Corrigan constants, whereas p represents the critical para­
meter of this equation. The validity of this model is restricted
to p values greater or equal to 1. Therefore, for p < 1, it is said
that the model is inaccurate to describe the experimental data,
even though a good mathematical correlation is observed.
Several other models have been reported in the literature,
(10)
such as Flory-Huggins, Hill, Toth, among others. However,
for many of the papers cited in this study, the previously
discussed models were used to represent the vast majority of
the adsorption equilibrium of chemically modified
polysaccharides.
Adsorption Kinetics
Adsorption kinetics is essential to determine the interaction
between the adsorbate and adsorbent, and to analyze the
suitability of a given sorbent for the removal of heavy metal
ions in aqueous systems.[20] From the evaluation of the
 SEPARATION & PURIFICATION REVIEWS 7

adsorption kinetics, two important features are the adsorption

mechanism and the uptake rate. This uptake rate determines
the residence time required for completing the adsorption.
The following models are commonly used to describe the
dynamic of adsorption:

Pseudo-first-order Model
The kinetics equation of Lagergren may have been the first
attempt to describe the adsorption on liquid-solid systems
based on the solid capacity. This model is based on the
assumption that the adsorption rate is related to the difference
in saturation concentration, the number of metal ions
adsorbed through time, and the number of free sites available Figure 2. Intraparticle and external film diffusion mechanisms. δ is the boundary
for sorption.[68] The Lagergren model can be expressed in layer thickness; CS is the pollutant concentration on the particle surface.
differential form as follows:
dq Therefore, the Weber-Morris model is often used to ana­
¼ k1 ðqe qÞ (13) lyze the rate-limiting step.[70] Weber and Morris noticed that
dt
in many adsorption cases, the variation on the uptake has
where k1 (min−1) is the pseudo-first-order rate constant and
a proportional relationship with t0.5 rather than the contact
qe (mg/g) stands for the adsorption capacity at equilibrium.
time t.[71] Thus, it suggests that if the linear plot passes
The following equation gives the solution for this equation for
through the origin, the adsorption process is controlled by
the initial conditions: q(0) = 0 and q(t) = qt.
intraparticle diffusion. However, if the Weber-Morris plot has
�
qt ¼ qe 1 e k1 t (14) a non-zero intercept value, then the boundary layer influences
the kinetic mechanism.[72] Thus, more than one straight line
However, many authors prefer to use this model on its line­ with different slopes could be evidenced, which implies that
arized form, which is: the adsorption process involves more than one sorption rate.
lnðqe qt Þ ¼ lnðqe Þ k1 t (15) The model is described as follows:

qt ¼ kip t0:5 þ c (19)

Pseudo-second-order Model
In this model, the rate-limiting step involves chemisorption,
i.e., the removal is due to physicochemical interactions
between adsorbate and adsorbent.[69] It is assumed that the
adsorption capacity is proportional to the number of active
sites occupied on the sorbent and it can be expressed as:
dq
¼ k2 ðqe qÞ2 (16)
dt
Again, the pseudo-second-order rate constant is represented
by k2 (g/mg min), while qe (mg/g) represents the uptake at
equilibrium. The solution for this differential equation using q
(0) = 0 and q(t) = qt is given by the following equation:
1 1
¼ þ k2 t (17)
ðqe qt Þ qe
Here also the most popular form of this model is its linearized
form given by:
t 1 1 �1 must be done, and applying the initial conditions qt
¼ þ t (18)
qt k2 qe 2 qe
Intraparticle Diffusion Model (Fickian Diffusion Law or
Weber-Morris Model)
Diffusion processes influence the transport of the heavy metal
anions from the bulk to the adsorbent surface, i.e., external
diffusion or boundary layer diffusion and pore or intraparticle
diffusion (Figure 2).[20] This process is important for meso­
porous materials in which diffusion in the pores plays an
essential role in the adsorption process.[41]
0.5
where kip (mg/g min ) is the intraparticle diffusion constant
whereas c (mg/g) is related to the boundary layer thickness.
The information that could be obtained from the Weber-
Morris plot is illustrated in Figure 3.
Elovich
The Elovich equation is another commonly used model for
describing the kinetics of heterogeneous chemisorption of
nonelectrolytes.[64] However, it has been widely used to
describe the adsorption of gases onto solid materials as well
as to describe the process of heavy metal adsorption from
aqueous solutions. The differential form of the Elovich equa­
tion is generally expressed as follows[73]:
dqt βqt
¼ αe (20)
dt
To simplify the Elovich equation, the assumption that αβt
(0) = 0 and qt(t) = qt, the equation becomes[69,74]:
1 1
qt ¼ lnðαβÞ þ lnðtÞ (21)
β β
where α (mg/g min) represents the initial adsorption rate, and
β represents the extent of the surface covered. A plot of qt
versus ln(t) shows a linear relationship with a slope of 1/β and
intercept 1/β ln(α β). This way, the Elovich equation is suc­
cessfully used to describe the second-order kinetics assuming
that the solid surface is energetically heterogeneous.[71]
8 M. E. GONZÁLEZ-LÓPEZ ET AL.

Figure 3. Weber-Morris plots of pollutant adsorption, qt, versus the square root of the contact time, t (eq. 19).

Bangham This expression is called the linear driving force rate law and
The Bangham model can be seen as a generalization of the is usually applied to describe the solute mass transfer through
Weber-Morris model or the application of the Freundlich the liquid film.
model to kinetics.[75] The equation is: The film diffusion mass transfer rate equation presented by
Boyd et al.[76] is:
dqt kB ðqe qt Þ � �
¼ (22) qt
dt tZ ln 1 ¼ KFD t (26)
qe
where kB (min−Z) is the Bangham adsorption rate constant.
Applying the condition qt (0) = 0, and introducing a dimen­
sionless constant, Z, the expression can be rearranged as: 3De
� � �� KFD ¼ (27)
r0 Δr0 k0
qe
ln ln ¼ lnðkB Þ Z lnðtÞ (23) where KFD (min−1) is the liquid film diffusion constant, De
qe qt
(cm2 min−1) is the effective liquid film diffusion coefficient, r0
(cm) is the radius of adsorbent beads, ∆r0 (cm) is the thick­
Liquid Film Diffusion ness of the liquid film, and k’ is the dimensionless equilibrium
The liquid film diffusion model assumes that in liquid/solid constant of adsorption.
adsorption systems, the rate of solute accumulation in the
solid phase is equal to solute transfer across the liquid film
according to the mass balance law.[76] Adsorption Thermodynamics

@q The importance of the thermodynamic study of the adsorption

Vp ¼ kf As ðC Ci Þ (24) lies in elucidating the nature of the process in terms of endo or
@t
exothermicity, randomness, and more importantly,
where the rate of solute accumulation is equaled to Vp @q @t , spontaneity.[20,21] These properties could be estimated through
whereas q represents the average solute concentration in the the change of the thermodynamic functions, i.e., enthalpy (ΔH),
solid, and VP is the volume of the particle. Also, the rate of entropy (ΔS), and Gibbs free-energy (ΔG). The procedure for
solute transfer across the liquid film is proportional to the estimating these thermodynamic properties is often carried out
surface area of the particle As, and the concentration driving through the following steps: firstly, adsorption isotherms are
force (C - Ci), where kf represents the film mass transfer obtained at different temperatures with intervals ranging from
coefficient. The last expression can be rearranged as 5–15°C. Since the effect of temperature is observed at early stages
a function of the surface area per unit volume, S0, then, the of the adsorption, an isotherm model (principally Langmuir
expression can be written as[77]: model) could be used to calculate a rate constant, KL, which is
related to the slope of the first stage of adsorption (also the
@q relationship between qe/Ce could be used for this purpose).
¼ kf S0 ðC Ci Þ (25)
@t Finally, plots of the logarithm of the rate constant against the
 SEPARATION & PURIFICATION REVIEWS 9

� �
reciprocate of absolute temperature are built according to the C0 kTh qTh m
Van’t Hoff equation, and the values for ΔH and ΔS are obtained ln 1 ¼ kTh C0 t (31)
Ct Q
from the slope and intercept, respectively, according to the
following equation: where Q is the volumetric flow rate (mL/min), m is the
adsorbent mass (g), and C0 (mg/L) represents the inlet con­
ΔH ΔS centration, whereas kTh (L/mg/min) is the Thomas constant
lnðKL Þ ¼ þ (28)
RT R and qTh (mg/g) represents the adsorption capacity of the fixed
Then, the change of Gibbs free-energy is calculated according bed. Both constants
� kTh� and qTh could be obtained from the
C0
to this relationship: linear plot of ln Ct 1 versus t from the slope and intercept,

ΔG ¼ ΔH TΔS (29) respectively.

For positive ΔH values, the process is known to be endother­

mic, while it is exothermic for negative values (ΔH < 0).
Adsorption is related to temperature as a function of the
mobility of heavy metal ions.[21] The ∆H value also indicates
if the adsorption is driven by strong attraction forces.[78]
Then, positive values ΔS values indicate that the randomness
at the solid-liquid interface increase during the adsorption,
whereas negative values (ΔS < 0) would indicate a decrease in
the degree of freedom of the adsorbed ions at the interface.[2]
Besides, if both ΔH and ΔS are positive values, this indicates
that chemisorption is the dominant mechanism during the
adsorption.[26] Finally, adsorption is spontaneous, i.e., energe­
tically favorable, if the change of Gibbs free-energy has
a negative value (ΔG < 0). Thus, the adsorption is more
favorable as ΔG negative values become larger.[49,79]
Breakthrough Curves
The continuous-flow operation of adsorption is carried out in
fixed-bed columns. The time-dependent saturation curve of
the sorbent is called the breakthrough curve. It is the plot of
the normalized dimensionless concentration at the exit of the
bed (C/C0) versus time.[20] It informs on the operation and
dynamic response of an adsorption column which are related
to the feasibility and effectiveness of the process.[80] To esti­
mate the breakthrough time, tb, defined as the time when
C/C0 reaches the maximum permissible limit of the pollutant
(generally, C/C0 = 0.1) and the exhaustion time, te, defined as
the time when the bed is nearly saturated (C/C0 = 0.9), break­
through curves are modeled using various equations.
Thomas Model
One of the most widely reported models for the prediction of
breakthrough curves is the Thomas model.[81] This model was
developed from the equation of mass conservation in a flow
system and assumes plug flow along the fixed-bed while
neglecting axial dispersion in the column. It also assumes
a Langmuir kinetics of adsorption-desorption and considers
that the driving force is governed by a second-order reversible
kinetics.[80,82] The non-linear equation for this model is:
Ct 1 time t of a column of bed height z using the parameters kBDST
¼ �� � � (30)
C0 1 þ exp kTh ðqTh m C0 Qt Þ
Q
However, it is commonly expressed by its linear form
given by:
Adams-Bohart Model or Bed Depth Service Time (BDST)
Model
This model is one of the most commonly used models to
describe the first part of the breakthrough curve of fixed-bed
column adsorption (up to 10–50% of the saturation point)
since it predicts the relationship between the depth and ser­
vice time of the column.[83] The model predicts the service
time before regeneration of the column is required.[84,85] It is
used to scale-up reliably the column to larger flow rates and
inlet concentrations without further experimental tests. It
assumes a non-instantaneous equilibrium in which the adsor­
bate is directly adsorbed onto the surface of the adsorbent
with a rate of adsorption that is proportional to a fraction of
the uptake capacity.[86,87] Adsorption is governed by the
unused capacity of the sorbent since intraparticle and external
film diffusion resistances are neglected.[80,82,83] This model
was developed according to a mass balance and quasi-
chemical kinetic rate expressions according to the following
equations:
@q
¼ kα qC (32)
@t
@C kα
¼ qC (33)
@z v
The solution of these expressions could be arranged to relate
the process conditions and operating parameters with service
time by the following equation[88]:
Ct 1
¼ � � �� (34)
C0 1 þ exp kBDST C0 NBDST z t
Ci v
Also, this equation is given on its linear form by:
� �
Ct z
ln ¼ kBDST C0 t kBDST NBDST (35)
C0 v
where kBDST (L/mg min) is the kinetic constant, NBDST is the
adsorption capacity of the bed (mg/L), z represents the bed
length, and v stands for the linear velocity (cm/min).
Generally, the BDST model is employed to predict the service
and NBDST previously calculated from experimental tests car­
ried out at different linear velocity values v, according to the
following equation proposed by Hutchins as a linear relation­
ship between bed length z and service time t[89,90]:
10 M. E. GONZÁLEZ-LÓPEZ ET AL.
� �
NBDST z 1 C0
t¼ ln 1 (36)
C0 v kBDST C0 Ct
Generally, from this equation the adsorption capacity para­
meter NBDST and the rate constant for solute transfer from the
liquid to the solid phase kBDST could be obtained from the
slope, which represents the requires for the adsorption zone to
travel a unit length through the adsorbent,[88] and intercept of
the plot of service time t versus bed length z, respectively.
Moreover, the critical bed length zc is defined as the minimum
value to guarantee that the outlet effluent would not exceed
breakthrough concentration (Cb) at time t = 0 and it is given
by the following equation[91,92]:
� �
v C0
zc ¼ ln 1 (37)
kBDST NBDST Cb
Yoon-Nelson Model
The Yoon-Nelson model was initially developed to describe the
breakthrough behavior of adsorbate gases on activated charcoal.
Its primary assumption is that the rate of decrease in the prob­
ability of adsorption for each molecule is proportional to the
probability of each site’s adsorption and the probability of
breakthrough.[80,93] It is given by the following equation:
Ct expðkYN t τkYN Þ
¼ (38)
C0 1 þ expðkYN t τkYN Þ
or in its linear form by the equation:
� �
Ct
ln ¼ kYN t τkYN (39)
C0 Ct
where kYN (min−1) is a proportional constant, and τ repre­
sents the time when Ct = 0.5C0. Therefore, owing to the
symmetrical nature of the breakthrough curve, it is expected
to become completely saturated at t = 2τ since the amount of
the metal adsorbed in the fixed bed is half of the total metal
entering within the 2τ period.[84] Both parameters kYN and τ
� �
could be obtained from the linear plot ln C0Ct Ct versus t.
POLYSACCHARIDES-BASED SORBENTS
The abovementioned theoretical background represents an
essential and useful resource for understanding the desirable
features that a sorbent must possess to be considered as
a potential sorbent for a given application. In recent years,
the development of polysaccharides-based sorbents, mainly
cellulose, chitosan, and other natural polymers like lignin,
has become of great interest due to their attractive physical
and chemical properties and the wide range of possibilities by
which they can be modified [19,72]. As a result of this interest,
a large amount of literature is available describing the adsorp­
tion of heavy metals by employing these potential sorbents.
Thus, this section is focused on highlighting some interesting
polysaccharides-based sorbents according to their synthesis
methods and chemical modifications, as well as the character­
istics of the removal of chromium from aqueous solutions.
Particularly, the effect of adsorption parameters, e.g., pH,
equilibrium, kinetics, thermodynamics, and mechanism, are
described in detail.
Chitosan
Chitosan is a cationic polysaccharide, namely (1,4)-2-amino-
2-deoxy-β-D-Glucose, obtained by the partial alkaline deace­
tylation of chitin, which is readily available in prawns, crabs,
and lobsters, and represents one of the most available and
cheapest biopolymers in nature.[22] It is a biodegradable, bio­
compatible, and nontoxic co-polymer, consisting of glucosa­
mine and N-acetylglucosamine units.[94] It has cationic
properties due to the abundant amino groups responsible
for metal ion scavenging.[1,3,95] However, it presents some
drawbacks such as mechanical and chemical instability, low
surface area, and susceptibility to swell and to dissolve in acid
media, which ultimately leads to decreased adsorption capa­
city after few adsorption/desorption cycles.[10,11]
In recent years, novel chitosan sorbents have been devel­
oped to increase the adsorption capacity and to improve
chemical stability and reusability. These novel chitosan sor­
bents include impregnated chitosan sorbents, crosslinked
chitosan sorbents, and chitosan composites. Moreover, the
specific adsorption characteristics in terms of pH effects, iso­
therms, kinetics, thermodynamics, and the mechanism of the
reaction are discussed.
Novel Chitosan Sorbents
Chitosan composites were prepared through physical meth­
ods, chemical methods, or both. For instance, physical mod­
ifications include the preparation of chitosan beads,
membranes, films, or nanoparticles, all promoting an increase
in adsorptive properties, porosity, surface area, number of
adsorption sites, enhanced swelling, as well as mechanical
and diffusion properties.[47] On the other hand, chemical
modification involves the use of crosslinking agents to
increase the chitosan chemical stability or toward introducing
functional groups to increase binding capacities.[22]
An interesting approach was to impregnate the chitosan
surface with scavenging moieties. Hua et al.[79] tested impreg­
nation with quaternary ammonium groups, preparing
10–30 µm chitosan well-shaped microspheres using a quatern­
ary ammonium salt. After Cr(VI) adsorption, the IR intensity
of the amino signals was significantly decreased, suggesting
the effective chelation of the chromium atoms by the amino
groups. At optimal conditions, the modified chitosan effec­
tively adsorbed 39 mg/g of chromium, which represented
a 97% removal efficiency.
Following this strategy, Kumar et al.[96] impregnated tetra­
octylammonium bromide to chitosan using a sonication-
assisted method to ensure a good impregnation of the ionic
liquid via hydrogen bonding and electrostatic interactions
between these components. It was demonstrated that these
interactions mainly occur between chitosan hydroxyl groups
and the ionic liquid quaternary ammonium cations. The ionic
liquid induced a positive co-operative effect for the uptake of
hydrochromate anions (HCrO4−) with a reported adsorption
capacity of 64 mg/g. Similarly, Kulkarni et al.[97] immobilized
1,5 diphenyl carbazide in crosslinked chitosan films, which
enhanced the removal efficiency of chromium up to 166 mg/g.
This enhancement was due to the incorporation of a selective

sequestrating agent and the crosslinking agent introducing
hydrophilicity and porosity to the film.
As mentioned, a big disadvantage of chitosan is its
weakness in acidic conditions since it is soluble in dilute
mineral acids.[94] Crosslinking brings an enhanced chemical
resistance to the chitosan structure and increases its
reusability.[98] Several chemical crosslinking agents have
been used, such as glutaraldehyde, epichlorohydrin, and
diglycidyl ether.[3,95] However, some of these chemical
reagents are presumably toxic in their free form. In parti­
cular, epichlorohydrin hydrolyzes into a chloropropanol
compound, which is considered carcinogenic and
genotoxic.[2] Therefore, the use of other crosslinking agents
is highlighted. For instance, Mirabedini et al.[2] prepared
a magnetic chitosan hydrogel film crosslinked with glyoxal.
The magnetite (Fe3O4)/chitosan sorbent exhibited magnetic
nanoparticles in the form of small seeds which led to
a maximum Cr(VI) adsorption capacity of 27 mg/g at pH
4 whereas up to three desorption cycles were conducted
with a very slight decrease from 79 to 75% in the Cr(VI)
removal capacity due to the strong glyoxal crosslinking.
The positive effect of the incorporation of such magnetic
particles could be due to an increased specific area induced by
the reduction of the chitosan crystallinity, as reported by
Chagas et al.[99] for their synthesized magnetite/chitosan
beads. Iron atoms disturb the crystalline nature of the poly­
mer by interrupting hydrogen bonding between its chains by
becoming complexed with the oxygen and nitrogen atoms.
This disturbance leads to a disorganization of the chains that
ultimately derives in a highly rough surface with an increased
specific area. Thus, the incorporation of iron potentiated
chromium uptake leading to a maximum capacity of
175 mg/g for the 10 wt.% magnetite loaded sorbent.
According to this, Zhang et al.[100] prepared a titanium-
loaded chitosan sorbent with a maximum capacity of 171 mg/
g with an enhanced reusability since 65% of the capacity
remained after six cycles. A detailed description of the
mechanism involved in the Cr(VI)-chitosan adsorption is
proposed in this paper. However, in this case, Cr(VI) was
adsorbed by electrostatic forces between Ti+4 and HCrO4−
and ligand exchange with Cl− and HCrO4−.
Crosslinked Chitosans
The conventional method for the formation of chitosan par­
ticles consists of a crosslinking reaction taking place on
a reversed suspension.[79,95] However, other methods could
be carried out. For instance, Wu et al.[101] developed a drop-
sphere method to synthesize spherical and uniform chitosan
particles that were crosslinked using epichlorohydrin through
the hydroxyl groups. The observed shift of their characteristic
peaks in the FTIR spectrum allowed to follow the crosslinking
process. After Cr(VI) adsorption, few bright spots were
observed in SEM micrographs due to the presence of accu­
mulated chromium. For this sorbent, the adsorption mechan­
ism was described to be ion-exchange rather than physical
adsorption.
Even though crosslinking increases the chitosan chemical
stability, it also reduces its adsorption capacity since the
SEPARATION & PURIFICATION REVIEWS 11
amino groups interact by covalent bonding with crosslinking
agents becoming blocked and the other binding sites are
sterically hindered.[102] To overcome this drawback, non-
amino-selective crosslinking agents can be used, or some
chemical modifications such as grafting functional groups
must be realized.[2] Li et al.[103] modified the chitosan mor­
phology from powder or flakes to nanofibers, enhancing its
Cr(VI) uptake capacity from 27 mg/g to 68 mg/g due to the
increased surface area. Chitosan nanofibers were prepared by
electrospinning using a 95% acetic acid solution achieving an
average diameter of 75 nm.
Amino and thiol groups can be bound to chitosan to
improve its heavy metal uptake capacity.[1,79,95] In this regard,
Sankararamakrishnan et al.[3] prepared a crosslinked chito­
san-xanthate sorbent using glutaraldehyde and CS2 for che­
mical modifications. This crosslinking allowed for a stable
adsorption capacity after repeated adsorption/desorption
cycles. However, it did not compromise the adsorption capa­
city due to the introduction of thiol functional groups. High
Cr(VI) adsorption values of 625 and 256 mg/g were obtained
for flakes and beads, respectively, compared to their 156 and
35 mg/g respective raw initial capacities. Similarly, Moreno-
López et al.[104] developed a crosslinked chitosan-xanthate
sorbent supported onto a low density polyethylene/agave
composite.[104] Besides achieving the reusability of six adsorp­
tion/desorption cycles due to the crosslinking with adipoyl
chloride, the maximum adsorption capacity of 285 mg/g was
observed due to the incorporation of xanthate groups. The
raw chitosan-coated sorbent adsorbed only 200 mg/g Cr(VI).
Other efforts have been done to crosslink chitosan ioni­
cally. For example, Bhatt et al.[78] crosslinked chitosan using
an organic acid. It is noteworthy that the adsorption (with
a maximum capacity of 192 mg/g) resulted in a complete
reduction of Cr(VI) to Cr(III). In another study, Bhatt et al.­
[105]
observed ionic crosslinking through hydrogen bonding
and π-π supramolecular interactions using another organic
carboxylic acid. After the adsorption, observations using scan­
ning electron microscopy with energy dispersive X-ray
showed a full bright surface of the porous material confirming
the chromium uptake. We confirmed these observations: after
chromium adsorption, the composition contrast observed in
Figure 4 was obtained by retrieving the signal of the back­
scattered electrons.
The principle for crosslinking chitosan without compro­
mising its adsorption capacity consists of carrying out Schiff
base reactions to protect the chitosan amino groups.[98,101] Li
et al.[95] developed a highly crosslinked thiocarbohydrazide
(TC) chitosan gel by carrying out a Mannich reaction between
TC’s terminal amino groups and the intermediates from the
Schiff base reaction of chitosan amino groups and formalde­
hyde used as linkage. These findings were confirmed via FTIR
with the appearance of a peak at 1545 cm−1 due to the –C = S
double bonds. The presence of the aminothiourea functional
groups enhanced the adsorption leading to a Cr(VI) capacity
of 145 mg/g.[95]
Shi et al.[106] chose to crosslink chitosan onto different
clays: zeolite and montmorillonite. For this purpose, the
Schiff base was reacted with benzaldehyde, halogenated, and
crosslinked with epichlorohydrin, and its functionality was
12 M. E. GONZÁLEZ-LÓPEZ ET AL.
Figure 4. SEM micrographs of chitosan composite after Cr(VI) adsorption using a) electron back scattered diffraction and b) secondary electrons.
further increased through a ring-opening reaction with poly­
ethylene polyamine to increase the number of amino groups.
It was expected that chitosan active sites increase the Cr(VI)
adsorption in comparison with raw clay materials. However,
the chitosan/clay ratio was selected at 40:1 for zeolite and 20:1
for montmorillonite to prevent the adsorption from decreas­
ing due to a too small clay porous structure and/or specific
area. When this material was used as a sorbent, the maximum
Cr(VI) uptake capacities were respectively 29 and 23 mg/g for
the chitosan modified by zeolite and by montmorillonite
compared to 4.9 mg/g for the raw chitosan sorbent. In this
case, the presence of zeolite significantly increased the adsorp­
tion capacity. In some cases, the zeolite exchangeable cations
could hinder the interactions between chitosan and chro­
mium ions. This was observed by Habiba et al.[11] who pre­
pared by electrospinning a ternary composite of chitosan,
zeolite, and polyvinyl alcohol (PVA) that had a maximum
adsorption capacity of only 9.2 mg/g. The authors highlighted
the importance of maintaining the zeolite crystalline structure.
However, a good stability was observed since no decrease in
the uptake capacity was seen after five cycles, indicating the
feasibility of this sorbent for practical application.
Chitosan Composites and Adsorption Parameters
Besides zeolite and montmorillonite mentioned above, bento­
nite was also used as an adsorbent by Moussout et al.[107]
Specifically, they obtained a 5% bentonite-chitosan composite
in which chitosan was intercalated between the clay interlayer
spaces. This was due to the strong interactions between chit­
osan functional groups and bentonite silicate layers. This
material was tested for chromium removal of simulated pol­
luted aqueous solutions and in a real effluent from the tan­
ning industry. For simulated solutions, a 59 mg/g adsorption
capacity was obtained enough to treat effectively the real
effluent from the tanning industry despite the presence of
other species.
Recently, chitosan-silicon dioxide membranes have been
prepared and used as sorbents. SiO2 is an amorphous porous
polymer in which silanol groups are responsible for
adsorption. Firstly, Deng et al.[1] synthesized a chitosan-SiO2
membrane in the form of particles. However, in a further
study, they prepared a similar membrane using carboxy­
methyl chitosan to increase the efficiency of the sorbent by
incorporating more amino and hydroxyl groups.[10] The
enhanced capacity was related to the ability of carboxymethyl
groups to chelate metal ions due to the lone electron pairs that
are capable of constituting coordination bonds forming stable
chelates.
pH Effects
It has been demonstrated that pH has a strong influence in
the adsorption process by controlling the protonation of the
chitosan surface and the speciation of the chromium ions.­
[1]
On this regard, in aqueous solutions, Cr(VI) is present
in the form of oxyanions with a pH dependent equilibrium
such as[10,46,96]:
H2 CrO4 $ HCrO4 þ Hþ pKa ¼ 4:1 (40)
HCrO4 $ CrO4 2 þ Hþ pKa ¼ 5:9 (41)
Cr2 O7 2 þ H2 O $ 2 HCrO4 pKa ¼ 2:1 (42)
The latter indicates that molecular H2CrO4 is present at pH
around 1–2, unable to interact via electrostatic forces,
whereas all other anionic species: Cr2O7−2, HCrO4−, and
CrO42-, appear as pH increases.[1,10,103] In particular,
HCrO4− is predominant in the 2–6 pH range while at higher
pH values, the ratio of CrO4−2/HCrO4− starts to rise as
shown by Figure 5.[10,79] In the case of activated carbon,
the adsorption is reported to be favored at acidic pH due
to the strong acidic conditions that cause a highly proto­
nated adsorbent surface, which results in a high uptake of
Cr(VI) in the anionic form.[26] On the other hand, the lower
sorption of Cr(VI) on carbon with increasing pH is generally
attributed to an increased electrostatic repulsion between the
negatively charged metal species and negatively charged
carbons.[26] Moreover, it has been reported that sorbents
with groups containing nitrogen, such as NH, NH2, and

Figure 5. Speciation diagram of chromium (VI) as function of pH.
pyridine, also enhance Cr(VI) adsorption being protonated
at acidic pH values.[41]
Particularly, chitosan has a reported pKa value between 6.3
and 7.0; thus, it is expected that its amino groups become
protonated as -NH3+ in a 2–6 pH range and stay neutral
above pH 8.[10,101] Therefore, the adsorption of chitosan-
based sorbents is optimal at pH between 3 and 6. Above pH
6, the removal capacity is expected to decrease due to depro­
tonated chitosan adsorption sites with less affinity for CrO4−2
anions, and also due to other ions competition.[2,79,106]
However, novel chitosan-based sorbents are being developed,
aiming to increase the adsorption capacity and chemical sta­
bility by combining properties of different components. Thus,
the charge of the sorbent surface strongly depends on the
grafted functional groups.
For instance, chitosan-SiO2 membranes exhibited
a maximum uptake capacity of 0.02 mg/g at pH 3.0 for raw
chitosan and 81 mg/g for carboxymethyl chitosan at pH 5.0.[1,10]
A shift in the optimal pH was observed with the incorporation of
carboxymethyl groups. Moreover, when raw-chitosan was used
80 min were needed to reach equilibrium when only 60 min
were needed with carboxymethyl chitosan.
The embedded chitosan with ionic liquid carried out by
Kumar et al.[96] led to interesting findings related to pH. In
the 3–4 pH range, a co-operative triangular interaction
between chitosan, ionic liquid, and chromium occurred. The
ammonium cation formed H-bonds with chitosan whose pro­
tonated amino groups further interacted with the hydrochro­
mate anions.
In the case of crosslinked chitosan resins, Wu et al.[101]
reported that the maximum uptake capacity of 113 mg/g was
found at pH 3.0 with protonated chitosan amino groups
interacting with Cr2O7−2 and HCrO4− chromium species. In
fact, above pH 5, the adsorption sharply decreased.
Sankararamakrishnan et al.[3] also observed an optimal pH
SEPARATION & PURIFICATION REVIEWS 13
of 3.0 with a crosslinked chitosan-xanthate sorbent. However,
they reported that at the end of the adsorption process, the
pH of the solution increased to 5.5 due to HCrO4− reduction
and H+ consumption.
A similar pH 3 optimal condition was reported for the
ionically crosslinked chitosan sorbent developed by Bhatt et ­
al.[78] Furthermore, Bhatt et al.[105] reported that the point of
zero-charge of the ionically crosslinked with a carboxylic acid
adsorbent was 9. Thus, at pH 2, the hydroxyl, amino, and
carboxyl groups were protonated favoring the adsorption,
leading to a maximum Cr(VI) capacity of 129 mg/g.
Chagas et al.[99] added magnetic particles to the sorbent
whose surface became positively charged in an acid medium
due to Fe-OH2+ groups. The Cr(VI) adsorption was maxi­
mum at pH 3 and decreased when the pH increased due to
the competition of the hydrochromate ion and the OH−
anions. It was observed that not only hydroxyl anions com­
pete but sulfate anions also. Li et al.[103] found that for
a nanosized chitosan sorbent able to take 132 mg/g Cr(VI)
at pH 5 could take only 68 mg/g at pH 3 adjusted by H2SO4
due to SO4−2 competition. This sulfate competition also
explained the decrease in the adsorption capacity in pH values
above the zero-point of charge (pHzpc) of the crosslinked
thiocarbazide-chitosan sorbent developed by Li et al.[95]
Since the pHzpc of the sorbent was determined to be 6, the
optimum pH for chromium adsorption was set at 4.3 due to
the chromium speciation and the generation of positive active
sites, mainly –NH3+, –NH2+ and –SH+.
Adsorption Equilibrium
Most of the chitosan-based sorbents are feasibly described
using the Langmuir model. This isotherm describes the for­
mation of a monolayer within a limited number of energeti­
cally homogeneous sites and assumes that no interactions
occur between adsorbed molecules.[97] Raw chitosan-SiO2
14 M. E. GONZÁLEZ-LÓPEZ ET AL.

and carboxymethyl chitosan-SiO2 membranes were more
accurately described by the Langmuir isotherm rather than
Freundlich isotherm, indicating a monolayer reaction with
a calculated maximum capacities of 210 and 81 mg/g,
respectively.[1,10]
Crosslinked particles are also correctly described by the
Langmuir isotherm. Monolayer adsorption was observed
between 30°C and 50°C for a crosslinked resin synthesized
by Wu et al.[101] An increase in the Cr(VI) uptake capacity
was observed at 50°C due to the endothermic nature of the
process. The maximum Cr(VI) adsorption capacity was
113 mg/g. Moreover, from the Langmuir model, the separa­
tion parameter RL could be calculated to determine whether
the adsorption is favorable or unfavorable, and many of the
chitosan-based sorbents had RL numbers lower than 1.[99]
Although, most of the chitosan-based sorbents present favor­
able adsorption, irreversible adsorption is observed if RL
approximates zero. This is the case of two crosslinked chit­
osan-xanthate sorbents developed by Sankararamakrishnan
et al.[3] with RL of 0.0076 and 0.0004 for an initial Cr(VI)
concentration of 1 g/L which is an indication of poor sorbent
reusability.
The Langmuir model parameters of selected chitosan-
based sorbents are listed in Table 3. At this point, it is
important to notice that the KL Langmuir constant is an
indicator of the behavior of a given sorbent at low Cr(VI)
concentrations, which could provide insights into meeting
regulatory limits. When KL is small, it means that the equili­
brium concentration at the liquid-phase (Ce) could be high
even if adsorption performance in terms of capacity is high.
Therefore, a large KL value is desirable for adsorption-
favorable materials. In other words, KL indicates how
pronounced is the linear stage of the equilibrium at low
concentrations. It also tells how close to low concentrations
would the maximum adsorption capacity be achieved. The
latter means that for a similar value of qmax, the high KL
sorbent will achieve its maximum adsorption at a lower
Cr(VI) concentration with also a lower Ce value.
Given this, the following paragraphs intend to compare
some other isotherm models used for data fitting, such as
Freundlich, Temkin and, Halsey models; and also, to highlight
the information that could be obtained from these models
where good correlation is shown despite Langmuir model
presented a higher correlation in many cases. For example,
the ionic liquid impregnated chitosan sorbent reported by
Kumar et al.[96] had a r2 = 0.99 correlation with the
Langmuir isotherm better than with all other models:
Freundlich, Redlich-Peterson, and Temkin had r2 = 0.94,
Elovich r2 = 0.65, and Dubinin-Radushkevich r2 = 0.47.
Using the Langmuir constant, KL, the dimensionless separa­
tion parameter, RL, was calculated to be 0.76 (eq. 2), indicat­
ing favorable Cr(VI) adsorption and proving the efficacy of
the co-operative triangular interaction. However, the
Dubinin-Radushkevich model allowed estimating the mean
free energy of adsorption as 0.255 kJ/mol (eq. 8) from which
the authors stated that physical adsorption occurred.
For chitosan-clays sorbents, Shi et al.[106] reported
a slightly higher correlation with Freundlich rather than
Langmuir isotherms. It may suggest that the initial monolayer
Cr(VI) adsorption could be followed by multilayer and het­
erogeneous adsorption with these modified sorbents. The
Freundlich parameter 1/n was lower than 0.5 (n > 2), indicat­
ing favorable adsorption. Bhatt et al.[78] used Freundlich,
Temkin, and Halsey isotherms to study the Cr(VI) adsorption
equilibrium with a crosslinked chitosan sorbent, reporting
a 192 mg/g maximum capacity. Although the Langmuir cor­
relation was high, the Freundlich constant n was higher than
one, a sign of favorable adsorption (eq. 3). The Temkin model
confirmed these findings suggesting that electrostatic interac­
tions were the dominant mechanism. In another work, the
authors alleged that chemisorption, or electrostatic interac­
tions occurred since the bTe constant, related to the heat of
adsorption, was high: 25 J/mol (eq. 10). Moreover, the Halsey
and Elovich models returned correlations r2 > 0.98 in both
cases, hence a small contribution of multilayer adsorption was
also considered.[105]
Similar findings were reported by Moussout et al.[107] for
a different chitosan-clay sorbent. In this case, the chitosan-
bentonite sorbent followed the Redlich-Peterson model,
which includes characteristics of Langmuir and Freundlich
in a wide range of concentrations. Based on this, it could be
said that the sorbent surface or the active binding sites were
rather energetically heterogeneous, and Cr(VI) monolayer was
not the only adsorption taking place. Similarly, Li et al.[103]
observed that their nanosized chitosan sorbent exhibited both
Langmuir and Freundlich adsorptions. They suggested that

Table 3. Langmuir Equilibrium Parameters of Chitosan Sorbents.

Experimental
conditions**
C0 ρads teq
Adsorbent qmax (mg/g) Ce (mg/L)* KL (L/mg) RL (-) (mg/L) (g/L) pH (h) Ref.
[99]
Chitosan-Fe3O4 beads 175 3000 0.003 0.656 2.5–750 1.0 3.0 5
[97]
Diphenyl carbazide immobilized chitosan 166 3 3.010 0.007 10–100 - 2.0 96
[96]
Ionic liquid impregnated chitosan 63 560 0.016 0.760 - 8.0 3.5 0.5
[79]
Chitosan microspheres 39 4 2.780 0< RL<1 - 5.0 5.0 0.8
[3]
Crosslinked chitosan xanthate flakes 625 3000 0.003 0.008 50–1000 2.0 3.0 16
Crosslinked chitosan xanthate beads 256 9000 0.001 0.0004
[2]
Fe3O4/chitosan hydrogel 27 35 0.261 0.113 5–30 1.0 4.0 1.8
[94]
Crosslinked chitosan micro/nano particles 124 100 0.086 0<RL<1 50–400 0.8 2.0 3
[102]
Chitosan graphene oxide nanocomposite 92 115 0.076 0< RL<1 10–500 0.05 3.0 5
[98]
Crosslinked magnetic chitosan resin 58 430 0.021 0.10 10–300 0.5 2.0 8
*Ce = equilibrium concentration calculated or estimated at 90% of maximum adsorption capacity.
**C0 = range of initial concentrations, ρads = adsorbent dosage, teq = time for equilibrium.
 SEPARATION & PURIFICATION REVIEWS 15

multilayer Cr(VI) adsorption occurred once monolayer
deposition becomes hindered by a limited inner diffusion. It
could also be an indication that the entire surface area of the
sorbent is not being exploited due to low exposure.
The Sips isotherm associates features of both Langmuir
and Freundlich isotherms (eq. 4). At low concentrations, the
Sips isotherm fits the Freundlich model, while at higher con­
centrations, it is closer to the Langmuir model.[99] The Sips
model was used by Chagas et al.[99] to describe Cr(VI) adsorp­
tion of magnetite-chitosan beads, with a calculated maximum
capacity of 175 mg/g.
Adsorption Kinetics
Practical applications need a good knowledge of both
adsorption thermodynamics and kinetics to establish the
rate-limiting steps.[22] The Cr(VI) adsorption dynamics in
chitosan sorbents occurs in multiple steps; 1) initially, the
open high surface area and available active sites are covered
by extra and intra-particular diffusion; 2) as adsorption
progresses, intraparticle or pore diffusion becomes the rate-
limiting step,[105] 3) interactions between the adsorbate and
the sorbent play an essential role in the adsorption
kinetics.[10] The pseudo-first-order and pseudo-second-
order models are the most commonly reported equations
modeling this kinetics. The second-order model describes
most of the chitosan-based sorbents since chemisorption,
with sharing and exchange of electrons between Cr(VI) and
chitosan has been demonstrated to be the rate-limiting
step.[106]
Using chitosan nanofibers, Li et al.[103] detailed the mass
transfer steps consisting of external diffusion from the bulk
to the solid-liquid interface, and diffusion inside the nano­
fibers as illustrated by Figure 2. They suggested that both
monolayer and multilayer adsorptions occurred. As diffu­
sion became limited, multilayers formed when monolayer
adsorption was no longer favored. Fitting to the pseudo-
second-order model observed in this case, they proposed
that the chitosan-Cr(VI) electron exchange was the rate-
controlling step. Bhatt et al.[78] also used the pseudo-second
-order kinetic model to establish that complexation was the
rate-limiting step of their Cr(VI)-chitosan adsorption, che­
misorption is predominant rather than physisorption.
However, some Cr(VI) physisorption was controlled by
more than one step since a boundary layer and pore diffu­
sion were detected using the Bangham model.[78] An
approach to study pore diffusion or intraparticle diffusion
is the use of the intraparticle diffusion model employing
Weber-Morris plots (eq. 19).[70] The analysis of the inter­
cept and slope values of one or multiple straight lines
informs on the single-step or a multi-step nature of adsorp­
tion (Figure 3).[97,108]
Boundary layer and intraparticle diffusion controlled the
Cr(VI) rate of adsorption of the Bhatt et al.[105] ionically
crosslinked chitosan sorbent and Moussout et al.[107] chito­
Interestingly, the Cr(VI) adsorption kinetics on diphenyl-
carbazide immobilized chitosan films was described by a first-
order model.[97] Thus, the rate-controlling mechanism was
external mass transfer. However, the authors also used
Weber-Morris plots to determine that pore and film diffusion
co-occurred during the adsorption. Thermodynamics
returned an initial endothermic nature of the process reflect­
ing a non-spontaneous adsorption, however at larger times,
∆G became negative, changing to a spontaneous and irrever­
sible adsorption.
Thermodynamics
In general, the thermodynamics of adsorption on chitosan
sorbents describe a spontaneous process according to the
∆G negative values.[105,107] However, the nature of the adsorp­
tion has been described to be exothermic (∆H > 0) or
endothermic (∆H < 0) by several authors. Table 4 includes
Cr(VI) thermodynamic parameters for chitosan sorbents.
Adsorption Mechanism
The conventional chromium adsorption mechanism for chit­
osan sorbents was described as follows: 1) the negative
HCrO4− anions are adsorbed by the positively charged -
NH3+ groups of the sorbent in acidic medium[98,106]; 2) the
adsorbed Cr(VI) is reduced to Cr(III) by added electron
donator groups such as thiol, amino, and/or carboxyl groups,
mainly) and protons of the acid medium; 3) the Cr(III)
oxyanions stay complexed by the positively charged sites or
are released back to the solution by an ion-exchange mechan­
ism as illustrated by Figure 6A.[97] The pH level must be
acidic since a pH increase neutralizes the -NH3+ groups inhi­
biting Cr(VI) complexation. In the work of Li et al.,[95]
protonated –NH3+ and –SH+ groups adsorbed HCrO4−
anions reducing them to Cr(III) staying complexed by the
ammonium groups. The process was ruined at elevated pH.
Sankararamakrishnan et al.[3] reported a pH increase from 3
to 5.5 at the end of the Cr(VI) adsorption/reduction. In other
words, this change in final pH value is a strong indication that
reduction is taking place in the adsorption mechanism.
This mechanism was commonly observed by numerous
authors: Chagas et al.[99] using a chitosan/magnetite nano­
composite to adsorb Cr(VI) reducing it to Cr(III) staying
adsorbed by –H2N-Cr(III) bondages. Kulkarni et al.[97] incor­
porated carbazide into chitosan films also adsorbing Cr(VI)
and reducing it to Cr(III). Bhatt et al.[78] reported the very
same mechanism with chitosan added carbonyl groups. The
Table 4. Thermodynamic Parameters of Chitosan Sorbents.
∆H ∆S ∆G
Adsorbent (kJ/mol) (J/mol K) (kJ/mol) Ref.
Thiocarbohydrazide crosslinked 59 250 −11.1 [95]
chitosan
Trimesic acid crosslinked chitosan −19 −57 −1.8 [105]
[96]
Ionic liquid impregnated chitosan −90 −257 −13.9
Chitosan microspheres 16 75 −6.6 [79]

san-bentonite sorbent. Wu et al.[101] observed an adsorption Bentonite chitosan composite −0.5 −1.3 −0.1 [107]
[2]
kinetics exhibiting three different straight-lines. They assigned Fe3O4/chitosan hydrogel −23 −64 −3.5
[100]
Titanium crosslinked chitosan 3.4 37 −6.9
the first straight line to external diffusion, the second one to Chitosan Graphene oxide 13 90 −15.6 [102]

intraparticle diffusion, and the third one to adsorbate- nanocomposite

[98]
Crosslinked magnetic chitosan resin 20 65 −0.6
adsorbent interactions.
16 M. E. GONZÁLEZ-LÓPEZ ET AL.
Figure 6. Mechanism of chromium adsorption onto A) chitosan-based sorbents and B) cellulose-based sorbents.
surface complexation adsorption model was also suggested by
Shi et al.[106] to describe the mechanism of crosslinked chit­
osan-clay sorbents.
To sum up, the vast majority of chitosan-based sorbents
adsorb Cr(VI) oxyanions in acidic media by electrostatic
interaction with the protonated amino groups (Figure 6).
Many of the sorbent modification introduces new electron-
donor groups, which trigger the Cr(VI) reduction to its less-
dangerous Cr(III) species Cr(III), which stay chelated or, in
very acidic medium, is released as Cr3+ to the solution.
Cellulose
Cellulose is another extensively available polysaccharide gen­
erated from repeating β-D-glucopyranose units, which are
covalently linked through acetal functions between the hydro­
xyl groups positioned at equatorial place of C4 and C1 atoms
(β-1,4-glucan).[109] As a result of these interactions, cellulose
is a large chain polymer with a particular structure that
provides attractive characteristics like hydrophilicity, chirality,
biodegradability, and a wide range of reactions by which it
can be modified to change its properties.[109,110] Hydroxyl
groups located at the positions C2, C4, and C6 of the repeti­
tive unit of the cellulose backbone are targeted for etherifica­
tion, esterification, halogenation, or oxidation reactions.[57,110]
Modified cellulose demonstrated capabilities for the removal
of heavy metals, including Cr(VI), in water streams.[111]
Novel Cellulose Sorbents
Cellulose by itself possesses low scavenging capacity for heavy
metals. Thus, it must be modified. Dong and Zhao[112]
explored the use of ionic liquids followed by the grafting of
glycidyl methacrylate moieties to functionalize microspheres
of microcrystalline cellulose, leading to a Cr(VI) uptake of
182 mg/g. Yang et al.[113] modified cellulose nanofibers by
TEMPO (2,2,2,6-tetramethyl-1-piperidinyloxy) oxidation and
subsequently coupled cysteine. These modified cellulose

nanofibers were embedded in polyacrylonitrile to enhance
their mechanical properties, and used to remove Cr(VI) and
Pb(II). Specifically, the removal of Cr(VI) was 87 mg/g. On
the other hand, Zhong et al.[114] modified cellulose with
amine and carboxyl groups. This material was tested in the
uptake of Cu(II) and Cr(VI), yielding a maximum capacity of
chromium removal of up to 227 mg/g.
The modern trend is to combine two or more materials
seeking the addition of their properties or even synergistic
effects.[29,115] Hokkanen et al.[116] used a hydroxyapatite/cel­
lulose-based material in the removal of Cr(VI), obtaining
a mediocre adsorption capacity of 47 mg/g. Grafting polymers
onto cellulose surface gave brittle materials. TiO2 was used to
improve the grafted cellulose mechanical strength. Anirudhan
et al.[111] synthesized a polyglycidylmethacrylate-γ-TiO2 cellu­
lose showing a maximum removal capacity of 124 mg/g.
On the other hand, polymers containing amine groups are
frequently used to improve the sorbent hydrophily and Cr(VI)
uptake capacity. Qiu et al.[117] synthesized a polyaniline-ethyl
cellulose material by a surface-initiated polymerization
method, but the Cr(VI) adsorption capacity was merely reach­
ing 39 mg/g. Liu et al.[118] obtained better results incorporat­
ing polyethyleneimine into cellulose via an amidation
reaction. Their composite achieved a high maximum Cr(VI)
removal of 358 mg/g. Other similar tentatives produced cel­
lulose-based material with fast Cr(VI) uptake, high adsorption
capacity, and regeneration, as reported by Zhang et al.[119]
They developed a cellulose-based ion exchange sorbent by
radiation-induced grafting of styrene onto cellulose micro­
spheres followed by acetylation and amination processes
obtaining a Cr(VI) uptake capacity of 123 mg/g.
Inexpensive lignocellulosic materials were recently tested
for Cr(VI) adsorption.[19,21] Khelaifia et al.[120] tested raw date
stones without any physical or chemical treatment for Cr(VI)
removal. The uptake could not pass 20 mg/g. Babu and
Gupta[23] heated neem leaves and treated them by HCl. The
Cr(VI) removal raised to 63 mg/g. Recently, biomass-based
composites were prepared and tested. Akram et al.[29] pre­
pared a composite from mango kernel and ferric chloride that
showed an impressive removal capacity of 320 mg/g.
Unfortunately, most of the lignocellulosic materials possess
low Cr(VI) adsorption capacities; their low cost is the only
appealing factor that is lost if modifications implying
a number of reagents and steps are needed to reach acceptable
Cr(VI) uptake capacity.
Adsorption Parameters on Cellulose-based Sorbents
pH Effects
At its pHpzc the adsorbent has an equal number of positive
and negative charges. Below this pH value, protonated species
give a positive charge to the adsorbent surface. Above the
pHpzc, the adsorbent surface has an excess of negative
charges.[121,122] The chromium speciation diagram (Figure 5)
shows that a useful sorbent must have a pHpzc lower than 6 to
increase chromium affinity in acidic media.[18,46] Obviously,
the pHpzc value of cellulose-based materials is strongly depen­
dent on functional groups existing in either raw or modified
materials. Lin et al.[123] showed that corncob linked to
SEPARATION & PURIFICATION REVIEWS 17
branched polyamide had a high pHpzc around 8 with
a positive adsorbent surface at pH lower than 8 which was
favorable for the removal of Cr(VI) at pH 2 with an adsorp­
tion capacity of 48 mg/g. Sun et al.[124] prepared a cellulose
coated magnetic silica modified with primary and secondary
amino groups. The pHpzc of this material was also around 8
and a good adsorption capacity of 171 mg/g was achieved at
pH 2. Xu et al.[125] prepared a biosorbent from cotton stalk
peel by amination reaction with a mediocre initial uptake at
pH 2 that was raised to 129 mg/g by increasing the pH to 3
due to an optimal protonation of active amine sites interact­
ing with Cr(VI) ions. In contrast, at higher pH values, the
sorbent surface became negatively charged and the Cr(VI)
adsorption vanished. Other works aimed to optimize Cr(VI)
adsorption in milder acidic conditions. Zhou et al.[126] pro­
posed a modified cellulose-containing β-cyclodextrin and
quaternary ammonium groups in which the Cr(VI) adsorp­
tion value reached 61 mg/g at pH 4. Thus, the optimal pH
values for interaction between cellulose-based materials and
Cr(VI) is between 2 and 5.
Adsorption Equilibrium
Langmuir and Freundlich isotherms are the best to describe
the Cr(VI) equilibrium adsorption of cellulose-based sor­
bents. Chromium adsorption using London plane leaves
was accurately described by Langmuir isotherm indicating
a monolayer coverage. The maximum capacity was
83 mg/g.[127] Sharma et al.[128] evaluated Cr(VI) adsorption
onto microcrystalline cellulose immobilized zero-valent iron
nanoparticles of high surface area, a large number of active
sites and fast electron transfer. The Langmuir model showed
the best fitting of experimental data with a maximum Cr(VI)
adsorption of 59 mg/g.[77]
Hokkanen et al.[116] compared the Langmuir, Freundlich,
and Sips isotherm models to describe Cr(VI) adsorption on
hydroxyapatite micro-fibrillated cellulose. The Freundlich
model fitted best the experimental data while the Sips para­
meter KS was 0.3 (close to 0) confirming the Freundlich
behavior (eq. 4). Khelaifia et al.[120] obtained a Sips parameter
KS of 0.14, small enough to correspond to a Freundlich
adsorption. Sarkar and Sarkar[129] used Langmuir,
Freundlich, and Temkin models to investigate Cr(VI) adsorp­
tion onto Fe(III)-cellulose nanocomposite, the Langmuir
model best fitted the Cr(VI) adsorption data. Pourfadakari
et al.[130] found a better modeling by Langmuir for nanosized
cellulose fibers rather than by the other used models of
Freundlich, Dubinin-Radushkevich, and Temkin.
Table 5 shows that most of the published data rely on
the Langmuir model. Helpful information can be obtained
from other models. Using the Dubinin-Radushkevich model
(eqs. 6–8), Moussavi and Barikbin[108] found that chemi­
sorption was the dominant process of Cr(VI) adsorption on
a green pistachio hull sorbent. Also using the Dubinin-
Radushkevich model, Omidvar Borna et al.[131] calculated
a 2.76 kJ/mol mean energy of Cr(VI) adsorption a clear sign
of physisorption onto a Hibiscus Cannabinus kenaf sorbent.
The Langmuir isotherm fitted the sawdust sorbent tested by
Gupta and Babu.[132] However, the Redlich-Peterson and
Koble-Corrigan isotherms were also appropriate suggesting
18 M. E. GONZÁLEZ-LÓPEZ ET AL.

Table 5. Langmuir Cr(VI) Equilibrium Parameters of Cellulose Sorbents.

Experimental
conditions**
C0 ρads
Adsorbent qmax (mg/g) Ce (mg/L)* KL (L/mg) RL (-) (mg/L) (g/L) pH teq (h) Ref.
[118]
Carboxylated cellulose/polyethyleneimine 358 295 - 0.190 10–200 0.1 3 -
[129]
Cellulose coated Fe(III) 126 8 - 0.008 - 3.0 2 6
[108]
Pistachio hull 116 120 0.075 0 < RL < 1 50–200 5.0 2 0.5
[127]
London plane leaves 68 250 0.042 0.130 50–300 2.0 3 72
[115]
Fe3O4 coated cellulose/hydrotalcite 29 6000 0.002 0.039 80–140 0.1 3 -
Fe3O4 coated cellulose/hydroxyapatite 27 4000 0.002 0.029
[120]
Date stones 20 750 0.012 - 5–100 1.0 2 1
[116]
Cellulose/Hydroxyapatite 115 565 0.016 - 0.01–0.5 0.8 5 12
*Ce = equilibrium concentration calculated or estimated at 90% of maximum adsorption capacity.
**C0 = range of initial concentrations, ρads = adsorbent dosage, teq = time for equilibrium.

a combination of heterogeneous and homogeneous adsorp­ Adsorption Mechanism

tion sites on this cellulose-based sawdust sorbent. The max­ The mechanism of chromium removal from aqueous solu­
imum Cr(VI) adsorption capacities were coherent; 42 mg/g tions by cellulose-based sorbents is described by a diffusion
with the Langmuir model and 32 mg/g with the Dubinin- stage but later controlled by chemisorption at the interface.
Radushkevich model. The mean adsorption energy sug­ The Cr(VI) adsorption reaction on cellulose-base sorbents is
gested a physical Cr(VI) adsorption. more complex and affected by more factors than that in
chitosan-based sorbents. The mechanisms involved chemical
adsorption, chelation, surface complexation, pores, ion
Adsorption Kinetics exchange, hydrogen bridges, electrostatic attraction, surface
Pseudo-first-order and pseudo-second-order kinetic models adsorption, and entrapment in inter and intra-fibrillar capil­
are the most commonly used to represent the Cr(VI) laries (Figure 6B).[117,129,136–138]
adsorption mechanism and cellulose-based sorbent effi­ Cellulose amination is a common pathway to increase the
ciency helping to optimize process conditions and affinity of the polysaccharide for chromium ions by adding
parameters.[53] A pseudo-first-order model represented the cationic ligands mimicking the protonated amines of chito­
diffusion and mass transfer controlled Cr(VI) adsorption by san-based sorbents.[133] Amination also induced Cr(VI) com­
the aminated-succinate nanocrystalline cellulose developed plexation as demonstrated by Zhou et al.[139] Similarly to
by Singh et al.[133] Chemisorption was the limiting rate of chitosan-based sorbents, adsorbed Cr(VI) can be reduced to
adsorption for the amino-functionalized magnetic cellulose Cr(III) by adjacent electron-donor groups. Cr(III) can be
adsorbent of Sun et al.[124] Liu et al.[118] also fitted their complexed by hydroxyl or other functional groups in the
results by a pseudo-second-order model. The rate constant cellulose network.
k2 decreased with increasing initial Cr(VI) concentration, Ion exchange is a desired mechanism. Cellulose succina­
a sign that the equilibrium time is concentration tion followed by derivatization with triethylenetetramine were
dependant. performed by Gurgel et al.[140] The created active sites allowed
The two pseudo-first and pseudo-second-order kinetic to adsorb Cr(VI) ions by ion exchange with iodine. Poly
models have some limitations regarding synergistic beha­ (glycidyl methacrylate) functionalized with ammonium qua­
vior between diffusion mechanism, chemisorption ternary groups were grafted to cellulose to create active sites
mechanism or thermodynamics. Zhong et al.[114] simu­ for ion exchange with metal ions.[111] Zhong et al.[114]
lated cellulose-biomass data by the pseudo-first-order described an amphoteric cellulose adsorbing Cr(VI) ions by
model, pseudo-second-order model, Elovich equation, electrostatic forces, then reducing them into Cr(III) by elec­
and intraparticle diffusion model. The data agreed well tron donor groups and complexing the reduced Cr(III) by
with the pseudo-second-order model, diffusion was hydroxyl and carboxyl adjacent groups.
involved but other mechanisms such as boundary layer
diffusion were implicated in the Cr(VI) sorption.
Bhattacharya et al.[134] reported a complex Cr(VI)
Table 6. Thermodynamic Parameters of Cellulose Sorbents.
adsorption mechanism on different low-cost adsorbents.
∆H ∆S ∆G
Some authors tried to develop original kinetic models. Adsorbent (kJ/mol) (J/mol K) (kJ/mol) Ref.
For example, Park et al.[135] associated ionic adsorption Carboxylated cellulose/ −2.7 10 −5.8 [118]
and redox reaction between Cr(VI) and their lignocellu­ polyethyleneimine
[29]
losic sorbent in their kinetic model. Mango kernel composite −68 −184 −12.2
[124]
Cellulose coated magnetic silica- −43 115 −8.2
g-GMA-g-EDA
[123]
Corncob-g-polyamide 82 38 −11.7
Thermodynamics Cellulose coated Fe(III) 22 110 −9.6 [129]
[127]
Thermodynamic studies of Cr(VI) adsorption onto cellulose London plane leaves 10 44 −2.8
[115]
Fe3O4 coated cellulose/hydrotalcite 0.2 30 −10.8
and cellulose-based sorbents retuned ∆G negative values.­ Fe3O4 coated cellulose/hydroxyapatite 2.1 30 −10.7
[88,134] [120]
But the adsorption could be exothermic, (∆H > 0), or Date stones 24 92 −2.7
[116]
Cellulose/Hydroxyapatite 4.0 50 −10.8
endothermic (∆H < 0) as listed in Table 6.

To summarize, compared to chitosan (Figure 6) cellulose
does not possess amino groups making positively charged
functional groups in acidic media. So cellulose chemical mod­
ifications are needed to introduce functional groups that can
directly adsorb Cr(VI) oxyanions. However, in contrast with
chitosan, cellulose possesses a large number of hydroxyl
groups that can trigger chromium reduction naturally. Also,
chromium cations are more likely to form complexes and less
susceptible to be released into the solution (Figure 6B).
Other Polysaccharides
Starch
Other polysaccharides were reported in the literature for the
removal of heavy metals from which starch and alginate are
the most often reported. Starch is a nontoxic, biodegradable,
abundant, and low-cost polysaccharide based on D-glucose
chains. It possesses several hydroxyl functional groups for
pollutants binding.[141,142] The source of starch influences its
adsorptive performance because smaller particle sizes of the
granules increase the surface area. Also, the Cr(VI) affinity is
higher in amorphous starch regions.[143] Similarly to cellulose,
chemical modifications have been carried out to develop
cationic, anionic, and amphoteric starches for a better heavy
metal removal efficiency.[144]
Crosslinked insoluble cationic starch is popular for the
removal of the Cr(VI) oxyanions.[145] Amino-starch synthe­
sized with ethylenediamine exhibited Cr(VI) adsorption with
fast kinetics at pH 4, but with a low adsorption capacity of
15 mg/g.[144] An amphoteric starch synthesized with qua­
ternary ammonium and carboxymethyl groups evidenced
a better adsorption capacity of 31 mg/g.[146] Crosslinking
starch enhances the adsorption process for which epichlor­
ohydrin can be used.[143] The degree of cationization and
crosslinking influences the adsorption performance.
Optimizing these variables, the adsorption capacity could
be increased up to 73 mg/g.[145]
Due to its abundance and low-cost, starch has also been
used to develop green nanocomposites to improve its
adsorption capacity. Cationic starch favors the intercalation
of silicate layers of clays. A cationic starch/montmorillonite
nano-composites exhibited an adsorption capacity of 21 mg/
g even in the presence of competitive ions.[147] Magnetite
nanoparticles were functionalized with starch leading to
a removal of 27 mg/g.[141] Using starch as a low-cost and
stabilizer support for nano-scale zero-valent iron particles to
prevent its agglomeration, a 100% Cr(VI) removal efficiency
at pH 6, with reduction to Cr(III) was obtained.[142] The
adsorption capacity was an acceptable 73 mg/g.[148]
Alginates
Alginate, or sodium alginate, is a linear polysaccharide based
on α-L-glucuronate and β-D-mannuronate units randomly
arranged. Water-insoluble gels are formed by crosslinking
with calcium ions. These gels were widely investigated for
the removal of heavy metal ions from water streams.[149,150]
Unfortunately, the Cr(VI) adsorption by alginate gels is lower
than 8 mg/g requiring additives and/or modifications to be
efficient.[151] Incorporating carboxymethyl cellulose to
SEPARATION & PURIFICATION REVIEWS 19
alginate into binary beads increased the adsorption capacity
to a mediocre 17 mg/g.[150]
Composites exhibit desirable properties with the combina­
tion of its constituents.[152] Iron oxide-alginate nanoparticles
exhibited good permeability and uptake capacity in batch
experiments of 17 mg/g, which led to a possible column
operation.[149] Alginate chains could intercalate into clay gal­
leries enhancing the Cr(VI) adsorptive performance: an algi­
nate/montmorillonite/polyaniline had a capacity of 30 mg/
g.[153] As discussed throughout this paper, adsorption affinity
drastically increases by incorporating chitosan to any given
composite sorbent. A chitosan/alginate sorbent had a capacity
of 40 mg/g.[152] As an interesting perspective, some by-
products generated during the extraction process of alginate
could exhibit better affinity toward Cr(VI) oxyanions with
reduction to less toxic Cr(III) by different added groups.[154]
Lignin
Despite lignin is not a polysaccharide by definition, it is
another essential natural biopolymer. Lignin is amorphous,
highly crosslinked, three-dimensional, and aromatic
extracted from biomass coming from the wood and paper
industries.[155] It is the second most abundant natural poly­
mer derived from wood after cellulose. It can be derived to
possess hydroxyl, carbonyl, methoxyl, and sulfonic acid
groups (ligno-sulfonates).[156,157] The lignin composition
and structure depend on its extraction process and source.
It is always composed of propyl-phenolic subunits that pos­
sess suitable groups for heavy metals adsorption.[158]
Cationic metals, such as Ni(II), Cu(II), Cd(II), and Pb(II)
were extracted by lignins. Non-sulfonated lignins are typi­
cally suitable for such adsorption due to their insolubility in
water and chemical resistance.[159–161]
Due to the anionic nature of hexavalent chromium in
solution, very few reports are found in the use of lignin for
its uptake. Cr(VI) uptake can only be performed by compo­
sites of lignin with other materials. Lignin offers stability,
surface area and electron-donor groups and the other material
must have positive sites for oxyanion adsorption. Nair et al.­
[155]
prepared a very stable chitosan-lignin composite for
Cr(VI) adsorption, however its maximum capacity was only
18 mg/g, which is low in comparison with reported values for
other metals. Therefore, the use of lignin as a C(VI) adsorbent
remains uncertain as it has been proven to be effective for the
removal of cationic pollutants.
EXPERIMENTAL PARAMETERS
Effect of Co-contaminants or Co-existing Ions
Real effluents differ from simulated laboratory solutions con­
taining a variety organic and inorganic matter at different
concentrations. Obviously, these dissolved components,
mainly inorganic electrolytes can interfere with Cr(VI)
adsorption. Cations will interfere with the negatively charged
sorbent sites or bind directly with Cr(VI) oxyanions. Anions
will interfere with the positively charged sorbent sites. These
adsorptions may modify sorbent electric double layer and
electrostatic interactions.[162] Anions may be beneficial
20 M. E. GONZÁLEZ-LÓPEZ ET AL.
forming water-insoluble metal-anion complexes with heavy
metal ions that will precipitate.[163] Real effluents co-existing
ions are: anions, mainly Cl−, F−, NO3−, HCO3−, CO32-, SO42-
or PO43-, and cations such as Na+, K+, Ca2+, Mg2+, Zn2+ or
Fe3+.[43,100,103,115] Their competitive effect on sorbent Cr(VI)
removal efficiency must be studied.[103]
For chitosan-based sorbents, the competitive effect of
cations is less critical since all Cr(VI) pollutants adsorb on
positive sites unaffected by cations due to electrostatic repul­
sion. Na+, Ca2+, and Mg2+ showed less than 2% reduction of
Cr(VI) adsorption capacity on a chitosan-based sorbent.[103]
In the case of anions, alteration of Cr(VI) removal efficiency
was also very low for nitrate, chloride, fluoride, and carbonate
ions demonstrating the high selectivity of chitosan toward the
HCrO4− anion. Sulfate and phosphate add some measurable
minor effects affecting adsorption in the order: SO42- > PO43-
> NO3− > Cl−.[22] It is not surprising that bivalent anions
cause a greater hindrance than monovalent anions.[16] Anion
interference follows the mechanism[22]:
R NH2 þ Cl þ H2 O $ R NH3 þ Cl þ OH (43)
R NH2 þ NO3 þ H2 O
$ R NH3 þ NO3 þ OH (44)
2 ðR NH2 Þ þ SO4 2 þ 2 H2 O
$ ðR NH3 þ Þ2 SO4 2 þ 2 OH (45)
Anion interference is concentration-dependent. Between 200
and 500 mg/L of chloride, nitrate, or sulfate concentrations
the Cr(VI) adsorption of a chitosan-based sorbent was
decreased by more than 40%.[100]
In the case of cellulose, chloride, nitrate, and sulfate anions,
as well as calcium, and magnesium cations had minor effect
on Cr(VI) adsorption efficiency. However, the HCO3− anion
had a strong effect because it changes the pH affecting the
adsorption site ionization. Besides, chlorine ions restrict
HCO3− mobility resulting in lower Cr(VI) uptakes.[164]
Interestingly, Ca2+ ions could bridge chromium oxyanion
and negatively-charged functional groups, producing
a synergistic effect on the Cr(VI) adsorbed amount.[116,165]
Industrial wastewater could include other pollutants such
as surfactants. Tween 80, SDS, and CTAB decreased the
Cr(VI) mango kernel sorption capacity by up to 60%. The
surfactant may cover the sorbent surface decreasing the num­
ber of available binding sites.[29] Surfactants may also increase
Cr(VI) uptake with cellulose-based materials.[162]
The multi-metal competitive effect must be specifically
studied. Competitive adsorptions of Pb(II), Ni(II), Cu(II),
and Zn(II) have been tested. Lead could reduce the Cr(VI)
adsorption capacity by 70% or by 53% when another cation
was also present.[40] This behavior was explained by the affi­
nity strength toward other metal species and competition for
the occupation of the same sites. Mono, binary, and multi-
metal systems have been evaluated with Ni(II), Cd(II), and
Cr(VI) on sunflower biomass. Ni(II) was better adsorbed than
the other metals due to its smaller hydrated radii, higher
electronegativity, and higher standard reduction potential.[166]
A synergistic effect on binary adsorption of Cu(II) and Cr(VI)
was found on a chitosan-Fe(III) composite.[167] The adsorbed
cationic Cu(II) provided additional binding sites for the
Cr(VI) oxyanions. Also, the presence of Cr(VI) caused proton
consumption through ligand exchange and redox reaction
facilitating Cu(II) adsorption.
Reusability
The regeneration capacity of the sorbents is important in
terms of the cost-effectiveness of the process.[19,21] In the
regeneration process, spent adsorbent is restored to its origi­
nal adsorption capacity by stripping the adsorbed ions and
recycling it back to the process.[168] Desorption and regenera­
tion studies help in recycling the adsorbent by removing
Cr(VI) loaded on it. They also help in elucidating the adsorp­
tion mechanism and predicting the interactions between
metal ions and the adsorbent.[30] Cr(VI) desorption is simply
accomplished by adjusting the solution pH. Common deso­
rption agents are dilute acid or dilute hydroxides: HCl,
HNO3, H3PO4, and NaOH.[112,118,120,126,129,132,138] Organic
acids or inorganic salts may be necessary to break electrostatic
or chemical interactions: NaCl, NaHCO3, ethylenediaminete­
tra-acetic acid (EDTA), sodium citrate, sodium oxalate,
sodium tartrate have been used as regenerate agents.[95,113,125]
The most used HCl and NaOH regenerating agents may
decrease the metal adsorption abilities by hydrolyzing some
sorbent surface groups and metal-binding sites.[19] Thus, only
a fraction of the original adsorption capacity is restored.[99]
Table 7 summarizes the number of regeneration cycles as
well as the restored adsorption capacity for some polysacchar­
ides-based sorbents. The problem is that sorbent regeneration
is costly and polluting. So it must be evaluated if the regen­
erated lower adsorbent adsorption capacity is sustainable in
term of cost, secure development, and pollution.[57]
Continuous-flow Adsorption in Fixed-bed Columns
Continuous-flow adsorption represents the most valuable
and economic scheme for adsorption as a process for efflu­
ent treatment, and it is generally carried out in vertical
fixed-bed columns using upward flow.[169] Before conduct­
ing the discussion on this process, the capacities of poly­
saccharide-based sorbents must be compared to its
carbonaceous counterparts. Table 8 summarizes the max­
imum removal capacities of relevant sorbents clearly show­
ing that polysaccharide-based sorbents beat carbonaceous
sorbents for Cr(VI) removal.
Figure 7 shows the typical column arrangement. The col­
umn has a cross-sectional area A and is packed with particles
of a given sorbent at specific bed length L. The particle
external porosity is the free volume between adjacent sorbent
particles depending on particle size and shape. The particle
internal porosity is the internal volume inside sorbent parti­
cles through which the adsorbate solution can flow.[170]
Generally, the columns are operated vertically with an upward
 SEPARATION & PURIFICATION REVIEWS 21

Table 7. Regeneration Cycles and Retained Cr(VI) Adsorption Capacity of adsorptions that have a potentially higher adsorption capa­
Polysaccharide-based Sorbents.
city than batch adsorption for the same sorbent. An adsor­
Reusability Retained bate concentration gradient move with the flow in the
cycles capacity
Adsorbent n (%) Ref. column while this gradient naturally decreases in batch
Crosslinked chitosan-xanthate flakes 10 20 [3] adsorption.[82] Column adsorption can be scaled-up at pilot
Crosslinked chitosan-xanthate beads or semi-pilot scale if certain process parameters are estab­
[29]
Mango kernel composite 6 98
Cellulose/[APMIm]NO3 6 97 [112] lished. The breakthrough time, tb (C/C0 = 0.1) is the concen­
[95]
Thiocarbohydrazide crosslinked 6 80 tration when the maximum recommended limit is reached
chitosan
[100] ,[172] and the exhaustion time, te, is defined as C/C0 = 0.9.
Titanium crosslinked chitosan 6 65
Cellulose coated magnetic silica- 5 100 [124] Table 9 lists the Cr(VI) fixed-bed column adsorption studies
g-GMA-g-EDA with other heavy metal studies to generalize the effect of
Cellulose-g-GMA-D-GluN+ 5 100 [126]

PVA/zeolite/chitosan electrospun 5 100 [11] fixed-bed length (L), volumetric flow rate (Q), and inlet
composite concentration (C0) and on the breakthrough curves and
[98]
Crosslinked magnetic chitosan resin 5 90 adsorption capacity.
[111]
Cellulose-g-GMA-g-Ti 5 90
[129]
Cellulose coated Fe(III) 5 89
[102]
Chitosan/graphene oxide 5 85
nanocomposite Effect of Fixed-bed Length
[10]
Carboxymethyl chitosan-SiO2 5 75
membrane Fixed-bed columns are strongly dependent on the bed
[118]
Carboxylated cellulose/ 5 52 height; thus, the shape and slope of the breakthrough change
polyethyleneimine
Date stones 5 50 [120] with this parameter since more active binding sites are
[99]
Chitosan-Fe3O4 beads 5 50
[138]
available for adsorption with an extended mass transfer
Cellulose-g-poly(amidoamine) 3 76 zone.[91,174] Figure 9A shows steeper breakthrough with
[2]
Fe3O4/chitosan hydrogel 3 75
Trimesic acid crosslinked chitosan 3 38 [105] shorter columns. Longer columns increase the breakthrough
[78]
EDTA Crosslinked chitosan 3 - time from zero, at the critical bed length, to larger times, and
thus increase the volume that can be treated at the same
removal percentage.[83,85,91] In a small bed length, axial dis­
Table 8. Comparison of the Cr(VI) Adsorption Capacities of Polysaccharide-based
persion can no longer be neglected in the mass transfer,
Sorbents Against Carbonaceous Sorbents. reducing cation diffusion.[82] Chen et al.[174] did not
Adsorption capacity reported a doubling of Cr(VI) continuous-flow adsorption
Adsorbent (mg/g) Ref. by modified corn stalk reporting 134 mg/g with a 1.4 cm
[39]
Polyacrylonitrile-CNT/TiO2-NH2 714 column and only 175 mg/g when bed length was more than
[3]
Crosslinked chitosan-xanthate flakes 625
Carboxylated cellulose/polyethyleneimine 358 [118] doubled to 2.9 cm. The columns may have been too short.
[51]
Fe3O4/Graphene 280
[47]
But with a similarly short 2.5 cm column filled by 2 g of
Activated alumina CNT 264 a chitosan-ionic liquid sorbent, Kumar et al.[96] were able
[3]
Crosslinked chitosan-xanthate beads 256
Reduced graphene oxide/NiO 198 [45] to treat 700 mL of Cr(VI) solution in two hours at 6 mL/min.
[99]
Chitosan Fe3O4 beads 175 Interestingly, their breakthrough curve presented an abnor­
[97]
Diphenyl carbazide immobilized chitosan 166
Activated carbon from wood apple shell 152 [28] mal behavior due to the swelling of the exhausted adsorbent
[129]
Cellulose coated Fe(III) 126
[27]
particles.
Carbon spheres 117
Pistachio hull 116 [108] The influence of bed length on the parameters of the
models is as follows: with the Adams-Bohart model (eqs.
34–37) the parameter kBDST increases with increasing bed
length, contrarily as in the other models. In the Thomas
flow produced by peristaltic pumps delivering a specific flow model (eqs. 30–31) the values for kTh decreases with increas­
rate.[171] ing bed length while the bed capacity qTh increases.[91] In the
The transient operation of these fixed-bed columns is Yoon-Nelson model (eqs. 38–39) the parameter kYN decreases
governed by diffusion, and convective flow, i.e., the flux of while τ increases at larger bed heights.[174]
polluted solution, and a term of adsorption described with
a concentration gradient.[170] Thus, the initial section of the
Effect of Flow Rate
bed starts to saturate at the early stages of the process (t < tb),
whereas the concentration remains practically zero at the rest The flow-driven nature of a fixed-bed column enhances
of the column. This concentration wave gets displaced to Cr(VI) adsorption by promoting a very efficient use of the
higher sections of the column along with operation time, sorbent porosity. Cr(VI) is somewhat pushed inside the sor­
passing through breakthrough point until reaching an outlet bent pores. Reducing the flow rate give more time to adsor­
concentration equal to the inlet concentration, yielding bate ions to diffuse into the pore active binding sites.[175]
a typical sigmoidal shaped curve for the column operation Figure 9B illustrates the effect of the volumetric flow Q on the
as it is illustrated in Figure 8.[169] C/Co parameter. Obviously the steepness of the curve
The majority of Cr(VI) adsorption studies were carried increases as the flow rate becomes larger and both break­
out in batch, and laboratory-scale processes. Few reports are through and exhaustion times occur faster.[83,91] However,
found in the literature regarding fixed-bed column a faster flow rate will reduce the treated volume before the
22 M. E. GONZÁLEZ-LÓPEZ ET AL.
Figure 7. Fixed-bed column operation diagram.
Figure 8. Transient operation of a fixed-bed adsorption column. tb, breakthrough time at which 10% of the Co pollutant inlet concentration is seen at the column
outlet; te, exhaustion time at which 90% of Co exit the column.
saturation point and decrease the column life time since
solute is leaving the column before the equilibrium
occurred.[82]
With xanthated chitosan and plain chitosan flake columns,
Chauhan and Sankararamakrishnan[90] observed shorter and
sharper breakthrough times increasing the flow rate from 5 to
8 mL/min with a reduced Cr(VI) adsorption on both col­
umns. The slope change of the breakthrough curve occurs
due to the rapid mass transfer that promotes the saturation of
the active sites.[85] These effects are also observed in the
parameters of the dynamic models. For the Thomas model,
increased flow rates were associated to larger kTh and smaller
 SEPARATION & PURIFICATION REVIEWS 23

Table 9. Optimal Conditions for Fixed-bed Column Adsorption for Different Pollutants.
Optimal conditions
L Q C0 qmax Vtreated
Sorbent Adsorbate (cm) (mL/min) (mg/L) (mg/g) (L) Ref.
[173]
Chitosan/MWCNT/Fe3O4 Cr(VI) - 4 50 351 13
[90]
Chitosan flakes 20 5 10 202 1
Xanthated chitosan 20 5 10 130 2
[174]
Modified corn stalk 1.4 10 300 93 1.7
[96]
Tetraoctyl-ammonium bromide chitosan 30 6 30 64 0.7
[131]
Hibiscus Cannabinus kenaf 15 2 0.5 0.02 0.05
[121]
Grafted crosslinked chitosan beads 35 10 10 0.21 2.7
[156]
Lignosulfonate-modified graphene hydrogel Pb(II) 1.2 - 400 1308 0.04
[83]
Biosorbent 31 10 20 108 1.7
[80]
Watermelon rind 5 1 1000 90 0.09
[85]
Allspice residue 15 20 15 16 6.8
[89]
Aspergillus niger biomass Cu (II) 2.1 5.2 10 13 2.5
[82]
Coconut shell 20 10 10 7.2 67
[83]
Biosorbent 31 10 20 63 2.6
Zn (II) 35 2.0
Cd(II) 38 4.2
[91]
Wheat straw 200 300 100 13 111
[84]
Wheat bran Se(IV) 25 1.7 1 73 2.3
Se(VI) 63 2.2

qTh values (eq. 30). Chen et al.[174] used the Adams-Bohart
model (eq. 36) and reported a 36% increase in kTh from 2.2 to
3.0 × 10−4 mL/min mg with a decreasing kBDST parameter
when increasing flow rate from 10 to 15 mL/min. Beheshti
et al.[173] worked with a chitosan/MWCNT/Fe3O4 filled col­
umn obtaining a calculated capacity qTh of 351 mg/g at
a 4 mL/min flow rate.
Effect of Inlet Concentration
The main adsorption driving force is a concentration
gradient.[29] Thus, the inlet concentration has a strong effect
on the shape and slope of the breakthrough curve. At higher
values of inlet concentration, mass transfer resistance becomes
smaller due to a higher concentration gradient.[21] But this is
associated to a faster breakthrough and saturation.[82,83]
Increasing inlet concentration, C0, leads to higher adsorption
capacities since the greater concentration gradient yields to
a faster transport or increase in mass transfer coefficient and
shorter breakthrough and exhaustion points.[174] Chen et al.­
[174]
reported an almost doubling adsorption capacity from
264 to 504 mg/g when the Cr(VI) inlet concentration raised
from 100 to 300 mg/L. The exhaustion time decreased from
264 to 168 min.
In terms of Adams-Bohart modeling parameters, the kBDST
and NBDST values became smaller at higher inlet concentra­
tions in the same way than kTh since the driving force was the
concentration gradient. However, for the parameters kYN and
τ of the Yoon-Nelson model, a decrease was observed with
increasing inlet concentrations due to the faster column
saturation.[85,174] The Thomas model explains the decreasing
adsorption capacity with the qTh parameter (eq. 31) that
decreases with lower inlet concentration since mass transfer
is slower, and adsorption is favored at higher inlet concentra­
tions if residence time is sufficient with an adapted flow
rate.[85]
Column Regeneration
Regeneration is critical being linked to re-use of the fixed-bed
columns reducing the operational and maintenance costs by
avoiding the use of fresh adsorbent and allowing to recover
adsorbed ions.[84,92] Column regeneration is carried out by
desorbing adsorbed metal ions using a small volume of appro­
priate eluting solution. Desorption efficiency is flow rate-
independent so the desorbing elution is done as quickly as
possible.[89] The composition of the working regeneration
solution depends on the type of adsorbent and adsorption
mechanism.[83] Many eluting solutions have been used to
regenerate the fixed-bed: either basic, Na2CO3, KOH,
NaOH, or acidic, HCl, H2SO4, HNO3, among others.
Regeneration must not damage the sorbent nor diminish
its adsorption capacity.[25] The lignosulfonate-modified gra­
phene hydrogel sorbent prepared by Li et al.[156] had
a capacity of 1308 mg/g under column adsorption. It main­
tained 82% of its adsorption capacity after ten regeneration
cycles. Similarly, the sorbent based on chitosan/MWCNT/Fe3
O4 reported by Beheshti et al.[173] was regenerated using
HNO3 and retained most of its initial 350 mg/g capacity
after five cycles. Lakshmipathy and Sarada[80] successfully
regenerated three times their watermelon rind filled column
in 15 min using 0.1 M HCl retaining 95% of the original
Pb(II) capacity. After some damaging regeneration elutions
using acidic solutions, the Abdolali et al.[83] biosorbent col­
umn could be restored using CaCl2 that could displace excess
protons and create new binding sites. Their breakthrough
curves showed no significant changes after three such cycles.
Unfortunately, most of the time column regeneration leads
to adsorbent degradation hence shorter breakthrough times.­
[84]
The column life factors were modeled by simple linear
regression equations proposed by Volesky et al.[172] The col­
umn adsorption performance after n cycles is expressed in
terms of breakthrough time, tb, and adsorption capacity, q:
tb ¼ tbi þ KL n (46)
24 M. E. GONZÁLEZ-LÓPEZ ET AL.
Figure 9. Effect of A) bed length and B) flow rate on the breakthrough curves. z, column length; Q, inlet effluent flow rate (relative units).
q ¼ qi þ KL n
From these regressions, the KL value in min/cycle and mg/g
cycle allows to predict the number of cycles before complete
column saturation (tb = 0 and q = 0).[92] Hasan et al.[84]
calculated the life factor of a column packed with wheat
bran for Se(IV) and Se(VI) removal. They observed that
their column would retain enough capacity and acceptable
breakthrough time after 12 cycles for Se(IV) and six cycles
for Se(VI) and would be completely saturated after 56 and 18
cycles, respectively.
These parameters are of great importance in terms of the
feasibility and cost-effectiveness of the high-scale operation
and represent an indication that functional adsorption capa­
city is retained after column regeneration.[84,121] However,
column desorption still needs to be optimized in terms of
high heavy metal concentration into the smallest possible
volume from which the metallic form of the ion could be
(47)
recovered using other methods.[82]
CONCLUSIONS AND PERSPECTIVES
Adsorbents based on polysaccharides, mainly chitosan, cellulose,
and other natural polymers like lignin, can remove Cr(VI) from
aqueous media. The effect of pH, equilibrium, kinetics, thermo­
dynamics, and the mechanism was generalized. The trend is to
use extensively available materials as adsorbents, such as raw
chitosan and lignocellulosic resources and wastes, and to develop
cost-effective adsorbents by increasing adsorption capacities
through physical or chemical modifications. Chitosan represents
the most valuable resource for the removal of Cr(VI) oxyanions
and anionic pollutants due to the large presence of amino

groups. Therefore, efforts have been directed to improve its
chemical stability and reusability, while retaining or increasing
its adsorption capacity. These approaches include chitosan phy­
sical modification toward the preparation of beads, membranes
or nanoparticles, and chemical modification that included
the impregnation of the surface with scavenging moieties, the
incorporation of new functional groups, including magnetic
nanoparticles, and crosslinking using nontoxic and non-amino-
selective reagents. Chitosan-based composites with other
materials such as silicon or clays increased the low chitosan
surface area.
Cellulose, starch, alginates and lignin are more selective to
cationic pollutants. However, cellulose can be easily chemi­
cally modified, hence modifications were done aiming to
enhance chromium removal. Cellulose was coupled to ionic
liquids and functional groups. Cellulose composites were pre­
pared with cationic structures. Here also, the trend is to use
raw or modified lignocellulosic wastes rather than cellulose
itself due to economic reasons. Following this, lignin is
a promising sorbent with a large specific area. It must produce
valuable composite sorbents. But more research is required on
the use of lignosulfonates that are too water soluble. The
efficiency of these sorbents is strongly pH dependent due to
their ionization degree and chromium speciation. The optimal
binding capacities are obtained in a 3 to 6 pH range. Although
the vast majority of the sorbents cited are described by
Langmuir monolayer adsorption equilibrium and pseudo-
second-order kinetics, the theoretical approach of this paper
highlights less known models to elucidate the complex
mechanism that involves physical pore and film diffusion,
chemical adsorption, chelation, complexation, ion exchange
or entrapment in inter and intra-fibrillar capillaries.
Sorbent regeneration using simple eluting solutions is diffi­
cult, and the use of organic acids or inorganic salts is necessary.
However, there is a critical urge to analyze the cost and pollu­
tion caused by the sorbent modification methods and regen­
erations. These processes not only increase the operating costs
but they also cause secondary pollution. Column continuous-
flow adsorption represents the most valuable and economic
scheme for Cr(VI) adsorption as a process for effluent treat­
ment. The slope and shape of the breakthrough curves are
dependent on bed length, volumetric flow rate, and inlet con­
centration, which should be optimized in terms of maximizing
contact time, seizing sorbent adsorption capacity, and avoiding
the solute leaving the column before the equilibrium is reached.
Also, the regeneration and subsequent reuse of the fixed-bed is
critical significantly reducing the operational and maintenance
costs and pollution. From this literature review, it can be seen
that the use of polysaccharides as Cr(VI) sorbents in batch and
semi-continuous systems is an area of great interest and an
opportunity to direct the efforts to provide greener state-of-the
-art sorbents and technology for the Cr(VI) removal from
polluted water streams.
Acknowledgments
Two of the authors (M.E. González-López and C.M. Laureno-Anzaldo)
acknowledge the financial support of the Mexican National Council for
SEPARATION & PURIFICATION REVIEWS 25
Science and Technology (CONACyT #481448 and #701030) for their
scholarships.
Funding
This work was supported by the Consejo Nacional de Ciencia
y Tecnología [481448,701030].
ORCID
Martín Esteban González-López http://orcid.org/0000-0002-3614-
5725
Cesar Mario Laureano-Anzaldo http://orcid.org/0000-0003-3944-9430
Aida Alejandra Pérez-Fonseca http://orcid.org/0000-0003-2443-3882
Martín Arellano http://orcid.org/0000-0002-7446-8461
Jorge Ramón Robledo-Ortíz http://orcid.org/0000-0002-1309-6203
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