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Removal of organic pollutants from wastewater using chitosan: a literature

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DOI: 10.1007/s13762-018-2061-8

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Removal of organic pollutants from
wastewater using chitosan: a literature
review

R. R. L. Vidal & J. S. Moraes

International Journal of
Environmental Science and
Technology

ISSN 1735-1472
Volume 16
Number 3

Int. J. Environ. Sci. Technol. (2019)

16:1741-1754
DOI 10.1007/s13762-018-2061-8

1 23
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 Author's personal copy
International Journal of Environmental Science and Technology (2019) 16:1741–1754
https://doi.org/10.1007/s13762-018-2061-8

REVIEW

Removal of organic pollutants from wastewater using chitosan:

a literature review
R. R. L. Vidal1   · J. S. Moraes1

Received: 12 June 2018 / Revised: 25 September 2018 / Accepted: 8 October 2018 / Published online: 27 October 2018
© Islamic Azad University (IAU) 2018

Abstract
The production of organic effluents derives from several industry areas, and the increase of this production accompanied
those industries growth. The components of those effluents have high toxicity, which may cause serious damages to the
affected environment. For this reason, the research for alternative materials (derived naturally or from industrial residues)
for wastewater treatment has increased. Thus, biopolymers, such as chitosan, are a sustainable alternative, since they come
from renewable and biodegradable sources. Chitosan has properties, such as adsorption capacity and flocculation and coagu-
lation abilities, which allow it to replace, partially or completely, synthetic materials. Several methods have been applied
for the treatment of those organic effluents in order to achieve their maximum limit for wastewater disposal or reuse set in
each country. Among those treatments, adsorption can be considered the most advanced and efficient for residual treatment,
removing selectively several organic compounds. Therefore, this paper reviewed the applicability of chitosan in phenol and
oil removal from industrial effluents. Several authors highlighted its use as an environmentally friendly alternative, once
chitosan presented a pollutant removal capacity similar or even better than those commonly used materials. The majority of
the studies reviewed indicated the best condition for adsorptive capacity of natural or modified chitosans at acidic pH, due to
the great influence of the electrostatic attraction mechanism. In addition, the review encourages further researches for more
in-depth studies such as those of mechanism of adsorption, simultaneous pollutant adsorption and industrial-scale process.

Keywords  Adsorption · Biopolymer · Industrial effluents · Residual treatment

Introduction damage to the flora and fauna of the affected environment,

Food, textile and leather industries, vegetable oil processing
industry, oil and gas production companies and domestic
sewage are some of the most important sources of pollution
and their discharged wastewaters usually contain diverse
organic compounds (Aguilera et al. 2010; Dsikowitzky and
Schwarzbauer 2013; Wahi et al. 2013). Among those, some
lipophilic contaminants with functional groups are not com-
mon in nature (commonly present halogen substitutions and
a branched structure), persistent and highly toxic (Dsikow-
itzky and Schwarzbauer 2013). Those can cause serious
Editorial responsibility: M. Abbaspour.
* R. R. L. Vidal
rosangela.vidal@ufba.br
1
Departamento de Físico‑Química, Instituto de Química,
Universidade Federal da Bahia, Campus Universitário de
Ondina, Salvador, Bahia 40170‑115, Brazil
besides of being potentially carcinogenic to humankind
(Zhou et al. 2008). Therefore, the research for non-conven-
tional low cost and environmentally friendly remediation
caused an increase in the interest in natural-based materials.
According to Bailey et al. (1999) and Ali et al. (2012), those
alternative materials should have some common character-
istics such as abundance and easy acquisition in nature or
even derivate from a byproduct or waste generated by other
industry; economic viability; required little or no process-
ing and non-toxicity. Consequently, biopolymers, such as
chitosan, are a sustainable alternative, once they derive from
renewable and biodegradable sources.
Chitosan has a structure similar to those of chitin and
cellulose. However, chitosan presents greater solubility in
aqueous acid medium than its precursor polymer (chitin) and
cellulose, due to the presence of amine groups and primary
and secondary hydroxyl groups, responsible for its applica-
tion in multiple functions (Azevedo et al. 2007; Ahmad et al.
2005a; Pillai et al. 2009).

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1742 International Journal of Environmental Science and Technology (2019) 16:1741–1754
A considerable amount of the global production of chi-
tin and chitosan and its derivatives is used for wastewater
treatment (Sridhari and Dutta 2000). Intrinsic properties of
chitosan, such as its polycationic aspect, ability to conglom-
erate and precipitation in neutral or alkaline pH, besides its
long polymer chain, may facilitate the contact between the
polymer and the contaminated medium (Renault et al. 2009).
These characteristics along with its regeneration capacity
and its eco-friendly nature allow its use in adsorption pro-
cesses (Elanchezhiyan et al. 2016a; Farias et al. 2015). The
chelating property of chitosan justifies its potential applica-
tion in effluent treatment once it allows its interaction with
suspended or dissolved particles. The use of chitosan was
studied for drinking water treatment (Fabris et al. 2010);
dye removal (Ignat et al. 2012; Vakili et al. 2014; Khanday
et al. 2017); heavy metal removal (Jayakumar et al. 2007);
and treatment of oil in water emulsions (Ahmad et al. 2006a;
Grem et al. 2013; Meyssami and Kasaeian 2005; Srinivasan
and Viraraghavan 2010); in addition, it was discovered as an
effective remover of crude oil and its components in waste-
water (Dutta et al. 2004; Sridhari and Dutta 2000). Recently,
Desbrières and Guibal (2018) motivated the use of chitosan
for wastewater treatment and pollutant removal whatever
their nature.
Then, the purpose of the review was to compile relevant
studies from the last 15 years on adsorption process using
chitosan for organic pollutant removal, such as phenols and
oil, from industrial effluents. Those studies showed the great
efficiency of the adsorption method, highlighted the poten-
tial application of chitosan for this goal and showed the best
performance of the biopolymer compared to the most com-
monly used adsorbents. In addition, a review study about
chitosan and the adsorption process is also presented.
Chitosan
Chitosan is a natural, low-cost, abundant and biodegradable
amino polysaccharide. It has a unique structure formed by
units of 2-amino-(2-deoxy-d-glucopyranose) and 2-aceta-
mide-(2-deoxy-d-glucopyranose) bound by β(1 → 4) glyco-
sidic bonds (Azevedo et al. 2007; Philippova and Korcha-
gina 2012). Chitosan is commonly obtained from chitin by
deacetylation process (Crini 2006; Crini and Badot 2008;
Silva et al. 2006). Chitin is the second most abundant poly-
saccharide in nature, right after cellulose (Alves 2008). This
chitosan precursor is found in shells of arthropods (shrimp,
crab and insects) and may naturally occur in some fungi such
as Deuteromycetes and Zygomycetes (chitosan is also found
in the last one, including those fungi from genera Mucor)
(Cardoso 2008; Silva et al. 2006; Platzer 1987).
Chitin deacetylation is based on the process of amine
groups (‒NH 2 ) formation from acetamide groups
13
(‒NHCOCH3) through different methods such as the het-
erogeneous method, the most common one, which involves
a reaction with alkaline aqueous solutions at high tempera-
tures that can last more than 3 h depending on the reaction
parameters (Gonsalves et al. 2011). The degree of acety-
lation (DA) is a parameter that characterizes the average
content of chitin-remaining N-acetyl-d-glucosamine units,
which provides a variety of chitosans with different physico-
chemical properties, such as solubility, relative molar mass,
pKa and viscosity (Silva et al. 2006). The degree of deacety-
lation (DD) indicates the average value of d-glucosamine
units on chitosan chain in a range of 50–95%, depending
on the deacetylation method used (Fig. 1). The relationship
between these parameters is given by: DA (%) = 100 − DD
(%) (Gonsalves et al. 2011; Wang and Chen 2014).
The polycationic capacity of chitosan is directly pro-
portional to its solubility and to the distribution of the free
amino groups on its structure as consequence. This biopoly-
mer is insoluble in water, organic solvents and bases. How-
ever, it is soluble in solutions of acetic, formic or citric acids
under stirring and solutions of hydrochloric, perchloric and
phosphoric acids under stirring and heating a with pH lower
than 6.0. This occurs because this polysaccharide can be
considered a weak base since it has primary amino groups
with pKa between 6.3 and 7.2 (Crini and Badot 2008; Gon-
salves et al. 2011; Kumar et al. 2015). The ionic concentra-
tion is a factor of great importance on chitosan solubility,
once the pH significantly modifies the properties of chitosan
in solution. Chitosan solubilizes in acid aqueous medium
due to its reaction with hydronium (­ H3O+), producing a
cationic polyelectrolyte in which the amino groups at the
C-2 position of the d-glucosamine repeating unit are pro-
tonated (‒NH3+). On the other hand, as the pH increases
(values above 6.0), the amine groups of chitosan deprotonate
and the polymer precipitates. As the pKa value is highly
dependent on DA, the solubility of chitosan depends on the
degree and method of deacetylation used, the distribution of
the acetyl groups on its structure and its molar mass. Thus,
the higher the number of protonated groups, the greater the
inter-chains electrostatic repulsion and, consequently, the
Fig. 1   Chitosan structure with acetylated and deacetylated units
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International Journal of Environmental Science and Technology (2019) 16:1741–1754 1743
higher its molecule solvation in aqueous medium (Damian
et al. 2005; Gonsalves et al. 2011; Honarkar and Barikani
2009; Kumar 2000; Pillai et al. 2009; Rinaudo et al. 1999).
According to Azevedo et al. (2007), the use of natural
polymers for several applications resulted in progress in sci-
ence, once they have some advantages, such as biocompat-
ibility and biodegradability, besides their easy and abundant
availability. The fishing industries produce as waste exoskel-
etons of crustaceans and other marine animals, which are
considered as pollutants. The utilization of these residues to
produce chitosan promotes the reduction in the environmen-
tal impact caused by their accumulation. Those researchers
affirm that chitosan has an extensive network of application,
including its use in food area, biotechnology, materials sci-
ence, pharmaceuticals, genetic therapy and agriculture, as
well as environmental protection.
The chitosan can be used as a coagulant agent for the
removal of organic species as well as an adsorbent of phe-
nols from several industrial effluents. Hence, Grem et al.
(2013) evaluated the behavior of chitosan-based nanoemul-
sions for oily water treatment and they found these materials
were efficient on the decreasing oil content. The biopolymer
showed to be more effective for these applications than other
commonly used species, such as activated carbon and clays.
Additionally, Zhou et al. (2014) concluded that a modified
chitosan with salicylaldehyde and β-cyclodextrin was an
excellent adsorbent for the adsorption of phenol and four dif-
ferent chlorophenols from aqueous solution. As mentioned
above, the capacity of the toxic species removal by chitosan
was studied at laboratory level through batch experiments,
proving its efficacy, eco-friendly character and low toxicity.
Adsorption process
The International Union of Pure and Applied Chemistry
(IUPAC) defines the term adsorption as the “increase in the
concentration of a substance at the interface of a condensed
and a liquid or gaseous layer due to the operation of surface
forces” (McNaught and Wilkinson 1997). The adsorption
process depends on the adsorbates and adsorbents interac-
tions, so its main electromotive forces are solute hydropho-
bicity and electron affinity. A hydrophilic species in aque-
ous medium will have low affinity to hydrophobic adsorbent
species, and the solute electrostatic attraction or repulsion to
the adsorbent solid directly influences the adsorption process
(Aktas and Çeçen 2012; Okiel et al. 2011).
As a species approaches the solid surface, a balance of
attraction/repulsion energies occurs giving rise to two dif-
ferent processes. Usually, when the interactions between
adsorbate and adsorbent occur via intermolecular forces
(van der Waals force), the phenomenon is termed physi-
cal adsorption (physisorption), in which it could result in
multiple layers with equal heat of adsorption. In general,
the adsorbent–adsorbate bond is less energetic than that of
chemical adsorption. Chemisorption is characterized by the
chemical bonding of the species, justifying its higher energy
of adsorption. As a result, only a single molecular layer
or a fraction of a monolayer can be chemically adsorbed
(Rouquerol et al. 2014; Aktas and Çeçen 2012).
The adsorption process can be affected by some factors,
such as (1) the adsorbent surface area—the larger the avail-
able surface area for adsorption, the greater the adsorptive
capacity; (2) the porosity—pore size, shape, and distribu-
tion determine the adsorption capacity and velocity; (3) the
physical–chemical properties of the adsorbate—solubility,
polarity and the presence of substituent groups influence
the species adsorptive capacity; (4) pH—the solvent and the
adsorbate natures may change according to the pH of the
medium (species can attract or repel themselves by elec-
trostatic forces in an acid or basic environment) (Aktas and
Çeçen 2012; Jerônimo 2010; Gomes 2014a, b).
Furthermore, the adsorption process is limited by mass
transfer mechanisms besides its dependence on the charac-
teristics of the adsorbent and adsorbed species. As a result,
the equilibrium between the adsorbate and the adsorbent
does not occur instantaneously in the solution, with the
adsorption kinetics defined as the approximation rate for
that equilibrium (Gomes 2014a, b).
The mass transfer mechanism in bulk liquid medium is
spontaneous and occurs when the solute is carried from
the solution to the boundary layer surrounding the adsor-
bent surface, as shown in Fig. 2 (Aktas and Çeçen 2012).
After this step, it is necessary to transfer this solute from the
boundary layer to the outer surface of the adsorbent (mass
transport in the boundary layer). The particle is then trans-
ported to the adsorbent pores, step which depends on the size
and shape of the pores (intraparticle diffusion). Finally, there
is the formation of an adsorbent–adsorbate bonding (Aktas
and Çeçen 2012; Gomes 2014a, b). The adsorption equilib-
rium occurs when the adsorption rate equals the desorption
rate. The rate of adsorption is the highest during the initial
Fig. 2   Short mechanism of adsorption in a porous material
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moments, since there are more binding active sites available. and Standards: “effluents from any polluting source may
However, as these sites are occupied over time, the adsorp- only be released directly into the receiving body if they obey
tion rate decreases and the desorption process increases the conditions and standards provided in this article, sus-
until the equilibrium is reached (Silva 2010). The adsorp- ceptible to other applicable requirements.” This resolution
tion equilibrium is graphically represented by isotherms, indicates the limits for the content of oils for surface water
which show the relationship between the concentration of bodies such as 50 mg/l for vegetable oils and animal fats
the solute in the adsorbent solid surface and its concentra- and 20 mg/l for mineral oils (CONAMA 2005, 2011). The
tion in the liquid. There are different types of isotherms with CONAMA condition regarding the disposal of phenol-con-
related mechanisms and equations; among them Langmuir taining effluents into water bodies determines a maximum
and Freundlich isotherms are the most used to represent the limit of 0.5 mg/l of total phenols (substances that react with
adsorption equilibrium of liquid systems onto the solid sur- 4-aminoantipyrine) (Souza 2009; CONAMA 2011).
face of the adsorbent, such as industrial effluent treatment The United States Environmental Protection Agency (US
(Carvalho 2006; Silva 2010). EPA) and CONAMA establish the daily limit of total oil and
The adsorption process can occur through batch or fixed grease (TOG) content for produced water release as 42 mg/l,
bed systems. In the first case, a known mass of a solid adsor- with an average limit of 29 mg/l per month (Table 1). Based
bent is suspended in a certain volume of a known concentra- on the Convention for the Protection of the Marine Environ-
tion solute in order to obtain its final concentration in the ment of the North-East Atlantic (OSPAR Convention), the
liquid phase at the adsorption equilibrium. The adsorption average limit of oil dispersed for discharge into the North
capacity is calculated by the ratio of the adsorbate mass on Sea is 30 mg/l per month. The signatory countries of the
the adsorbent per initial adsorbent mass unit. In the fixed bed HELCOM Convention (Helsinki Commission), along with
column system, a low-cost operation in comparison with the Argentina and Venezuela, are the most restrictive countries
batch one, the solution passes continuously through a bed with average limits for TOG (between 15 and 20 mg/l) for
containing solid adsorbents (Carvalho 2006). the disposal of produced water. Colombia does not have an
The natural sorbents come from animal or vegetable average or maximum allowable value of TOG; however, it
waste (organic sorbents), or minerals (inorganic sorbents). states a percentage of 80% of oil removal, which relates the
These can absorb around 3–15 and 4–20 times their weight oil and grease content of the initial produced water and that
in oil, respectively, for organic and inorganic sorbents, for treated for disposal. In general, the average oil and grease
example (Wahi et al. 2013; United States Environmental content of some countries ranges from 15 to 50 mg/l (value
Protection Agency 2016). The use of unconventional and which is allowed in China) (Fraser et  al. 2006; Gomes
low-cost biomass allows not only the reduction in high 2014a, b; Gabardo 2007).
amount of solid waste, but also its great efficiency even
when applied in a low concentration solution (Tran et al.
2015). The research for natural sorbents (including agroin- Table 1  Limit of total oil and grease content acceptable by each
dustrial wastes) increased once common sorbents, such as country for produced water disposal in seawater
activated carbon and other synthetic materials (nanogels, for
Country Limit of TOG
example), have high production costs. Among these stud-
ied species are powdered rubber, fungal biomass, nutshells, Argentina Average: 15 mg/L
natural fibers (silk yarn, rice hulls), natural minerals (ben- Australia Average: 30 mg/L
tonite, vermiculite) and chitosan (powder or flakes) (Pintor Maximum: 50 mg/L
et al. 2016). Brazil Average: 29 mg/L
Maximum: 42 mg/L
Canada Average: 30 mg/L
Maximum: 44 mg/L
Organic effluents China Average: 30–50 mg/L
Maximum: 75 mg/L
Due to the increase in the volume of liquid waste by the Colombia 80% of oil removal
industries, it was necessary to implement a regulation to Mexico Average: 40 mg/L
dispose certain pollutants, in order to control their harmful Maximum: 100 mg/L
levels to man and other living beings. The Brazilian National United States Average: 29 mg/L
Environment Council (CONAMA) regulates, through Reso- Maximum: 42 mg/L
lution No. 357, of 2005, complemented and edited by Reso- Venezuela Average: 20 mg/L
lution No. 430, of 2011, the conditions and standards of HELCOM Convention Average: 15 mg/L
Alternative: 40 mg/L
effluents. According to CONAMA, in the Art. 16 of the most
OSPAR Convention Média: 30 mg/L
recent Resolution, Section II—Effluent Release Conditions

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International Journal of Environmental Science and Technology (2019) 16:1741–1754 1745
The US EPA listed phenol as a priority pollutant and
limited its maximum value for discharge as 0.1  mg/l.
According to Indian standards, the phenol limit for treated
effluent disposal is 1.0 mg/l into surface water and 5 mg/l
into public sewage or seawater (Galgale et al. 2014; Hus-
sain et al. 2015).
The oil itself is the main responsible for water contami-
nation, which occurs mainly during the stages of explo-
ration, production, transportation and refining in petro-
chemical industry, or during the use of the oil derivatives
(Oliveira 2012). Produced water is the most toxic oily
effluent in oil exploration and production stages. Most of
the volume of the produced water is derived from the for-
mation water, which arises from the backlog of fresh or
sea waters in fossil accumulation trapped by impermeable
rocks. Those traps are responsible for the formation of oil
millions of years ago (Gomes 2014a, b; Gabardo 2007).
It is denominated produced water from the moment it is
removed with oil and gas from the production wells (Mota
2010; Motta et al. 2013). Therefore, the produced water
has different compositions depending on where it was
generated, and may contain various salts, gases (such as
­CO2 and H ­ 2S) and dissolved organic compound contents,
besides suspended solids and other chemical species added
during the oil removal process (biocides, antifouling, anti-
corrosion products, etc.) (Fernandes Junior 2006).
Both natural and synthetic oils are potential environ-
ment pollutants due to their composition (Mota 2010).
When the oil gets in contact with aquatic environments,
a film can be formed on its upper layer (due to the lower
density of the oil based on that of the water), which
hinders gas exchange between the aquatic body and the
atmosphere, causing great damages to the fauna and flora
of the environment (Zhou et al. 2008). It can cause atmos-
pheric pollution by the process of evaporation of oil and
its hydrocarbons to the environment, and contamination
of sea or drinking waters, or groundwater, caused by the
percolation process of contaminants, strengthened by inap-
propriate disposal (Jamaly et al. 2015).
Besides the environmental aggravating factor, the
large production of oily wastewater represents an injury
to countries with water scarcity (Mota 2010). As a result,
these countries are developing more efficient and low-cost
technologies for pollutant removal in order to complement
their limited resources to assist their sociopolitical-cultural
demand (Cerqueira et al. 2014). In response to the social
concernment, the government implemented local standards
and laws, which drove further studies on the application of
natural materials, aiming to increase the efficiency of these
effluent treatments, in order to guarantee their adequate
disposal (Cerqueira et al. 2014; Milhome et al. 2009).
Chitosan use in phenol removal
Phenol is an organic pollutant present in several industrial
effluents from different operations, such as polymeric resin
production, oil refining, pesticides, pulp and paper manu-
facturing, and pharmaceutical industries (Galgale et al.
2014). Even in low concentrations, the disposal of phe-
nolic compounds into the environment, or even the degra-
dation of these substances, can cause serious damages to
the fauna and flora of the affected medium (Li et al. 2009).
Several methods of phenol removal from wastewater are
known, such as chemical oxidation or solvent extrac-
tion, by using membranes and by biological treatments
(Milhome et al. 2009). However, the removal of phenolic
compounds using biopolymers is one of the bioadsorption
methods that can be applied for the removal of this pol-
lutant in effluents.
Milhome et al. (2009) studied the adsorption process
of phenol by chitosan and its precursor polysaccharide,
chitin, from a petroleum refinery wastewater. This process
was carried out by varying some physicochemical param-
eters such as pH, conductivity, chemical oxygen demand
(COD), total oil and greases (TOG) and dissolved solids
(DS). Chitin and chitosan had maximum phenol adsorption
capacities of 1.96 and 1.26 mg/g, respectively, following a
Langmuir model (monolayer surface) for both adsorbents,
using an adsorbent dosage of 1 × 10−2 g/ml. The optimal
pH range was found to be 2.0–5.0; however, authors con-
ducted the experiments at pH 6. Chitin removed 52% of
COD and 92% of TOG while chitosan withdrew about 65%
of COD and 67% of TOG from wastewater. The authors
concluded the pore diffusion and surface diffusion were
involved in the adsorption rate. They also affirmed that
chitin and chitosan have good efficiencies that could be
comparable to other low-cost adsorbents like rice husk,
cooke breeze and grain rusk.
Li et al. (2009) studied the application of two functional
chitosan samples (comparing them to the natural chitosan
capacity), chemically modified by salicylaldehyde (CS-
AS) and by β-cyclodextrin (CS-CD), and a cross-linked
β-cyclodextrin polymer (EPI-CD), as adsorbents of phe-
nol, p-nitrophenol and p-chlorophenol from aqueous solu-
tions. The CS-CD and EPI-CD presented higher phenolic
adsorption capacities due to the central cavity of β-CD that
promotes hydrophobic interactions and hydrogen bonds to
organic species (especially those with phenol groups). The
higher p-chlorophenol adsorption capacity for CS-CD in
comparison with that of the EPI-CD shows the primary
and secondary hydroxyl groups of chitosan are impor-
tant to the adsorption process. The removal of phenol by
CS-AS probably occurs via π–π interaction between the
aromatic rings of salicylidene and phenol, and the higher
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1746 International Journal of Environmental Science and Technology (2019) 16:1741–1754
adsorption capacity of p-nitrophenol by this adsorbent may
be due to the interaction of the nitrogen in ‒NO2 group
with the aldehyde. The pH variation study showed when
the solution pH exceeded the phenol pKa values, they
had a negative character (phenolate ions). This explains
the decrease in the p-nitrophenol adsorption capacity by
CS-AS from pH 7.0, p-chlorophenol sorption by CS-CD
and phenol by EPI-CD from pH 9.0 onwards. For that rea-
son, Li et al. (2009) believe molecular interactions such
as hydrogen bonds, hydrophobic interactions and van der
Waals forces may favor the adsorption of phenols. The
regeneration process was also studied, and this regenerated
adsorbent could adsorb from 69.4 to 78.9% of adsorbate
compared to its first use, reused for up to six times.
Zhou et al. (2014) investigated the adsorptions of phenol,
2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,4-dichloro-
phenol (DCP) and 2,4,6-trichlorophenol (TtP) on a modified
chitosan with salicylaldehyde and β-cyclodextrin (CS-SA-
CD) from aqueous solution (comparing its performance with
the modified chitosan grafted with β-cyclodextrin, CS-g-CD,
and chitosan modified by salicylaldehyde, CS-SA). The
maximum adsorption capacities of phenol, 2-CP, 4-CP, DCP
and TCP on CS-SA-CD were around 60, 70, 96, 315 and
376 mg/g, respectively. It was observed that the CD group
in the modified chitosan structure enhanced the adsorption
of chlorophenols due to the interaction through hydrogen
bond among Cl atoms and –OH groups and through π–π
interactions. The adsorbent could be regenerated by wash-
ing it with ethanol, and its adsorption efficiency remained
around 80–91% of the original adsorption capacity.
Moosa et al. (2016) treated chitosan with granular active
carbon for phenol removal through adsorption process.
They obtained a maximum adsorption efficiency of 78% for
pure chitosan (CH), 90% for a 10 wt% chitosan treated with
granular activated carbon (CHGAC​1), 94% for a 20 wt% chi-
tosan treated with granular activated carbon (CHGAC​2) and
86% for the original granular activated carbon (GAC). The
higher adsorption capacity of CHGAC​2 in comparison with
the CHGAC​1 is due to the greater surface area of the first
one (795 and 750 m2/g, respectively), as well as its increased
functional group. Table 2 presents some characteristics of
different studies on the application of chitosan for phenolic
effluent treatment.
The study of the mechanism of adsorption phenolic com-
pounds by chitosan aiming the removal of these species from
industrial effluents can be used to understand their applica-
tion for residual oil removal. Guimarães (2013) and Grem
et al. (2013) affirm in their works that although there are
several studies about using chitosan in wastewater treatment,
few is found in the literature regarding its use in the treat-
ment of oily effluents. In this literature review, some authors
will be shown that have used the adsorbent property of chi-
tosan to treat oily effluents.
13
Chitosan in oil removal
The oil in effluents can be classified as free, dispersed,
emulsified (single or multiple emulsions) or dissolved
oil (Benito et al. 2010). The first categories of oil clas-
sification are the easiest to separate, since the oil is vis-
ible and distinct from the aqueous phase by the density
and appearance differences. Separation processes such as
gravity settling and skimming may be effectively applied.
However, most of these effluents are stable emulsions, in
which oil droplets are dispersed in an aqueous medium,
which makes the separation process more difficult (Ahmad
et al. 2006b; Angelova et al. 2011; Annunciado et al. 2005;
Pal 2011; Pereira and Garcia-Rojas 2015; Simonović et al.
2009; Tadrus 2013; Wahi et al. 2013). Furthermore, some
organic components of petroleum are soluble in aqueous
media, such as some aromatic compounds (phenols and
the so-called BTEX—benzene, toluene, ethylbenzene and
xylenes) and formic and propanoic acids (Sousa 2013).
This makes the treatment of crude oil effluent more com-
plex, once it involves a stable emulsion composed by solu-
ble substances (Oliveira 2012).
The most commonly used methods for oil removal in
effluents can be classified as chemical and photochemi-
cal (chemical adsorption, coagulation and flocculation,
electrocoagulation, flotation, radiation); physical and
mechanical (physical adsorption, skimmer, gravity sepa-
ration, micro- and ultrafiltration, membrane filtration); and
biological (use of microorganisms). These methods can
be applied separately or in combination of two or more
methods, depending on the requirement or not of water
reuse (Wahi et al. 2013).
The choice of the best pollutant removal technique
should consider the source, chemical composition and
effluent production process, as well as the cost–benefit
ratio and maximum available space for the equipment
installation, in order to raise the treatment quality of the
effluent, based on the maximum limit accepted of each
species in the residue. In this context, the adsorption pro-
cess is advantageous because of its simple operation and
high pollutant removal efficiency that does not require a
large space for equipment installation. On the other hand,
it is dependent on the adsorbent’s regeneration capacity,
which leads to waste production (Ahmadun et al. 2009;
Motta et al. 2013; Oliveira 2012).
Wahi et al. (2013) stated in their work that several stud-
ies have shown the oil adsorption is directly related to the
properties of the adsorbent functional groups, including
the O‒H, C=O and C‒O ones. Based on this, Ahmad
et al. (2005b) used two forms of chitosan, flake and pow-
der, for adsorptive treatment of palm oil effluent (POME).
Other natural adsorbents such as peat, clays and activated
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International Journal of Environmental Science and Technology (2019) 16:1741–1754 1747

Table 2  Some characteristics of different studies on the application of chitosan for phenolic effluent treatment
Absorbent Organic pollutant Adsorption capacity Dosage pH Adsorption efficiency References
(mg/g) (%)

Chitosan Phenol from a petroleum 1.26 1 × 10−2 g/ml solution 6.0 70–80 Milhome et al. (2009)
Chitin refinary wasterwater 1.96
CS Phenol, p-nitrophenol 2.22 for phenol 20 mg/25 ml solution 7.0 Not informed Li et al. (2009)
and p-chlorophenol 2.58 for p-clorophenol
from aqueous solutions 1.98 for p-nitrophenol
CS-AS 8.50 for phenol
20.49 for p-clorophenol
44.92 for p-nitrophenol
CS-CD 34.93 for phenol
179.73 for p-clorophenol
20.56 for p-nitrophenol
EPI-CCD 131.50 for phenol
74.25 for p-clorophenol
41.11 for p-nitrophenol
CS-g-CD Phenol, 2-CP, 4-CP, 26.60 for phenol 15 mg/25 ml solution 5.0 80–91 of original Zhou et al. (2014)
DCP and TPC from 32.13 for 2-CP adsorption ­capacitya
aqueous solutions 37.04 for 4-CP
65.36 for DCP
80.26 for TPC
CS-SA 7.23 for phenol
25.56 for 2-CP
31.27 for 4-CP
92.85 for DCP
104.28 for TPC
CS-SA-CD 59.74 for phenol
70.52 for 2-CP
96.43 for 4-CP
315.46 for DCP
375.94 for TPC
CH Phenol 8.1 mg/gb 1.2 g/50 ml solution 7.0 78.4 Moosa et al. (2016)
CHGAC​1 7.2 mg/gb 90.5
CHGAC​2 7.1 mg/gb 94.5
GAC​ 8.4 mg/gb 85.9
a
 This value is the efficiency of adsorption of the fifth-time-regenerated CS-SA-CD adsorbent after washing it with ethanol
b
 Values based on Langmuir isotherm constants

carbon have a negative point of requiring a preliminary
physical–chemical or biological treatment in order to
increase their adsorptive efficiencies. POME is a colloi-
dal suspension containing 95–96% of water, 0.6–0.7%
of oils and greases (about 4000–6000 mg/l of TOG) and
4–5% of total solids, and pH around 4.0–5.0. The work
was based on varying the initial oil concentration, contact
time, adsorbent dosage and pH, besides of equilibrium
and kinetics studies. The adsorption process is promoted
by the protonation of the biopolymer amine groups in acid
medium, leading to a species capable of adsorbing the
residual oil, which has anionic groups, making it possi-
ble to the residual oil to bind and bridge with chitosan in
order to destabilize the emulsion by charge neutralization
mechanism. Hence, the chitosan samples presented high
adsorptive capacity at the natural pH effluent. In general,
the powder chitosan presented higher oil removal content
than the flake form due to the larger surface area the first
one presents (20–30 and 5–10 m 2/g, respectively); this
requires a smaller amount of adsorbent to remove 99%
of POME. Ahmad et al. (2005b) proposed an adsorption
mechanism involving three steps: (1) residual ions diffu-
sion to the surface layer of the adsorbent (which could be
affected by the initial concentration and the contact time),
(2) diffusion into the adsorbent pores and (3) adsorption of
the oil on the internal surface of chitosan (the determining
step of the process). The authors stated that residual oil
adsorption by chitosan is very promising, with excellent
performance at small dosages of adsorbent.
Srinivasan and Viraraghavan (2010) evaluated the
removal efficiency of three types of oil (standard mineral,
vegetable and cutting oils) from water by four types of

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1748 International Journal of Environmental Science and Technology (2019) 16:1741–1754
biomaterials (chitosan, walnut shell and two fungal bio-
masses: Mucor rouxii and Absidia coeruela). In general,
due to the low stability of the vegetable oil emulsion (which
is predominantly composed of triglycerides) its removal
capacity was maximum in comparison with the other types
of oil for all biosorbents, reaching 99.9 mg/g by chitosan at
pH 5.0 (initial oil concentration of 200 mg/l). On the other
hand, cutting oil showed lower affinity for the adsorbents and
lower removal capacity consequently, because of its lowest
surface tension among the oils studied. The percentage of
cutting oil removal by chitosan was 97% against 80% by
A. coerula, the minimum value obtained at a pH of 5.0. In
general, chitosan presented greater oil removal for the three
types of oil studied, and greater removals were reached at
pH 5.0 over than at pH 7.6, suggesting that the acidic media
catalyzed the reaction of –NH2 groups in chitosan with the
oil molecules, according to what was proposed by Ahmad
et al. (2005b).
Sokker et al. (2011) synthesized a chitosan-based poly-
acrylamide (chitosan-g-P(AAm)hydrogel) using grafting
method by gamma ray to investigate the adsorption of crude
oil from aqueous solution through batch adsorptions. The
proposed mechanism of adsorption may involve the same
steps stated by Ahmad et al. (2005b). The crude oil (initial
oil concentration 30 g/l) adsorption on the hydrogel (1.0 g)
was found to be higher at pH 3.0 (2.4 g/g) compared with
pH 7.0 (1.6 g/g) and 9.0 (2.0 g/g). The adsorption capacity
decreased for crude oil from sea water (1.8 g/g) in compari-
son with those obtained in aqueous solution at pH 3.0 and
9.0, once the osmotic pressure between the network of the
polymer and the salt solution environment decreases as the
salt content increases. The authors concluded the prepared
hydrogel could be applied as an adsorbent of crude oil in
wastewater.
Grem et  al. (2013) affirmed that adsorption is gener-
ally the most appropriate technique for the treatment of
oily effluents, once it is capable of removing organic and
inorganic pollutants, besides its efficiency and cheapness.
They pointed disadvantages of using chitosan, such as its
tendency to agglomerate and to form gels when used in its
natural form, besides its solubility in acidic media, hinder-
ing the recycling process. In addition, they affirmed the low
internal surface area of chitosan restricts the access to non-
exposed adsorption sites (amine groups), which decreases
its adsorption rate and capacity. However, such issues can be
minimized by a chemical modification of chitosan with some
substances, such as reticulating agents, which increase its
performance as an adsorbent. Thus, one advantage of such
biopolymer is the capability of being molded into differ-
ent shapes depending on its final application. Therefore, the
authors prepared microspheres of reticulated chitosan with
sodium triphosphate (STP), a multivalent anionic salt, and
studied its application in crude oil (19.7° API) removal from
13
saline water in a packed column. The cyclic conformation
of carbons in the main chain of chitosan chemical structure
gives it low polarity character and allows it to attract struc-
tures like hydrocarbons by van der Waals interactions, and
the presence of polar groups (‒NH and ‒OH) can influ-
ence the adsorption of weakly polar species in the oil by
covalent bonds. Those chitosan microspheres showed an oil
removal efficiency above 90%, with an initial oil concen-
tration of approximately 200 mg/l, demonstrating that the
eluted samples had low enough concentration to be disposed
in Brazilian water bodies (29 mg/l per month, indicated by
CONAMA).
Pitakpoolsil and Hunsom (2014) studied the use of chi-
tosan flakes in biodiesel effluent treatment, once biologi-
cal treatment (considered the most efficient and most eco-
nomical process in biodiesel effluents treatment) generates
a large amount of low-density sludge with low and slow
decomposition efficiency. They evaluated the effects of
adsorption time, effluent pH, adsorbent dosage and mix-
ing speed variations. The pH increase of 2.0–4.0 resulted
in an increase in the removal efficiency, since it decreased
the swelling and fragility of the biopolymer. On the other
hand, the increase in pH from 4.0 to 8.0 resulted in a reduc-
tion in oil removal, once the amino groups of chitosan lose
their cationic character, which causes an electrostatic repul-
sion between the biopolymer surface and the biodiesel. It
was observed a reduction of 66.2% of oil and grease content
(initial TOG of 680–1130 mg/l) under optimal conditions
in a single adsorption process; however, the remaining con-
tent of oil and grease was still higher than the Thai govern-
ment standard for disposal into the environment (5 mg/l).
After the fourth repetitive adsorption process, the value of
oil removed reached up to 95.8%. The authors also studied
the reuse of chitosan by washing it with different concentra-
tions of NaOH. The treatment with the solution of higher
concentration (0.20 M NaOH) caused a greater desorption
process (40% of oil removal). However, the regenerated chi-
tosan adsorptive capacity decreases with an increase in the
number of regeneration cycles.
Farias et al. (2015) studied the diesel removal capac-
ity from natural chitosan beads and cross-linked chitosans
with glutaraldehyde (GLA) and epichlorohydrin (ECH) in
batch adsorption systems. The experiment was based on the
contact of 0.3 g of chitosan beads in diesel oil solutions
of different concentrations (200–900 mg/l). The authors
showed that cross-linked chitosans have higher diesel oil
sorption capacity (reaching 1.82 mg/g of diesel oil removal
for GLA cross-linked chitosan) compared to natural chitosan
(1.065 mg/g of pollutant removal). The authors affirm the
molecular mass, the charge density and other surface char-
acteristics (porosity and roughness) contribute to a greater
agglomeration of the chitosan with the diesel oil. Therefore,
Farias et al. (2015) concluded that the use of chitosan for
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International Journal of Environmental Science and Technology (2019) 16:1741–1754 1749
diesel oil removal in organic solution is feasible according
to the obtained results.
Elanchezhiyan et al. (2016b) also studied the cutting oil
removal from oil in water emulsion by chitosan beads (CB),
carboxylated chitosan beads (CCB) and lanthanum-incor-
porated carboxylated chitosan beads (La-CCB). Parameters
such as contact time, pH, sorbent dosage and the initial oil
concentration were evaluated in order to obtain maximum
adsorption. According to the results, 400  mg La-CCB
removed about 85% of the 4% oil in water emulsion initial
concentration (40 g of cutting oil in 1000 ml of distilled
water) at a pH 3.0. Under the same conditions, the other
biopolymers presented a percentage of cutting oil removal of
less than 20%, which demonstrates the introduction of lan-
thanum in the structure of the carboxylated chitosan beads
increases their hydrophobicity and their affinity with the cut-
ting oil in emulsion consequently. Authors affirm their work
offers a potential platform for the expansion of technology
for oil removal.
Additionally, Elanchezhiyan et al. (2016a) studied the
behavior of a zirconium–chitosan hybrid composite as an
oil sorbent from emulsions of cutting oil in deionized water
through variation in some physical–chemical parameters
such as contact time, pH, sorbent dosage and the initial oil
concentration of the emulsion. The zirconium–chitosan com-
posite sorption capacity showed to be higher than that of the
natural chitosan, once it has more active sites available on its
surface. The maximum sorbent (chitosan and its composite)
sorption was reached at pH 3.0, since under this condition
the oil in water emulsion is destabilized; besides that, the
acid medium catalyzes the formation of hydrogen bonds
between the sorbent surface and the cutting oil droplet. The
pH point of zero charge ­(pHpzc) of the species was also stud-
ied, which indicated the zirconium–chitosan hybrid compos-
ite ­pHpzc is 6.38. At a pH lower than 6.38, the active sites of
the sorbent are positively charged, which favors the adsorp-
tion of the cutting oil in emulsion; pH values above the p­ Hpzc
disfavor the adsorption process because the surface of the
sorbent is negatively charged, limiting the formation of
hydrogen bonds. The effects of adsorbent dosage and the ini-
tial oil concentration indicated that the maximum percentage
of cutting oil removal was achieved using a mass of 400 mg
at 4% initial oil concentration. Finally, the authors concluded
that the hydrophobic properties of chitosan enhance with the
presence of zirconium on its structure, leading to an increase
in its adsorptive capacity of hydrophobic components. In
a more recent study, Elanchezhiyan et al. (2016c) synthe-
sized chitosan/aluminum–zirconium mixed oxide (CS/
AZMO) and chitosan/lanthanum–zirconium mixed oxide
(CS/LZMO) in order to evaluate their adsorption capacities
for oil removal from cutting oil in distilled water emulsion.
The CS/LZMO obtained a maximum cutting oil removal of
92% at a 4% initial cutting oil concentration and pH of 3.0,
while CS/AZMO obtained 74% maximum oil removal under
the same conditions. The synergistic effect of the biopolymer
and the mixed oxides contribute in the cutting oil removal by
hydrophobic interaction and electrostatic attraction (van der
Waals forces). The authors concluded the composites have
tremendous performance in oil recovery, being an effective
and eco-friendly sorbents for oil sorption.
Recently, Elanchezhiyan and Meenakshi (2017) synthe-
sized chitosan/Mg–Al layered double hydroxide compos-
ites (CS-LDHCs) by co-precipitation method for cutting oil
removal from oil in deionized water emulsions. The maxi-
mum cutting oil removal was reached at pH 3.0, in which the
tension between oil and water phases was reduced, improv-
ing the free cutting oil molecules to adsorb on the surface of
the composite through hydrophobic interactions. CS-LDHCs
showed an adsorption capacity of 78% (from a 4% initial
cutting oil concentration) while LDHC (the layered dou-
ble hydroxide material) presented only 30% of cutting oil
removal. This result shows CS-LDHCs as a potential and
very effective oil adsorbent of oil from wastewater.
All the above-mentioned studies conclude chitosan
improves the removal process of different types of oil from
wastewater, highlighting its eco-friendly approach for this
purpose. Some characteristics of those different studies on
the application of chitosan for oil effluent treatment are sum-
marized in Table 3.
Conclusion
This state-of-the-art review justified the necessity of using
alternative adsorbents for organic effluents treatment, show-
ing that adsorption has been highlighted the most practi-
cal, eco-friendly and economic technique among the others.
Under this scope, chitosan drew attention in several studies.
The researches reviewed by this work showed that the use
of chitosan-based biosorbents for organic pollutant removal
from effluents is a promising alternative to substitute the
commonly used materials of higher cost, such as activated
carbon. Its application in effluent treatment was studied both
in its natural (powder or flake types) and in modified forms
(formation of chitosan beads, cross-linking, graphitization
or composites production).
However, choosing the best chitosan adsorbent is not pos-
sible once there is no in-depth study comparing their advan-
tages and the best adsorption conditions. This is because
these materials’ adsorptive capacity depends not only on
the adsorbate properties or on the intrinsic characteristics of
chitosan (as polysaccharide origin and degree of deacetyla-
tion), but also on the conditions of the medium such as pH,
ionic strength, rotation speed, the initial oil concentrations,
contact time and temperature. The results of the reviewed
works show comparisons between the adsorptive capacities
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Table 3  Some characteristics of different studies on the application of chitosan for oil effluent treatment
Adsorbent Organic pol- Initial oil con- pH Dosage Adsorption Oil removal (%) References
lutant centration capacity

Flake CS Palm oil effluent About 2.0 g/l 4.0 0.5 g/l emulsion About 0.45 g/g 80 Ahmad et al.
Powder CS (POME) About 0.55 g/g About 99 (2005b)
Mucor rouxii Standard 200 mg/l 7.6 0.2 g/l emulsion Not informed 67 for SMO Srinivasan and
mineral oil 89 for VO Viraraghavan
(SMO), veg- 65 for CTO (2010)
etable oil (VO) 5.0 72.2 mg/g for 77 for SMO
and cutting oil SMO 93 for VO
(CTO) 92.5 mg/g for 84 for CTO
VO
84.0 mg/g for
CTO
Absidia coeruela 7.6 Not informed 61 for SMO
87 for VO
61 for CTO
5.0 72 for SMO
91 for VO
80 for CTO
Chitosan 7.6 Not informed 96 for SMO
99 for VO
89 for CTO
5.0 99.9 mg/g for 99 for SMO
VO 99 for VO
97 for CTO
Walnut shell 7.6 Not informed 38 for SMO
60 for VO
73 for CTO
5.0 83 for SMO
96 for VO
96 for CTO
Chitosan-g- Crude oil 30 g/l 3.0 1 g/100 ml 2.4 g/g Not informed Sokker et al.
P(AAm) 7.0 emulsion 1.6 g/g (2011)
hydrogel
9.0 2.0 g/g
Chitosan micro- Crude oil 200 mg/l Not informed Not informed Not informed Above 90 Grem et al. (2013)
esphere
Chitosan flakes Biodiesel efflu- 680-1130 mg/la 4.0 3.5 g/l emulsion Not informed 66.2%b Pitakpoolsil and
ent 95.8%c Hunsom (2014)
Chitosan Diesel oil solu- 200 mg/l Not informed Not informed About 1.1 mg/g About 22 Farias et al.
EPH-cross- tion About 1.6 mg/g About 24 (2015)
linked chitosan
GLA cross- About 1.8 mg/g About 39
linked chitosan
Chitosan beads Cutting oil 40 g/l 3.0 400 mg/25 ml Not informed 8 Elanchezhiyan
Carboxylated emulsion emulsion Not informed 20 et al. (2016b)
chitosan beads
Lanthanum- 21.24 mg/kg at 85
carboxylated 303 K
chitosan beads 21.33 mg/kg at
313 K
21.30 mg/kg at
323 K

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Table 3  (continued)
Adsorbent Organic pol- Initial oil con- pH Dosage Adsorption Oil removal (%) References
lutant centration capacity

Chitosan Cutting oil 40 g/l 3.0 400 mg/25 ml Not informed About 13 Elanchezhiyan
Zirconium– emulsion emulsion 20.83 mg/kg at 79 et al. (2016a)
chitosan 303 K
composite 21.63 mg/kg at
313 K
23.99 mg/kg at
323 K
CS/AZMO Cutting oil 40 g/l 3.0 250 mg/25 ml 24.65 mg/kg at 74 Elanchezhiyan
emulsion emulsion 303 K et al. (2016c)
22.75 mg/kg at
313 K
23.97 mg/kg at
323 K
CS/LZMO 200 mg/25 ml 24.31 mg/kg at 92
emulsion 303 K
24.48 mg/kg at
313 K
24.97 mg/kg at
323 K
CS-LDHCs Cutting oil 40 g/l 3.0 250 mg/25 ml 24.43 mg/kg at 78 Elanchezhiyan
emulsion emulsion 303 K and Meenakshi
25.41 mg/kg at (2017)
313 K
26.65 mg/kg at
323 K
LDHCs Not informed 30
a
 In total oil and grease content (TOG)
b
 Efficiency of the first-adsorptive process for TOG content
c
 Efficiency of the fourth-adsorptive process, for TOG content, by regeneration processes with NaOH

of the commonly used adsorbents and chitosan materials,
without comparing the adsorptive capacities among different
chitosan-based materials. It was observed that most of the
researches studied in this review concluded that the adsorp-
tive capacity of chitosan or its derived materials was maxi-
mal at acidic pH, which indicates a great influence of the
electrostatic attraction mechanism in the adsorption process.
In general, a considerable amount of the reviewed studies
did not present comparisons between the adsorption efficiency
of the modified chitosan and that for the natural one in order
to show how the modification on its structure improves its
adsorption capacity. In the case of oil removal, there are also
no studies using one, two or three hydrocarbon molecules
present as larger quantities in oil sample used to simulate the
adsorption efficiency models. Models could contribute to elu-
cidate the adsorption mechanism, once it involves the interac-
tion of chitosan (pure and modified) with the oil phase (crude,
diesel or vegetal oils, etc.) in aqueous medium (salty or not).
This literature review shows that most of the studies mention
the development of organic–organic or inorganic–organic
materials, in which the latter are the best in terms of adsorp-
tion efficiency. However, few studies on multiple adsorption,
regeneration, recovery, selective extraction of some adsorbed
components, storage of materials after adsorption are found
in the literature.
Additionally, an important topic for further studies on
the potential of chitosan for organic pollutant removal from
effluents is its application at industrial scale. Thus, a research
on the simultaneous removal of several pollutants is of great
interest for the industry, as well as the kinetics and thermody-
namics studies of the adsorption process using real effluents.
Furthermore, more work is necessary to know details about the
regeneration process of those materials, once it is extremely
important to determine the economic viability of the adsorbent
and determine the reuse of this material in order to reduce its
disposal.
Acknowledgments  The authors are grateful to CNPq and UFBA for
financial support.

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1752 International Journal of Environmental Science and Technology (2019) 16:1741–1754

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