Arabian Journal of Chemistry (2020) 13, 1821–1830

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Removal of pentachlorophenol pesticide from

aqueous solutions using modified chitosan
Aparajita Shankar a,1, Manasa Kongot b,1, Vipin Kumar Saini a,*, Amit Kumar b,*

a
School of Environment and Natural Resources, Doon University, Dehradun, Uttarakhand 248012, India
b
Centre for Nano and Material Sciences, Jain University, Jain Global Campus, Kanakapura, Ramanagara, Karnataka 562 112, India

Received 17 October 2017; accepted 25 January 2018

Available online 6 February 2018

KEYWORDS Abstract For the development of a bioadsorbent with enhanced adsorption properties to remove
Pesticide removal by pentachlorophenol (PCP) pesticide from aqueous solutions, a modified chitosan material CHTA (1)
adsorption; was successfully obtained by crosslinking of chitosan (CHT) (I) with 2-hydroxy-1-naphthaldehyde.
Chitosan; Functionalized chitosan CHTA was further modified by grafting with CuCl2 to prepare CHTAC
Endocrine disruptor (2). The obtained products were characterized with the necessary chemical and spectroscopic tech-
compound; niques and were studied as an adsorbent for PCP removal from aqueous solutions. The adsorption
Wastewater treatment; capacity of 1 and 2 improved by 94% and 76% respectively as compared to CHT. Kinetics and
Pentachlorophenol removal; thermodynamic studies were carried out to understand equilibrium data of uptake capacity and
Surface modification kinetic rate of adsorption. Desorption properties and reusability of prepared materials were evalu-
ated up to three consecutive adsorption-desorption cycles with different desorbing agents.
Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction et al., 2014). It is a widespread environmental pollutant and

causes endocrine disruption (Orton et al., 2009). Therefore,
Pentachlorophenol (PCP) is one of the common pesticide and PCP removal from aqueous solution is an objective of environ-
fungicide used in wood protection industry which contami- mental and scientific concern. Adsorption based techniques are
nates soil and groundwater, especially around wood preserving known for their efficiency, selectivity, and safety in water treat-
facilities. Poisoning from PCP causes leukemia, peripheral ment applications. The cost and efficiency of these techniques
neuropathy and several other neurological disorder (Ali are regulated by the adsorbents employed in the process (Ali
and Gupta, 2007). It is well known that use of low-cost natural
* Corresponding authors. materials and by-products can improve the cost-effectiveness
and sustainability of these techniques. But quite often, the
E-mail addresses: vksaini.senr@doonuniversity.ac.in (V.K. Saini),
amit.kumar@jainuniversity.ac.in (A. Kumar). adsorption properties of these low-cost materials are not com-
1
Authors have contributed equally. parable to the commercially available adsorbents (Gupta et al.,
Peer review under responsibility of King Saud University. 2009). Improvement or modifications in adsorption properties
of these materials are therefore a requisite before perfoming
their application studies.
Chitosan (a natural amino polysaccharide) has been used as
Production and hosting by Elsevier a bioadsorbent for water treatment, biopesticide, antibacterial

https://doi.org/10.1016/j.arabjc.2018.01.016
1878-5352 Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1822 A. Shankar et al.

agent or as drug carrier (Ravi Kumar, 2000). Adsorption prop- tosan material will enhance the PCP adsorption due to coordi-
erties of chitosan are originated from a large number of pri- natively unsaturated copper metallic site if any (Song et al.,
mary and secondary hydroxyl (AOH) and primary amine 2016).
(ANH2) groups that act as active adsorption sites. As a result, In this study, the surface of chitosan flakes (CHT) was
its surface acts as a complexing medium for ionic species dur- functionalized by two consecutive methods which involved
ing adsorption process that distinguishes it from several other cross-linking with 2-hydroxy-1-naphthaldehyde to obtain
adsorbents. These properties, along with its biocompatibility CHTA followed by further grafting with CuCl2 to synthesize
and cost effectiveness makes it a suitable candidate for adsorp- CHTAC. The prepared materials were used for the adsorptive
tive removal of organic and inorganic pollutants such as dyes, removal of PCP from water samples in a batch process. The
phenols, pharmaceuticals, pesticides, fungicides and heavy effects of modification were henceforth explored in terms of
metal ions (Wan Ngah et al., 2011) from wastewater. adsorption capacity and selectivity.
The amino group on chitosan is particularly an advanta-
geous functional group that can be modified chemically to 2. Experimental
obtain chitosan derivatives with desired adsorption character-
istics. Several researchers worked largely on modification of 2.1. Materials and methods
chelating functionalities, mainly by increasing amino groups.
For example, histidine, an amino acid with amino and imida-
All the chemicals and solvents were of AR grade, which were
zole side chain donor groups was added to improve chelation
used without further purification. Chitosan (CHT) flakes with
properties of chitosan (Beppu et al., 2004). Graftings of chi-
>75% degree of deacetylation and 2-hydroxy-1-
tosan with cationic surfactant hexadecylamine (Vakili et al.,
naphthaldehyde (98% pure) were obtained from Himedia Lab-
2016), amino silane and 3-aminopropyl triethoxysilane
oratories Pvt. Ltd, India. Copper chloride (97% pure), acetic
(APTES) (Vakili et al., 2015) were reported to improve the
acid (>98% pure), ethanol (99.9% pure), methanol (99%
adsorption of reactive blue 4 dye. Uptake of cadmium from
pure), and diethyl ether (99.5% pure) were obtained from S.
aqueous solution was improved by grafting with anionic sur-
D. Fine-Chem. Ltd., India. Pentachlorophenol (PCP) (97%
factant sodium dodecyl sulfate (SDS) (Pal and Pal, 2017). Tan-
pure) was obtained from Sigma-Aldrich. Chitosan and its
nic acid, a polyphenol was used to modify chitosan, where
modified derivatives (CHTA, and CHTAC) were characterized
improvement in adsorption of Al and Pb ions was reported
by different analytical techniques to analyze the change in their
(Badawi et al., 2017).
structural and surface properties. The specific surface area and
In an alternative way, chelating properties of chitosan have
pore volume were obtained from Microtrac BEL Belsorp Max,
improved by modification of amino groups into Schiff base
Japan. The Field Emission Scanning Electron Microscopy
with the help of active carbonyl groups (Gavalyan, 2016). Chi-
(FESEM) and Energy Dispersive X-ray Spectroscopic
tosan modified by thiourea and glutaraldehyde was reported
(EDAX) analysis were acquired from JEOL-JSM7100F. The
for adsorption of Hg ions (Donia et al., 2008). Effect of similar
ATIR spectra of materials were obtained from Bruker Alpha
modification for adsorptive separation of UO+2 2 , was investi-
Single reflection ATR module equipped with ZnSe crystal.
gated by Elwakeel and Atia (Elwakeel and Atia, 2014). Schiff’s
The point of zero charge pHzpc of materials was measured
base derivative of chitosan was prepared with 2-amino ben-
by following a method, given elsewhere (Babić et al., 1999).
zaldehyde, through an ion-imprinting technique, for selective
Briefly, for each material, 11 Erlenmeyer flasks, each with 20
removal of Pd which exhibited maximum adsorption capacity
mL of Millipore water were taken and their pH was main-
of 275 mg/g (Monier et al., 2016). Coupling of chitosan with 1-
tained from 2 to 12 by using sulfuric acid solution (5 N) and
vinyl 2-pyrrolidone and 4-amino acetanilide was also studied
sodium hydroxide solution (1 N), whenever required. Conse-
for the adsorption of anionic reactive dye (methyl orange)
quently, 0.02 g of material was added into each of these 11
(El-Sayed et al., 2016).
flasks and were stirred for overnight. The final pH of the solu-
The adsorption potential of chitosan Schiff base derivatives
tions was recorded using Metrohm pH meter.
is limited to the metal ions but not fully explored for emerging
organic contaminants (Kyzas and Bikiaris, 2015). It is
2.2. Chemical modification of chitosan (CHT)
expected that if aryl groups are introduced to chitosan surface
through Schiff base reaction, it may improve its adsorption
2.2.1. Modification of CHT with 2-hydroxy-1-naphthaldehyde to
properties towards organic contaminants. The modification
prepare CHTA
of chitosan into Schiff base containing aromatic substituent
groups followed by complexation with a transition metal ion The amine groups on CHT flakes were functionalized with 2-
can be the best approach for adsorption of organic contami- hydroxy-1-naphthaldehyde following a procedure (Scheme 1),
nants. This grafting and cross-linking technique improves the reported elsewhere (Jiao et al., 2011; Sobahi et al., 2014).
stability and adsorption properties in extreme media condi- Briefly, about 7 g of CHT flakes were dissolved in 20 mL of
tions (Wu et al., 2016). Furthermore, the addition of metal 1% acetic acid solution in a round bottom flask at room tem-
sites (electron deficient) to adsorbent surface can improve its perature. Hot methanolic solution of 2-hydroxy-1-
interaction with electron rich molecules, aromatic compounds naphthaldehyde (8 g in 50 mL), was slowly added to the
for instance. In this context, copper is one such metal which CHT solution. This reaction mixture was refluxed overnight
can be used for grafting into the chitosan material. A chitosan with continuous stirring to obtain the modified chitosan mate-
based organic-inorganic hybrid modified with copper has been rial CHTA. The excess of aldehyde were removed by repeated
previously used for the oxidative degradation and adsorption wash with methanol. The purified material so obtained was
of Reactive Blue 5 dye (Amreen et al., 2017). Hence it will then dried in an oven at 80 °C for 5 h and stored in a desiccator
be noteworthy to investigate if insertion of copper into chi- until further use.
Removal of pentachlorophenol pesticide from aqueous solutions using modified chitosan 1823

Scheme 1 Modification of chitosan (CHT) using 2-hydroxy-1-naphthaldehyde and CuCl2.

2.2.2. Modification of CHTA with copper chloride to prepare Similarly, the adsorption isotherms of all the three chitosan
CHTAC samples were obtained at 293, 303, and 313 K with typical
For incorporation of copper into the functionalized CHTA batch scale equilibrium-adsorption experiments. Here, the
(Scheme 1), a clear solution of copper chloride (5 g in 20 mL batch contains 10 glass vials each of 50 mL capacity, fitted
ethanol) was added to CHTA (5 g) and the mixture was with PTFE caps. Each vial was filled with 20 mL of PCP solu-
refluxed for 3 h. A dark green colored material CHTAC tion with concentration ranging from 10 to 130 mg/L, and
obtained, was filtered-off and washed repeatedly with ethanol 0.02 g of adsorbent sample. The complete batch was stirred
and diethyl ether. The purified sample was then dried in an in a water bath, for next 3 h, on a multipoint magnetic stirrer,
oven at 80 °C for 5 h and stored in a desiccator until further (Velp Scientifica). In the end, the equilibrium concentration of
use. PCP in liquid phase was analyzed, as detailed above.
Desorption study was carried out to test the reusability of
2.3. Adsorption and desorption experiments prepared materials for further adsorption cycles. The study
involved two parts, in first a suitable desorbing agent was iden-
tified to achieve maximum desorption, and in second the
Most of the adsorption experiments were carried out with all
adsorption-desorption cycles were carried out with selected
the three chitosan samples in batch mode. In these experi-
desorbing agent. The objective of the second experiment is to
ments, the effects of different parameters like contact time,
follow the loss of adsorption capacity with successive cycles.
pH, temperature, and initial concentration on amount of
For desorption test, five different desorbing agents namely
adsorption was observed. For these studies, a stock solution
HCl, HNO3, NaOH, NaCl, and H3PO4, each with 0.1 N were
of PCP, 1000 mg/L was prepared by using Millipore water
used. In these experiments after adsorption, 0.05 g of
and filtered through Durapore HVLP 0.45 mm 47 mm. For
exhausted adsorbent was added to 50 mL of each of the des-
adsorption experiments, a definite amount of adsorbent was
orbing agent solution. The solution was then stirred for 3 h
added to the standard PCP solution and then subjected to
at room temperature and the change in concentration of super-
given adsorption conditions like pH, temperature, and dura-
natant was observed to calculate the amount of desorption
tion. In the end of the experiment, the solution was filtered
(mg/g) as per the following equation,
out with a syringe filter (Cole-Parmer Nylon 25 mm, 0.45
mm) and the concentration of remaining PCP in liquid phase qed ¼
Ced
 Vd ð2Þ
was analyzed with UV spectrophotometer (Evolution 201, m
Thermo Scientific) at wavelength of 220 nm. Following mass Here, the qed is the amount of desorption from a unit mass of
balance equation (Eq. (1)) was used to calculate the amount chitosan materials in mg/g, and Ced is the concentration of
of PCP adsorbed on the material: supernatant in mg/L after desorption, m is the mass of
C0  Ce exhausted adsorbent in g and Vd is the volume of desorbing
qe ¼ V ð1Þ agent in L. The selected desorbing agent is used for reusability
W
test, where 0.1 g of the chitosan sample is stirred with 50 mL of
where, C0 and Ce are the initial and equilibrium PCP concen-
100 mg/L, PCP solution. After adsorption, the exhausted sam-
trations (mg/L) respectively, V is the volume of solution (L), w
ple is dried and desorbed with 50 mL of previously identified
is the mass of the adsorbent (g), and qe is the amount of PCP
desorbing solution. After desorption, the sample was washed
adsorbed (mg/g).
and dried again, before further adsorption. These
The effect of contact time on adsorption was observed with
adsorption-desorption cycles continued until the end of the
all the three samples. In this experiment, 0.2 g of sample was
third cycle. The change in adsorption and desorption amount
added to 200 mL of 150 mg/L PCP solution in a conical flask
after each cycle was calculated in terms of%, where, initial
of 250 mL capacity. The solution was stirred with a magnetic
adsorption amount was taken as 100%. For instance, the%
stirrer in a water bath at 293 K. While stirring, the aliquots
desorption was calculated as,
of 3 mL were sampled periodically, up to 3 h, and analyzed
for amount of adsorption. The effect of solution pH on the q
%Desorption ¼ ed  100 ð3Þ
adsorption of PCP by all the three samples was investigated qea
with pH gradient experiments. In this experiment, the pH of Here, the qea and qed are the amounts of adsorption and des-
the PCP solution (100 mg/L) was varied from 2 to 12, using orption with a unit mass of materials in mg/g. During this
0.1 N NaOH or 1.0 N HCl solutions. The adsorption experi- study, all the adsorption and desorption experiments were car-
ments were carried out at 293 K, with adsorbent dose of ried out, at least in duplicate, and from these experiments, the
0.02 g in 20 mL of solution. average value of amount adsorbed or desorbed is reported.
1824 A. Shankar et al.

The uncertainties in the results of batch experimental method

were found below ±2%. The effect of this maximum value on CHT
the resultant parameter is below ±4% and does not have a sig-
nificant influence on the interpretation of the results.

3. Results and discussion

3.1. Characterization of samples

Evaluation of structural properties is important for an adsor-

bent, therefore, FESEM micrographs and EDAX spectra of
CHT, CHTA, and CHTAC are presented in Fig. 1. The micro-
graphs show that the surface of all the three materials are non-
CHTA
homogenous and quite rough in nature and therefore provide a
suitable surface area for adsorption. It also indicates that the
structure remains unchanged even after modification and the
only difference is the impregnation of aldehyde group and cop-
per on the chitosan surface. Variation in surface morphology
from CHT to CHTA and then to CHTAC can be observed
from these images.
The EDAX analysis carried out for elemental analysis of
CHT, CHTA, and CHTAC and also for surface chemistry
shows that the modification with 2-hydroxy-1-
naphthaldehyde increases the content of carbon on the surface.
The wt.% of C in CHT is 32.6% and after the modification, it
was increased to 46.1%. Similarly, the incorporation of Cu CHTAC
(9.1 wt.%) and Cl (8.6 wt.%) in CHTAC surface is also con-
firmed with these results.
The ATIR spectra of all the three samples are obtained and
compared in Fig. 2. The analysis compares various functional
groups, present on the material surface, before and after func-
tionalization. In the case of CHT, the stretching at 1017 cm1
is attributed to CAOAC of the ring. The vibrational bands at
1648 cm1 and 1532 cm1 represent amide I band (the residual
acetamido groups that remain after deacetylation of chitin
during the production process of chitosan) and ANH2 bending
respectively. The CAH stretching can be assigned at 3081 cm1
and OAH group stretching can be confirmed from the vibra-
tional peak at 3348 cm1. Fig. 1 FESEM and EDAX spectra of chitosan and modified
In the IR spectra of CHTA, the stretching of CAOAC was chitosan.
confirmed at the peak of 1025 cm1. A new peak at 1635 cm1
was found which can be attributed to the imine bond (AC
‚N) formation by the condensation between the free amine
group of CHT and aldehyde group of 2-hydroxy-1-
naphthaldehyde. The vibrational band in the region of 2807–
3043 cm1 confirmed the presence of CAH stretching. The 70
OAH stretching was confirmed from the peaks of 3489, 60
3411 cm1.
In the CHTAC sample, the absorption band at 615 cm1
% Transmittance

50

confirms the presence of CuAO stretching. The band at 40

1623 cm1 attribute to the imine bond (AC ‚ N) whereas
30
ArACAH stretching was observed in the band range of
2886–3027 cm1. 20
The results of point of zero charge experiments are pre-
10
sented in form of pHZPC plots (Fig. 3) where final pH of the CHT CHTA CHTAC
solution is plotted as a function of initial pH of the solution, 0
4000 3500 3000 2500 2000 1500 1000 500
having material in contact. The change in surface chemistry
Wavenumber (cm-1)
on functionalization is evident from the difference in their iso-
electric points. Fig. 2 ATIR spectra of CHT, CHTA, and CHTAC.
The isoelectric points or pHZPC of CHT, CHTA, and
CHTAC samples are found to be at 7.7, 6.7 and 4.0, respec-
Removal of pentachlorophenol pesticide from aqueous solutions using modified chitosan 1825

14 45
Initial pH = Final pH
40
12
CHT
35
10 CHTA

amount adsorbed qt (mg/g)

30
CHTAC
8 25
Initial pH

6 20

15
4 CHT
10 CHTA
CHTAC
2
5

0 0
0 2 4 6 8 10 12 14 0 50 100 150 200
Final pH Time t (min)

Fig. 3 The point of zero charge (pHzpc) of CHT, CHTA, and Fig. 4 Effect of contact time on the adsorption of PCP by CHT,
CHTAC. CHTA, and CHTAC samples, with initial conc. 150 mg/L,
at 20 °C.

tively. It signified that these materials will retain positive

charge below a pH then their pHpzc and will retain a negative
charge at pH above these values. This observation can be the aromatic ring has increased the interaction of CHTA with
attributed to the dissociation of surface functional groups with PCP molecules. In the case of CHTAC, the addition of elec-
an increase in solution pH (Kosmulski, 2009). tron deficient (CuII) metal center in the structure has caused
The low-temperature nitrogen adsorption/desorption iso- lack of p electron density over the aromatic ring. This phe-
therms were obtained for all the three materials. BET surface nomenon reduces the interaction of PCP with the surface of
area and total pore volume were calculated from these iso- CHTAC as compared to CHTA.
therms (Table SI-1). The chitosan and modified materials Kinetic modeling helps to determine the rate of adsorption
are characterized by low values of the surface area ranging of PCP on the adsorbent’s surfaces. For this purpose, adsorp-
from ABET = 2.43 – 0.37 m2/g. The total pore volume of tion data obtained from kinetic experiments (Fig. 4) were
CHTA (1.76  103 cm3/g) is higher compared to CHT applied to different kinetic models to explain the rate of
(0.17  103 cm3/g) and CHTAC (0.71  103 cm3/g). Despite adsorption by these materials. Two kinetic models, namely
their low surface area, these materials are still useful for the pseudo-first order and pseudo-second order were employed
effective removal of inorganic and organic contaminants in this process. In the pseudo-first order, we assume the
(Wysokowski et al., 2014). adsorption to be completed in a single step and can be
expressed by the Lagergren rate equation (Eq. (4))
3.2. Rate of adsorption (Lagergren, 1898):
k1
Generally, the difference in adsorbent’s surface leads to a dif- logðqe  qt Þ ¼ log qe  t ð4Þ
2:303
ference in adsorption capacity and rate of adsorption. Kinetic
experiments were conducted to observe these differences with where qe stands, for the amount of PCP adsorbed (mg g1) at
all the three materials. In these experiments, the progress of equilibrium, qt (mg g1) is the amount of PCP adsorbed at
adsorption process was followed as a function of contact time. time t and k1 is the rate constant (min1). The results of the fit-
The results of these experiments are compared in Fig. 4. ting are compared in Table 1. The plot between log (qe–qt) and
All the samples show fast initial adsorption (up to 10–15 t showed low linear regression coefficient R2 value ranging
min) which is due to the availability of vacant sites for adsorp- from 0.85 to 0.91, suggesting poor fit of pseudo-first order
tion. Subsequently, the adsorption slows down gradually until model to adsorption data. In addition, the calculated qe value
a maximum adsorption capacity reached. Until that point, the from this model does not concur with the experimental results.
duration of contact time is considered as equilibration time. Altogether, these observations point that adsorption did not
After a certain time interval, there is no noticeable increase take place in single step with present adsorbate-adsorbent
in adsorption capacity with each material. The maximum systems.
adsorption capacity of these materials follows an order of Likewise, the pseudo-second order model Eq. (5) (Ho and
CHTA > CHTAC > CHT. The functionalization of chitosan McKay, 1999) can be expressed as:
surface has increased its adsorption capacity. The extent of t 1 1
increase is greater in the case of CHTA, as compared to ¼ þ t ð5Þ
qt k2 q2e qe
CHTAC. In CHTA the addition of 2-hydroxy-
naphthaldehyde through an imine linkage provide a suitable where k2 is the rate constant (g mg1 min1). The plot between
site for interaction with PCP. The AOH group connected to t/qt and t (Fig. SI-1) shows a straight line for all three adsor-
1826 A. Shankar et al.

Table 1 Kinetic parameters for the adsorption of PCP on different chitosan samples.
Samples Pseudo-first-order Pseudo-second-order
qe, exp qe, calc k1  10 2
R 2
qe, calc k2  103 R2
(mg g1) (mg g1) (min1) (mg g1) (g mg1 min1)
CHT 24.37 14.46 3.44 0.85 25.25 6.32 1.00
CHTA 39.07 21.90 3.10 0.88 40.02 4.78 1.00
CHTAC 35.37 22.05 3.03 0.91 36.63 3.80 1.00

bents. The linear regression coefficient R2 having value 0.998 speciation of PCP and the surface properties of different chi-
(rounded off as 1.00) indicates best fit of the model. The values tosan samples determine the adsorption of PCP at various
of calculated qe,calc are in agreement with the experimental qe,- pH gradient. The PCP is a weak acid and its pKa is 4.7, which
exp values (Table 1). The observations support the suitability of means at pH < 4.7 the PCP remain neutral (protonated) and
second order kinetics and thus suggests that the adsorption of at pH > 4.7, it deprotonates and remains as negatively
PCP on three samples took place in two steps, which are pos- charged species, PCP. At low pH the neutral form of PCP
sibly adsorption and diffusion. is dominant; this form of PCP is strongly hydrophobic and
During adsorption, the diffusion is a transport process, causes its high adsorption under these conditions (Li et al.,
which involves the movement of species from the bulk of the 2009; Zhou et al., 2014). As the pH of solution increases, the
solution to the solid phase. Besides, outer surface adsorption, solubility of PCP starts increasing and the distribution of anio-
there is a possibility of intraparticle diffusion from the outer nic PCP dominates (Mathialagan and Viraraghavan, 2009).
surface into the pores of the materials (Wu et al., 2009). The The PCP adsorption by all the three materials fall steeply in
overall adsorption process may indeed be controlled either the range of pH 3.0 to 8.0, which is due to high solubility
by one or more steps, e.g. film or external diffusion, pore dif- and low hydrophobicity of anionic PCP species. The extent
fusion, surface diffusion and adsorption on the pore surface, of adsorption by different chitosan samples is governed by
or a combination of more than one step. their surface properties, or in other words, surface charge on
Usually, a process is diffusion-controlled when its rate the sample, which depends on both the pH of the solution
depends on the rate at which adsorbate molecules diffuse and its pHzpc. In case of CHT, (Fig. SI-3) the surface charge
towards one another. The likelihood of intraparticle diffusion is positive at pH < 7.7, while tend to be negative at pH >
was explored by using the intraparticle diffusion model. Fol- 7.7. When pH is >8 more than 70% of PCP available as
lowing, Weber and Morris intraparticle diffusion model Eq. PCP, the electrostatic repulsion between this anionic form
(6) (Weber and Morris, 1962) was applied to kinetic data: and negatively charged CHT surface starts inhibiting adsorp-
tion. Nevertheless, PCP still remains adsorbed to negatively
qt ¼ kid  t0:5 þ C ð6Þ
charged surface, which is possibly due to p–p interaction
1/2
where kid (mg/min ) is the intraparticle diffusion rate con- between negatively charged CHT and p electron cloud on
stant and C (mg/g) is a constant related to the thickness of PCP (Li et al., 2009). At pH < 7 presence of hydroxyl group
boundary layer. The value of C is directly related to the extent and amino group on the surface provides suitable adsorption
of boundary layer effect (Ho et al., 2000). If the plot of qt sites and weak hydrophilicity of CHT surface facilitate the
against t0.5 gives a straight line, then the sorption process is adsorption to the negatively charged species. Under such con-
controlled only by intraparticle diffusion. However, if it shows ditions, the hydrogen bond formation between CHT surface
multi-linear plots, then two or more steps influence the adsorp- and PCP could be responsible for higher adsorption. The
tion process. Fig. SI-2 shows plots for all the three materials, CHTA and CHTAC samples follows, the same trend, (see
where every plot is composed of three different linear steps. Fig. SI-3) the relative amount of their adsorption is more evi-
It shows that the external resistance to mass transfer surround- dent at lower pH, where the effect of their surface charge is
ing the particles is significant only in the early stages of adsorp- dominant on adsorption process.
tion, which is represented by a first sharper step. The second
linear portion is the gradual adsorption stage with controlling 3.4. Isotherm modeling
intraparticle diffusion. The third step shows saturation of
adsorbent surface (Li et al., 2012). The deviation of straight Adsorption isotherm studies can help in interpretation of rela-
lines from the origin (Fig. SI-2) could be due to the difference tionship between equilibrium adsorption capacity and equilib-
in the rate of mass transfer in the initial and final stages of rium concentration at a definite temperature. The variation in
adsorption. Furthermore, such deviation indicates that the amounts of PCP absorbed per unit mass of CHT, CHTA, and
pore diffusion is not the only rate-controlling step. CHTAC as a function of equilibrium PCP concentration in the
solution at different temperature of 293 K, 303 K, and 313 K is
3.3. Effect of pH presented in Fig. SI-4. These equilibrium adsorption data were
applied to three different adsorption models, namely Lang-
The effect of solution pH on adsorption of PCP by different muir, Freundlich, and Redlich-Peterson models. The parame-
chitosan samples is compared in Fig. SI-3. It shows that, the ters obtained from fitting of these models on adsorption data
Removal of pentachlorophenol pesticide from aqueous solutions using modified chitosan 1827

are compiled in Table 2. The Langmuir isotherm model is ther, the suitability of the Langmuir isotherm to fit the data
believed to be suitable for homogeneous adsorption where at 293 K was confirmed by the exponent value m of the Red-
the adsorption process had identical activation energy and lich–Peterson model, which was equal to one. By taking into
was applicable to monolayer adsorptions without any interac- account the R2 and qmax values projected by Langmuir model,
tion among adsorbed species (Langmuir, 1916). The Langmuir it was observed that both the Langmuir and Redlich–Peterson
equation (Eq. (7)) is given as follows: isotherms could well describe the experimental adsorption
Ce 1 Ce data, however the Redlich–Peterson model was more suitable.
¼ þ ð7Þ
qe qmax b qmax
3.5. Thermodynamics of adsorption
Here, qe is the amount of PCP adsorbed on the adsorbent sur-
face (mg/g), Ce is the concentration of PCP at equilibrium (mg/ Adsorption of PCP on the surface of chitosan and its modified
g), qmax stands for saturation adsorption capacity (maximum forms varies with temperature ranging from 293 K to 313 K, as
monolayer amount) of PCP absorbed on adsorbent surface, evident from Fig. SI-4. The maximum adsorption capacity was
b is the Langmuir constant for adsorption energy (L/mg). observed at lower temperature condition that indicates the
The non-linear fitting of this equation can be observed in exothermic nature of adsorption. With the help of adsorption
Fig. SI-4. The results of fitting shows (Table 2) decrease in isotherm data, thermodynamics of PCP adsorption was inves-
adsorption energy ‘b’ and qmax with increase in temperature. tigated to evaluate the thermodynamic feasibility and the
For this model, the regression coefficient R2 values varies from spontaneous nature of the process. It involves estimation of
0.91 to 0.98 collectively for all the three materials. thermodynamic parameters such as the change in Gibbs free
Unlike Langmuir model, the Freundlich isotherm model energy (DG°), change in enthalpy (DH°) and the change in
describes the multilayer adsorption on heterogeneous surface entropy (DS°). These parameters are estimated from the varia-
(Freundlich, 1906). The equation (Eq. (8)) is expressed as: tion of the thermodynamic equilibrium constant ‘K’ as a func-
 
1 tion of adsorption temperature (Salvestrini et al., 2014). For a
log qe ¼ log Kf þ logCe ð8Þ given adsorption reaction, ‘K’ is determined using Eq. (10):
n
aa ms qe
where, Kf is Freundlich constant and n denotes affinity of K¼ ¼ ð10Þ
adsorption. The value of Kf and n is dependent on tempera- as me Ce
ture, adsorbate, and properties of adsorbent. The non-linear where, aa and as are the activity of PCP in adsorbed and solu-
fitting of this equation is presented in Fig. SI-4. Results show tion phase; qe is the surface concentration of PCP on the adsor-
that both the parameters decrease with temperature similar to bent; Ce is the PCP concentration in solution at equilibrium; ma
Langmuir isotherm model, here again the R2, values for fitting and ms are the activity coefficient of PCP in adsorbed phase and
varies from 0.91 to 0.98. solution phase respectively. The equilibrium constant K can be
Both of the above models, give similar degree of fitting, it is obtained by plotting ln(qe/Ce) versus qe, where the intercept at
therefore believed that adsorption of PCP on these materials the vertical axis yields the values of K (Table SI-2) (Zhou and
involves homogenous as well as heterogeneous surfaces. In Zhou, 2014). The DG°, DH° and DS° were calculated using
order to confirm this phenomenon, Redlich-Peterson model Eqs. (11)–(13).
(Redlich and Peterson, 1959) was applied to above adsorption
data. This model is a hybrid of both the Langmuir and Fre- DG ¼ RT ln K ð11Þ
undlich isotherms. The equation (Eq. (9)) for this model is:
DS DH
ACe ln K ¼  ð12Þ
qe ¼ ð9Þ R RT
1 þ BCm
e
DG ¼ DH  TDS ð13Þ
where A, B and m are the R–P constants. When the value of m
is equal to 1, the above equation is reduced to the Langmuir where T is the solution temperature in Kelvin, and R is the uni-
isotherm and if in case the value of m is much bigger than 1, versal gas constant (8.314 J mol1 K1). The values of Gibbs
the above equation is reduced to a Freundlich isotherm. Exam- free energy change DG° were calculated from Eq. (10) and
ination of fitting parameters in Table 2 shows that Redlich- compiled in Table SI-2. Except CHT, at 303 and 313 K, other
Peterson isotherm describes more accurately the adsorption materials (CHTA and CHTAC) show negative values of DG°
of PCP on CHT, CHTA, and CHTAC over the concentration with all the three temperatures. It indicates the feasibility
range studied. Since the method used to derive the isotherm and spontaneous nature of adsorption process at these temper-
parameters maximizes the linear coefficient of determination, atures. These results show that the functionalization of chi-
it is unsurprising that in all cases, the Redlich–Peterson iso- tosan surface increase the adsorption feasibility at higher
therms exhibit extremely high R2 values (ranging from 0.96 temperature. Similarly, the DH° values were determined from
to 0.99) indicating considerably better fit as compared to the the slope of the Van’t Hoff plot, between ln K and 1/T, on
preceding two-parameter isotherms. the basis of Eq. (11). (Fig. 5, Table SI-2). The DH° values were
From the Table 2, it is clear that the values of m are close to found to be 36.41 kJ mol1, 37.68 kJ mol1, and 26.22
unity, which shows that the isotherms are approaching Lang- kJ mol1 for the adsorption on CHT, CHTA, and CHTAC,
muir form. At 293 K, the Langmuir and Redlich–Peterson respectively. All these values confirm the exothermic nature
models gave the highest R2 value with each material, indicating of the adsorption and the possibility of physical adsorption.
that the adsorption isotherms of PCP on CHT, CHTA, and The change in entropy DS°, during adsorption was calculated
CHTAC can be best explained by these two isotherms. Fur- with Eq. (12). The negative values of DS° for adsorption on
CHT (122.84 J mol1 K1), CHTA (118.83 J mol1 K1),
1828 A. Shankar et al.

Table 2 Constants of Eqs. (7)–(9), derived from the fits of corresponding models to the experimental data for each chitosan sample.
Sample Temp Langmuir Freundlich Redlich peterson
2 2
(K) qmax b R Kf 1/n R A B m R2
(mg/g) (L/g)
CHT 293 21.29 0.04 0.98 2.56 0.42 0.95 2.53 0.66 0.64 0.99
303 18.58 0.03 0.97 1.64 0.47 0.98 2.09 1.01 0.56 0.96
313 13.13 0.03 0.91 1.21 0.46 0.98 1.28 0.62 0.64 0.99
CHTA 293 39.11 0.05 0.97 5.65 0.40 0.91 7.68 0.99 0.66 0.99
303 31.91 0.04 0.94 3.71 0.43 0.94 1.46 0.07 0.91 0.98
313 25.46 0.03 0.92 2.68 0.45 0.98 1.08 0.08 0.86 0.99
CHTAC 293 36.85 0.06 0.97 5.24 0.42 0.90 5.67 0.63 0.70 0.99
303 32.19 0.04 0.95 3.41 0.46 0.94 3.50 0.58 0.65 0.99
313 22.35 0.05 0.96 2.96 0.42 0.95 2.01 0.29 0.75 0.99

1.5 On the basis of above results, NaOH and H3PO4 are iden-
CHT tified as suitable desorbing agents for respective chitosan mate-
y = 3154x - 9.5977
CHTA rials and used in reusability tests. In these tests, three
R² = 0.9133
1 CHTAC consecutive cycles of adsorption-desorption were performed
on all the three materials using batch mode of operation.
ln K

The results of these tests are presented in Fig. 6, where regain-

0.5 y = 4532.6x - 14.293
ing of initial adsorption capacity after each cycle is compared.
R² = 0.9885 It clearly shows that for CHT and CHTAC, the loss of adsorp-
tion capacity is fast as compared to CHTA. In third cycles, the
0 CHT and CHTAC samples can maintain only 41% and 35%
of their original adsorption capacity, whereas CHTA can still
retain about 80% of its original adsorption capacity. These
-0.5
y = 4379.1x - 14.775 results highlight the reusability of CHTA for PCP removal
R² = 0.9999 applications, in comparison to other two materials.
Inorder to further support the reusability and stability of
the adsorbent material, EDAX analysis was performed for
-1
0.00315 0.0032 0.00325 0.0033 0.00335 0.0034 0.00345
all the three materials after adsorption (Fig. SI-6a–c) and des-
orption (Figure Fig. SI-7a–c). The atomic% of carbon
1/T increased from 42.6% to 49.5% for CHT, 58.5% to 61.7%
Fig. 5 Van’t Hoff plot for the estimation of thermodynamic
for CHTA, 50.4% to 58.9% for CHTAC and a new peak
for chlorine was observed in CHT and CHTA after the PCP
parameters.
adsorption experiments which accounts for the adsorption of
PCP. After the desorption experiments, for example using
NaOH, it was seen that the peak for chlorine vanished in
and CHTAC (79.80 J mol1 K1) suggest that there was a CHT and CHTA. The atomic weight% of carbon reduced
decrease in randomness at the solid/solution interface, and suf- and was nearly equal to the carbon wt% of the unused adsro-
ficient affinity of materials for PCP. bent materials which substantiates the retainment of adsorbent
material in its original form without occurrence of any chem-
3.6. Desorption and reusability ical reaction between PCP and adsorbent material. ATIR spec-
tra was also recorded for the materials after adsorption
The reusability of the developed adsorbents is a critical aspect (Fig. SI-8) and desorption (Fig. SI-9) experiments. All the
of an adsorbent, to ensure its sustainable use in adsorption three adsorbent materials showed characteristic stretching
based techniques. The low-values of heat of adsorption indi- vibrations of the functional groups as that observed in the
cate that the physical adsorption of PCP on chitosan based unused materials. A broad band was observed in the range
materials should be desorbed with a suitable desorbing agent. of 3281–3322 cm1 in CHT, CHTA and CHTAC after adsorp-
The effect of different desorbing agents was analyzed and com- tion of PCP. This can be accounted to the phenolic OAH
pared on all the three spent adsorbent materials. Results group in PCP adsorbed on the surface of the materials. After
showed that (Fig. SI-5), different desorbing agents show differ- desorption experiments, the broad band observed for OAH
ent% of desorption. The highest desorption with CHT (64%) group from PCP disappeared and in addition, all the charac-
and CHTA (90.3%) was achieved with NaOH, whereas with teristic vibrations of the materials were within the expected
CHTAC (60.1%) it was achieved with H3PO4. range. The retainment of all the group-specific stertching
vibrations in the materials after adsorption and desorption
Removal of pentachlorophenol pesticide from aqueous solutions using modified chitosan 1829

120 Appendix A. Supplementary material

CHT CHTA CHTAC
% of Original Capacity

100

80 Supplementary data associated with this article can be found,

60
in the online version, at https://doi.org/10.1016/j.arabjc.2018.
01.016.
40

20
References
0
Ads Des Ads Des Ads Des Ali, I., Gupta, V.K., 2007. Advances in water treatment by adsorption
Cycle 1 Cycle 2 Cycle 3 technology. Nat. Protoc. 1, 2661–2667. https://doi.org/10.1038/
Cycles of adsorption & desorption nprot.2006.370.
Ali, U., Syed, J.H., Malik, R.N., Katsoyiannis, A., Li, J., Zhang, G.,
Fig. 6 Effects of successive adsorption-desorption cycles on the Jones, K.C., 2014. Organochlorine pesticides (OCPs) in South
reusability of prepared chitosan materials. Asian region: a review. Sci. Total Environ. 476, 705–717. https://
doi.org/10.1016/j.scitotenv.2013.12.107.
Amreen, N., Shiva, A., Shahid, S. N., Mohammad, S. A., Anu, S.,
experiments and the appearance and disappearance of broad Prabha, B., Dutta, P. K., 2017. Cu(II)-carboxymethyl chitosan-
OAH peak before desorption and after desorption, respec- silane schiff base complex grafted on nano silica: Structural
tively explains the concept of physical adsorption and that evolution, antibacterial performance and dye degradation ability,
no chemical reaction occurred between the adsorbate PCP Int. J. Bio. Macromolecules. in press. https://doi.org/10.1016/j.
ijbiomac.2017.11.112
and the adsorbent materials.
Babić, B.M., Milonjić, S.K., Polovina, M.J., Kaludierović, B.V., 1999.
Point of zero charge and intrinsic equilibrium constants of
4. Conclusion activated carbon cloth. Carbon 37, 477–481. https://doi.org/
10.1016/S0008-6223(98)00216-4.
The surface modification of chitosan using 2-hydroxy-1- Badawi, M.A., Negm, N.A., Abou Kana, M.T.H., Hefni, H.H., Abdel
napthaldehyde and copper chloride leads to promising materi- Moneem, M.M., 2017. Adsorption of aluminum and lead from
wastewater by chitosan-tannic acid modified biopolymers: iso-
als CHTA and CHTAC respectively which were used as bioad-
therms, kinetics, thermodynamics and process mechanism. Int. J.
sorbents for PCP removal from aqueous solutions. Biol. Macromol. 99, 465–476. https://doi.org/10.1016/j.
Crosslinking of chemically modified chitosan derivatives ijbiomac.2017.03.003.
improved their interaction with PCP and thereby enhanced Beppu, M.M., Arruda, E.J., Vieira, R.S., Santos, N.N., 2004.
the ability to uptake PCP. At neutral pH, the highest adsorp- Adsorption of Cu(II) on porous chitosan membranes functional-
tion capacity was exhibited by CHTA (39.1 mg/g) followed by ized with histidine. J. Membr. Sci. 240, 227–235. https://doi.org/
CHTAC (35.4 mg/g) and CHT (24.4 mg/g). The rate of 10.1016/j.memsci.2004.04.025.
adsorption on all the three materials was found to follow a Donia, A.M., Atia, A.A., Elwakeel, K.Z., 2008. Selective separation of
pseudo-second-order model. The adsorption capacity of mate- mercury(II) using magnetic chitosan resin modified with Schiff’s
rials decreased with increase in pH, owing to increase of PCP base derived from thiourea and glutaraldehyde. J. Hazard. Mater.
151, 372–379. https://doi.org/10.1016/j.jhazmat.2007.05.083.
solubility. The amount of adsorption on chitosan and modified
El-Sayed, E.M., Tamer, T.M., Omer, A.M., Mohy Eldin, M.S., 2016.
materials decreases with increase in temperature from 293 K to Development of novel chitosan Schiff base derivatives for cationic
313 K. The thermodynamic study revealed that the adsorption dye removal: methyl orange model. Desalin. Water Treat. 57,
was favorable and exothermic in nature. Reusability of CHTA 22632–22645. https://doi.org/10.1080/19443994.2015.1136694.
was comparatively better than CHT and CHTAC and the Elwakeel, K.Z., Atia, A.A., 2014. Uptake of U(VI) from aqueous
materials did not show any chemical modification upon media by magnetic Schiff’s base chitosan composite. J. Clean. Prod.
adsorption. These results draw attention to the development 70, 292–302. https://doi.org/10.1016/j.jclepro.2014.02.017.
of a method for the improved removal of a water contaminant Freundlich, H., 1906. Over the adsorption in solution. J. Phys. Chem.
like PCP by the surface functionalization of naturally available 57, 385–470.
material like chitosan. Gavalyan, V.B., 2016. Synthesis and characterization of new chitosan-
based Schiff base compounds. Carbohydr. Polym. 145, 37–47.
https://doi.org/10.1016/j.carbpol.2016.02.076.
Acknowledgement Gupta, V.K., Carrott, P.J.M., Ribeiro Carrott, M.M.L., Suhas, 2009.
Low-cost adsorbents: Growing approach to wastewater treat-
The Authors acknowledge the financial support and research ment—a review. Crit. Rev. Environ. Sci. Technol. 39, 783–842.
infrastructure, provided by the School of Environment and https://doi.org/10.1080/10643380801977610.
Natural Resources, Doon University, Dehradun, Centre for Ho, Y.S., McKay, G., 1999. Pseudo-second order model for sorption
processes. Process Biochem. 34, 451–465. https://doi.org/10.1016/
Nano and Material Sciences, Jain University, Bangalore,
S0032-9592(98)00112-5.
DST India (SB/FT/CS-100/2013) (ECR/2017/001266), and Ho, Y.S., Ng, J.C.Y., McKay, G., 2000. KINETICS of pollutant
UGC India (MRP-MAJOR-ENVI-2013-35206). sorption by biosorbents: review. Sep. Purif. Methods 29, 189–232.
https://doi.org/10.1081/SPM-100100009.
Conflict of interest Jiao, T., Zhou, J., Gao, L., Xing, Y., Li, X., 2011. Synthesis and
characterization of chitosan-based Schiff base compounds with
aromatic substituent groups. Iran. Polym. J. 20, 123–136.
None.
1830 A. Shankar et al.

Kosmulski, M., 2009. pH-dependent surface charging and points of Song, K.S., Kim, D., Kyriaki, P., Coskun, Ali, 2016. Synthesis of
zero charge. IV. Update and new approach. J. Colloid Interface highly porous coordination polymers with open metal sites for
Sci. 337, 439–448. https://doi.org/10.1016/j.jcis.2009.04.072. enhanced gas uptake and separation. Appl. Mater. Interfaces 8,
Kyzas, G., Bikiaris, D., 2015. Recent modifications of chitosan for 26860–26867. https://doi.org/10.1021/acsami.6b09156.
adsorption applications: a critical and systematic review. Mar. Vakili, M., Rafatullah, M., Ibrahim, M.H., Abdullah, A.Z., Salama-
Drugs 13, 312. https://doi.org/10.3390/md13010312. tinia, B., Gholami, Z., 2016. Chitosan hydrogel beads impregnated
Lagergren, S., 1898. Zur theorie der sogenannten adsorption gelöster with hexadecylamine for improved reactive blue 4 adsorption.
stoffe, kungliga svenska vetenskapsakademiens. Handlingar 24, 1– Carbohydr. Polym. 137, 139–146. https://doi.org/10.1016/
39. j.carbpol.2015.09.017.
Langmuir, I., 1916. The constitution and fundamental properties of Vakili, M., Rafatullah, M., Salamatinia, B., Ibrahim, M.H., Abdullah,
solids and liquids. Part I. Solids. J. Am. Chem. Soc. 38, 2221–2295. A.Z., 2015. Elimination of reactive blue 4 from aqueous solutions
https://doi.org/10.1021/ja02268a002. using 3-aminopropyl triethoxysilane modified chitosan beads.
Li, J.-M., Meng, X.-G., Hu, C.-W., Du, J., 2009. Adsorption of Carbohydr. Polym. 132, 89–96. https://doi.org/10.1016/
phenol, p-chlorophenol and p-nitrophenol onto functional chi- j.carbpol.2015.05.080.
tosan. Bioresour. Technol. 100, 1168–1173. https://doi.org/10.1016/ Wan Ngah, W.S., Teong, L.C., Hanafiah, M.A.K.M., 2011. Adsorp-
j.biortech.2008.09.015. tion of dyes and heavy metal ions by chitosan composites: a review.
Li, Y., Du, Q., Liu, T., Sun, J., Jiao, Y., Xia, Y., Xia, L., Wang, Z., Carbohydr. Polym. 83, 1446–1456. https://doi.org/10.1016/
Zhang, W., Wang, K., Zhu, H., Wu, D., 2012. Equilibrium, kinetic j.carbpol.2010.11.004.
and thermodynamic studies on the adsorption of phenol onto Weber, W.J., Morris, J.C., 1962. Advances in water pollution research:
graphene. Mater. Res. Bull. 47, 1898–1904. https://doi.org/10.1016/ Removal of biologically resistant pollutant from waste water by
j.materresbull.2012.04.021. adsorption. Proceedings of the International Conference on Water
Mathialagan, T., Viraraghavan, T., 2009. Biosorption of pen- Pollution Symposium, Pergamon Press, Oxford, UK, 231-266.
tachlorophenol from aqueous solutions by a fungal biomass. Wu, F.-C., Tseng, R.-L., Juang, R.-S., 2009. Initial behavior of
Bioresour. Technol. 100, 549–558. https://doi.org/10.1016/j. intraparticle diffusion model used in the description of adsorption
biortech.2008.06.054. kinetics. Chem. Eng. J. 153, 1–8. https://doi.org/10.1016/j.
Monier, M., Abdel-Latif, D.A., Abou El-Reash, Y.G., 2016. Ion- cej.2009.04.042.
imprinted modified chitosan resin for selective removal of Pd(II) Wu, M.-T., Tsai, Y.-L., Chiu, C.-W., Cheng, C.-C., 2016. Synthesis,
ions. J. Colloid Interface Sci. 469, 344–354. https://doi.org/10.1016/ characterization, and highly acid-resistant properties of crosslink-
j.jcis.2016.01.074. ing b-chitosan with polyamines for heavy metal ion adsorption.
Orton, F., Lutz, I., Kloas, W., Routledge, E.J., 2009. Endocrine RSC Adv. 6, 104754–104762. https://doi.org/10.1039/
disrupting effects of herbicides and pentachlorophenol: In vitro and C6RA21993D.
in vivo evidence. Environ. Sci. Technol. 43, 2144–2150. https://doi. Wysokowski, M., Klapiszewski, Ł., Moszyński, D., Bartczak, P.,
org/10.1021/es8028928. Szatkowski, T., Majchrzak, I., Siwińska-Stefańska, K., Bazhenov,
Pal, P., Pal, A., 2017. Surfactant-modified chitosan beads for cadmium V., Jesionowski, T., 2014. Modification of chitin with kraft lignin
ion adsorption. Int. J. Biol. Macromol. 104, 1548–1555. https://doi. and development of new biosorbents for removal of Cadmium(II)
org/10.1016/j.ijbiomac.2017.02.042. and Nickel(II) ions. Mar. Drugs 12, 2245–2268. https://doi.org/
Ravi Kumar, M.N.V., 2000. A review of chitin and chitosan 10.3390/md12042245.
applications. React. Funct. Polym. 46, 1–27. https://doi.org/ Zhou, L., Pan, S., Chen, X., Zhao, Y., Zou, B., Jin, M., 2014. Kinetics
10.1016/S1381-5148(00)00038-9. and thermodynamics studies of pentachlorophenol adsorption on
Redlich, O., Peterson, D.L., 1959. A useful adsorption isotherm. J. covalently functionalized Fe3O4@SiO2–MWCNTs core–shell mag-
Phys. Chem. 63, 1024. https://doi.org/10.1021/j150576a611. netic microspheres. Chem. Eng. J. 257, 10–19. https://doi.org/
Salvestrini, S., Leone, V., Iovino, P., Canzano, S., Capasso, S., 2014. 10.1016/j.cej.2014.07.060.
Considerations about the correct evaluation of sorption thermo- Zhou, X., Zhou, X., 2014. The unit problem in the thermodynamic
dynamic parameters from equilibrium isotherms. J. Chem. Ther- calculation of adsorption using the langmuir equation. Chem. Eng.
modyn. 68, 310–316. https://doi.org/10.1016/j.jct.2013.09.013. Commun. 201, 1459–1467. https://doi.org/10.1080/
Sobahi, T.R.A., Abdelaal, M.Y., Makki, M.S.I., 2014. Chemical 00986445.2013.818541.
modification of chitosan for metal ion removal. Arab. J. Chem. 7,
741–746. https://doi.org/10.1016/j.arabjc.2010.12.011.