International Journal of Biological Macromolecules 80 (2015) 431–444

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

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

Application of chitosan-citric acid nanoparticles for removal of

chromium (VI)
Mahdiye Bagheri a , Habibollah Younesi b,∗ , Shaaker Hajati c,d , Seyed Mehdi Borghei e
a
Department of Environmental Science, Science and Research Branch, Islamic Azad University, Tehran, Iran
b
Department of Environmental Science, Faculty of Natural Resources, Tarbiat Modares University, Imam Reza Street, Noor P.O. Box 46414-356, Iran
c
Department of Physics, Yasouj University, Yasouj 75918-74831, Iran
d
Physics Department, Sharif University of Technology, Tehran P.O. Box 11155-9161, Iran
e
Sharif University of Technology – BBRC, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In the present study, CS–CA nanoparticle was prepared for forming a new amide linkage, by grafting
Received 8 April 2015 the amino groups of CS in the presence of carboxylic groups of CA that acts as cross-linking agent. The
Received in revised form 9 July 2015 as-prepared CS–CA nanoparticle samples were characterized by use of dynamic light scattering (DLS),
Accepted 12 July 2015
scanning electron microscopy (SEM), Fourier-transformed infrared spectroscopy (FTIR), X-ray diffraction
Available online 16 July 2015
(XRD) and X-ray photoelectron spectroscopy (XPS) techniques, which showed that the cross-linking agent
preserved during the chemical modifications. The adsorption capacity of the CS–CA nanoparticles for the
Keywords:
removal of Cr (VI) in aqueous solution was studied. The adsorption equilibrium data taken at the optimized
Chitosan–CA nanoparticle
Cr (VI)
condition, i.e., 25 ◦ C and pH of 3, were analyzed with the Langmuir, Freundlich and Redlich–Peterson
Isotherm isotherm models. The kinetics of Cr (VI) adsorption on CS–CA nanoparticles obtained at different initial
Kinetics concentrations were also analyzed using the pseudo-second-order model.
Desorption © 2015 Elsevier B.V. All rights reserved.

1. Introduction
Water is the most widely abundant occurring substance on
earth, used for drinking, hygiene, industry and agriculture. Unfor-
tunately, developing a modern civilization and societies shifting
toward industrialization has led to introducing different types of
toxic substances, harmful to the health of living organisms, into
the environment such as heavy metals in drinking water supplies
and wastewater discharge. Nowadays, water pollution by heavy
metals is one of the most serious environmental problems, as they
are nonbiodegradable, accumulate in the environment with a long
biological half-life, subsequently contaminating the food chain,
increasing cancer risk [1]. Chromium is one of the most dangerous
toxic heavy metals that get discharged into the environment as a
result of industrial applications, including metal smelting, mineral
ore, electroplating, paper pulp production, leather tanning, metal-
lurgical plants, nuclear power plants, pigment fabrication, timber
treatment and petroleum refining. Chromium exists in the environ-
ment mainly in two stable states, i.e. trivalent chromium [Cr (III)]
∗ Corresponding author.
E-mail addresses: hunesi@modares.ac.ir, hunesi@yahoo.com (H. Younesi).
and hexavalent chromium [Cr (VI)], Cr (VI) being five times more
toxic than Cr (III).
Beyond a certain concentration, the toxicity of Cr (VI) has serious
implications for human health such as damage to the physiol-
ogy of the body by its accumulation in the food chain, problems
ranging from simple skin irritation to lung cancer, head and neck,
kidney, liver and stomach injuries [2]. This element has been indi-
cated to be mutagenic and carcinogenic and is soaked up through
the skin and ingestion. So if untreated wastewater containing Cr
(VI) is discharged to surface waters, contamination that endangers
ecosystems also jeopardize people’s health seriously. The maxi-
mum allowable Cr (VI) in drinking water and that discharged to
the surface waters recommended by World Health Organization
(WHO) is 0.05 mg/l, while the drinking water standard for total
chromium is 100 ␮g/l according to the United State Environmental
Protection Agency (USEPA) [3]. In surface waters in Iran, levels up
to 84 ␮g/l have been reported.
In recent years, widely used treatment technologies such
as chemical precipitation, flotation, electrochemical deposition,
membrane filtration, ion exchange and adsorption have been
developed for removing heavy metals from wastewater. How-
ever, adsorption with unique features such as high metal-binding
capacity, adsorbents resistance in a wide pH range, easy operating
conditions and maintenance, lack of toxicity, availability and low

http://dx.doi.org/10.1016/j.ijbiomac.2015.07.022
0141-8130/© 2015 Elsevier B.V. All rights reserved.
432 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444
cost, with the capability of sorbent recovery and reuse, is an effec-
tive economic and relatively new technique that has been widely
used as the most versatile method [4]. Chitosan is an anti-bacterial,
renewable biopolymer with a proved, attractive feature in sur-
face adsorption and characteristics such as high biodegradability,
high biocompatibility, non-toxicity, biodhesion, immunogenicity
and the ability to form metal ion chelation with both cationic
and anionic compounds [5]. Chitosan can be produced artificially
using biotechnological techniques in growth medium in massive
amounts as a result of producing chitin from shellfish and crus-
tacean exoskeleton wastes and external walls of some fungi. The
recent efforts have focused on chemical modification of chitosan
using the reactive activities of primary and secondary hydroxyl-
and amine groups to control the reactivity of the polymer and
improve its capacity, selectivity and range of pH for optimal adsorp-
tion. Various physical or chemical modification techniques have
been used to increase the adsorption kinetics [6], by obtaining con-
ditioned polymer forms such as powder, nanoparticles and gels
(membranes, sponge, beads, fibers or hollow fibers). Large surface
area and small particle size favor the adsorption of heavy metal
ions.
The objective of the present study was to modify chitosan with
carboxyl functional groups using citric acid as a crosslinking agent
at different conditions (molar ratio of chitosan to citric acid). We
investigated the adsorptive removal of Cr (VI) from aqueous solu-
tion onto as-prepared carboxylated nanochitosan with different
process parameters such as pH, temperature, contact time, adsor-
bent dose and initial concentration of Cr (VI). The experimental data
were analyzed using the pseudo-second-order kinetic equations
and the Langmuir, Freundlich and Redlish–Peterson isotherms.
Finally, the reusability of carboxylated nanochitosan was evaluated
after three adsorption–desorption cycle.
2. Materials and methods
2.1. Materials
The starting materials for preparing the chitosan–citric acid
(CS–CA) nanoparticle were chitosan polymer (CA) with high
molecular weight (Mr = 600,000), a deacetilation content at 80%
purchased from Sigma-Aldrich Chemical Co. (UK) and potassium
persulfate (K2 S2 O8 , KPS), acetic acid (AA) and citric acid (CA)
(anhydrous 99%) purchased from the Merck company (Darmstadt,
Germany). Hydrochloric acid (HCl) and sodium hydroxide (NaOH)
used for pH adjustment were purchased from the Merck Company
(Darmstadt, Germany). Potassium dichromate salt (K2 Cr2 O7 ) for
adsorption experiments was prepared by diluting 1000 mg/l of a
standard solution of Cr (VI), purchased from the Merck Company
(Darmstadt, Germany), using de-ionized water. The pH of each
heavy metal solution was adjusted by adding diluted NaOH (1 M) or
HCl (1 M) using a pH meter (CyberScan, Singapore). The chemicals
used were of analytical grade and not purified further.
2.2. Preparation of chitosan nanoparticles
To prepare CS–CA nanoparticles was done according to the
methods of Heidari et al. [7] but using anhydrous CA as a crosslink-
ing agent. CS was dissolved in an aqueous solution of 1% AA in
a 250 ml, doubleneck, round-bottom flask and a condenser, then
stirred with a magnetic stirrer at 150 rpm for 3 h under nitrogen gas
atmosphere until a complete dissolution of CS to a clear and trans-
parent solution. The pH value of the above solution was adjusted
to 4, by adding 1 M HCl at ambient temperature, and stirred mag-
netically for 7 h at 70 ◦ C. The CA was also dissolved in de-ionized
water and the pH of the solution adjusted to 4 by adding 1 M NaOH.
In the present study, CS–CA nanoparticles were synthesized in dif-
ferent weight ratios (w/w) of CS–CA (1:1, 1:2, 1:3, 1:4 and 2:1%).
The CA solution was added drop-wise to that of the CS. Then as an
initiator, some 0.2 mmol of KPS was added to this CS–CA in a poly-
merization vessel; after formation of free radicals CA crosslinked
with CS, as the CA could produce esterification with the hydroxyl
groups and transamidation with the amino groups of CS to form the
crosslink. After refluxing at 70 ◦ C for 2 h under N2 protection, the
transparent mixture was held in an ice bath for 1 h. Then the white
product of CS–CA nanoparticles was collected by centrifugation
(236HK, Hermle, Germany) for 40 min at 4000 rpm. The particles
thus obtained were freeze-dried for 36 h using a freeze–dry system
(Opergn, Korea). The CS–CA nanoparticles were stored in a sealed
drying tube in the refrigerator at 4 ◦ C prior to use.
2.3. Characterization
The Fourier transform infrared (FT-IR) spectroscopy (Shimad-
zou, FT-IR1650 spectrophotometer, Japan) was used to identify
various functional groups of the samples by using KBr pellets made
from a mixture of the powder of each sample and assessed within
the range of 400–4000 cm−1 . The average diameter of the CS–CA
nanoparticles and particle size distribution was got by a Malvern
Zetasizer analyzer (Malvern Instruments Ltd) and to analyze the
size of the nanoparticles by using dynamic light scattering (DLS).
A scanning electron microscope (SEM, KYKY-EM3200, China) was
used to analyze the surface morphology of nanochitosan. The sam-
ples were dispersed on a double-faced carbon conductive tape and
then covered with gold film (KYKY-SBC12, China). The X-ray pow-
der diffraction patterns of CS and synthesized CS–CA nanoparticles
were obtained by a X’Pert MPD (Philips, Netherlands) diffractome-
ter. The X-ray source was Cu-K␣ radiation (40 kV, 30 mA) in the
2 range of 5–70◦ . The spectra were recorded at a scanning rate
of 2.4◦ min−1 . The crystallinity index (CI) was computed using the
following equation:
I110 − Iam
CI = × 100 (1)
I110
where I110 and Iam are the maximum intensity of the diffraction at
plane 110 and the intensity of the amorphous diffraction, respec-
tively. Results showed that the crystallinity index increases from
18 to 62% when CA was crosslinked with CS.
X-ray photoelectron spectroscopy (XPS) spectra were obtained
with a 8025-BesTec twin anode XR3E2 X-ray source system
(Germany). XPS data were taken using achromatic Mg-K␣
(1253.6 eV) and Al-K␣ (1486.6 eV) X-ray source, which operated at
15 kV. The XPS spectra taken from CS and CS–CA nanoparticles were
deconvoluted to obtain the contribution of the different chemical
bondings involved in the materials studied. It is worth noting that
the charging effect was compensated by using N1s corresponding
to C N bonding that appeared at the binding energy of 400 eV. The
spectra were acquired at low pass energy to enhance their resolu-
tion. Savitzky–Golay filtering was performed to smooth the spectra
[8,9].
2.4. Adsorption experiments
A stock solution of Cr (VI) was prepared in a 1 L volumetric flask
by dissolving 2.830 g of potassium dichromate in de-ionized water
and diluted up to mark. The sample solutions were transferred into
polyethylene bottles, which were stored in the refrigerator at 4 ◦ C
for future use. The effect of weight ratios, pH, contact time, adsor-
bent dose, Cr (VI) ion concentration, adsorption kinetics, adsorption
isotherm, thermodynamics of adsorption in a batch system and
regeneration studies on CS–CA nanoparticles were investigated in
this study. The experiments were replicated three times in order to
 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444
carry out the statistical analysis. The statistical analysis of the each
stage was carried out on a Microsoft-Excel 2010 spreadsheet.
2.4.1. Effect weight ratio of CS–CA nanoparticles on Cr (VI)
removal
The effect of CS–CA nanoparticles with different weight ratios
(1:1, 1:2, 1:3, 1:4 and 2:1) on the removal of Cr (VI) was studied
in different flasks containing 25 ml Cr (VI) solution (50 mg/l) at pH
5.0.
2.4.2. Effect of contact time on Cr (VI) removal
The effect of different contact times (10, 20, 40, 60, 110 and
120 min) was studied on the removal of Cr (VI) by optimized CS–CA
nanoparticles in different flasks containing 25 ml Cr (VI) solution
(50 mg/l) at a dose of 2 g/l, pH 4 and ambient temperature.
2.4.3. Effect of pH on Cr (VI) removal
The effect of different pH (2, 3, 4, 5 and 6) was studied on the
removal of Cr (VI) by optimized CS–CA nanoparticles in different
flasks containing 25 ml Cr (VI) solution (50 mg/l) at a dose of 2 g/l
and at ambient temperature (25 ◦ C).
2.4.4. Effect of dose of CS–CA nanoparticles on Cr (VI) removal
The effect of different adsorbent doses (0.5, 1, 1.5, 2, 2.5, 3 and
3.5 g/l) was studied on the removal of Cr (VI) by optimized CS–CA
nanoparticles in different flasks containing 25 ml Cr (VI) solution
(50 mg/l) at pH 4 and ambient temperature.
2.5. Equilibrium and kinetic of adsorption
The equilibrium and kinetics adsorption experiments were car-
ried out in 50-ml Erlenmeyer flask containing 25 ml of the metal ion
solution with different concentration of Cr (VI) solution (10, 30, 50,
70, 90 and 110 mg/l) prepared by appropriate dilutions of the stock
solution. After adjustment of pH at 5, a 5 g/l of the adsorbent was
added. The effect of different temperature (25, 35 and 45 ◦ C) was
studied on the removal of Cr (VI) by optimized CS–CA nanoparti-
cles in different flasks containing 25 ml Cr (VI) solution (50 mg/l) at
a dose 2 g/l and pH 4. All flasks were agitated on a shaker at 150 rpm
at room temperature and contact time of 120 min, until equilibrium
was reached. A 1 ml sample from each flask was taken after inter-
vals of 10, 20, 40, 60, 110 and 120 min, centrifuged at 4000 rpm for
40 min at ambient temperature and the residual Cr (VI) measured
spectrophotometrically in the supernatant. The atomic absorption
spectrometry with flame (AAS, Aanalyst 400, Perkin Elmer, USA)
was used to measure the concentration of Cr (VI) with a linear cal-
ibration curve obtained at concentration ranges varying from 1 to
10 mg/l for Cr (VI). The equilibrium adsorption capacity (qe ) onto
adsorbents was computed by the following equation:
(Co − Ce ) × V
qe =
m 2.303
where qe is the amount of metal ion adsorbed at equilibrium per
mass unit of adsorbent at mg/g, Co initial concentration of metal
ions in mg/L solution, Ce the equilibrium concentration of metal
ions in solution in mg/L, V the volume of the solution in ml, and m
the adsorbent weight in g. Furthermore, metal removal efficiency
was calculated by the following equation:
Co − Ct
R= × 100
Co
where R represents the adsorption efficiency percentage of metal
ions, and Ct the concentration of the metal ions at time t in mg/L
[10].
In order to evaluate equilibrium adsorption data for adsorbing
Cr (VI) from aqueous solution, three nonlinear isotherm models,
433
namely Langmuir, Freundlich and Sips were applied. The Langmuir
model assumes that (i) the adsorption is monolayer, (ii) there are a
fixed number of adsorbates places with equal free energy of adsorp-
tion onto the adsorbent surface, (iii) it has a homogeneous surface
structure with equally accessible sites, (iv) the adsorption process is
reversible and (v) no interactions between adsorbed species takes
place. The nonlinear form of Langmuir equation is expressed in the
following equation [11]:
qm bce
qe = (4)
1 + bCe
where qm is the maximum adsorption capacity in mg/g and b the
Langmuir constant in l/mg related to surface adsorption energy
and strength of adsorption joint sites. The Freundlich isotherm
model describes adsorption on heterogeneous systems. This model
is expressed as follows:
1/n
qe = Kf Ce (5)
where Kf is the Freundlich constant related to adsorption capacity
(mg/g), the larger value of Kf the greater adsorption capacity and n
the adsorption intensity, called heterogeneity factor and its value
is in the range of 0–1. The more heterogeneous the surface, the
closer the 1/n value is to zero [12]. The Redlich–Peterson adsorp-
tion isotherm is the combination of Langmuir and Freundlich and
contains three empirical coefficients A, B and g which derive from
the limiting behavior of the equation. It follows the Freundlich
isotherm at low sorbate concentrations and thus does not obey
Henry’s law, while it predicts a monolayer adsorption capacity
characteristic of the Langmuir isotherm at high adsorbate concen-
trations. The Redlich–Peterson equation may be expressed by the
following equation:
ACe
qe = (6)
1 + BCeG
where A (L/g) and B (L/mg)ˇ are the Redlich–Peterson empirical
coefficients and g is the exponent, that lies between 1 and 0 [13].
The controlling mechanism of adsorption process in adsorption
kinetic models, e.g., a mass transfer chemical reaction, provides
a great deal for understanding the adsorption process of Cr (VI)
onto CS–CA nanoparticles in a batch process. The pseudo-first-
order and pseudo-second-order equations were employed for the
uptake of Cr (VI) by CS–CA nanoparticles to test all experimental
data. The advantage of these equations is easy to use and analyze
the experimental data, involves the calculation of the rate constant
and equilibrium adsorption capacity, estimate the initial adsorp-
tion rate; all of which can be used to explain rate mechanism
of adsorption process. The linear form of pseudo-first-order and
pseudo-second-order equations can be expressed as follows:
k1
(2) log (qe1 − qt ) = log qe1 − t (7)
t 1 t
= + (8)
qt k2 q2e2 qe2
where qe and qt are the amounts in mg/g of adsorbed metal ion onto
adsorbent, at equilibrium and time t, respectively. Kinetic studies
were carried out using different initial Cr (VI) concentrations in
110 mg/l (10, 30, 50, 70, 90) but constant amount of 0.15 g CS–CA
nanoparticles (ratio of 3–1 CS–CA) with 50 ml working volume at
(3)
pH 3.
2.6. Thermodynamic of adsorption
The effect of temperature (25, 35 and 45 ◦ C) on the adsorp-
tion process was also evaluated in order to understand the
434 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444
thermodynamic parameters such as the Gibbs free energy (G◦ ),
enthalpy (H◦ ) and entropy (S◦ ), using the following equation:
G◦ = −RT ln Kd (9)
where R is the gas constant (8.314 J mol−1
K), T the absolute tem-
perature in Kelvin and Kd the distribution coefficient at different
temperature levels, which can be obtained from the following equa-
tion:
Co − Ce V
Kd = × (10)
Ce m
The standard Gibbs free energy was computed at different tem-
peratures according to the following equation [14]:
G◦ = H ◦ − TS ◦ (11)
where the values of change in enthalpy (H◦ in J mol−1 ) and change
in entropy (S◦ in J mol−1 K), respectively, were calculated from
linear coefficients obtained by regression when a plot of lnKd versus
1/T should be a straight line using the van’t Hoff equation:
S ◦ H ◦
ln Kd = − (12)
R RT
The activation energy of adsorption was obtained by the follow-
ing Arrhenius equation:
Ea
ln K2 = ln A − (13)
RT
where k2 is the rate constant from pseudo-second-order kinetic
model in g mg−1 min−1 , Ea is the Arrhenius activation energy of
adsorption and A the Arrhenius A factor.
2.7. Desorption experiments
In this study nanochitosan was made for proving it as an effec-
tive and cheap adsorbent, but for use in wastewater treatment, it is
necessary to generate this inexpensive adsorbent through a tech-
nically practical and economically feasible process. The generation
and reuse capacity of the adsorbent was examined in three succes-
sive adsorption/desorption cycles. An adsorption of metal ion was
carried out in a 10 ml of Cr (VI) solution at 100 mg/l. Then, metal
ions in the supernatant, obtained from centrifuging the sample for
10 min at a speed of 4000 rpm, was analyzed with AAS to deter-
mine the amount of metal ion left unadsorbed. Desorption was
performed using eluent of 1 and 2 M sodium chloride (NaCl) with
each fraction volume of 10 ml on a stirrer with a speed of 100 rpm
for 1 h at room temperature. After that, metal ion in each fraction
of elution was analyzed with AAS to calculate the Cr (VI) concen-
tration. The recovery percentage of metal ion was computed with
the following equation [15]:
Amount of metal ions desorbed
Metal recovery = × 100 (14)
Amount of metal ions adsorbed
3. Results and discussion
3.1. Characterization study
In the present study, a milky white color, powder form of CS–CA
nanoparticles was obtained, which was insoluble in water. The
particle size and the average particle size distribution for CS–CA
nanoparticles with different molar ratio of CS–CA (1:1, 1:2, 1:3,
1:4 and 2:1) were examined by zetasizer, shown in Fig. 1. As can be
seen from Fig. 1a, the smallest particle size (403.6 mm) corresponds
to nanochitosan with 1:2 ratio of CS–CA. The largest particle size
of CS–CA nanochitosan of about 1084 mm was observed with 1:3
ratio of CS–CA (Fig. 1e). It was revealed that the size of nanoparticles
increased with an increasing weight ratio of CS–CA.
Particle size and surface morphology of CS–CA nanoparticles
with different weight ratios of CS–CA was compared by SEM
images. The pure CS particle showed a continuous and smooth
surface (figure not shown), indicating a smooth integrity of sur-
face structure. The effect of weight ratio of CS–CA suggested that
the cross-linking reaction between CS and CA leading to increas-
ing stacked lentil-like nanoparticles with higher content of the
nanoparticles. The lentil-like shape on the images also suggested
that the CS–CA nanoparticle scattered in the same shapes and
forms, which allow controlling the size of nanoparticles. The SEM
images (Fig. 2a–e) reveals lentil-like shape of CS–CA nanopar-
ticles, which indicated the formation of more uniform particles
in these cases. The CS–CA nanoparticle with 2: 1 weight ratio
(Fig. 3c) showed lentil-shaped structure, while several fiber-like
shape can be observed in this image, which might be due to
molecular irregularity increasing with an increase of CS content in
CS–CA nanoparticles. This result was inconsistent with Heidari et al.
[7], who reported that a spherical and homogeneous shape was
observed in the chitosan-methacrylic acid (CS–MAA) nanoparticles.
Infrared spectroscopy is introduced as a valuable tool and a
well stabilized experimental technique for the analysis of struc-
ture and conformational changes in biopolymers. The FT-IR spectra
of pure CS and CS–CA nanopartilces are presented in Fig. 3. Com-
paring the results of FT-IR spectra of CS with CS–CA suggested
that the presence of carboxyl ( COO− ), amide I ( NH COO− ) and
amine II ( NH2 ) functional groups in the spectra of all weight
ratios of CS–CA confirms the formation of nanoparticles. It implies
that chitosan was covalently bonded with carboxyl group of cit-
ric acid through cross linkage reaction. Overlap of the symmetrical
peaks at 3400 and 3300 cm−1 are assigned to the stretching of
free amine ( NH2 ) and hydroxyl ( OH) functional groups in the
ring of CS. The peaks at 2920 and 2890 cm−1 are due to C H
stretching in the CS ring. However, the peaks at wave numbers
3470 and 618 cm−1 are related to the OH stretching and bend-
ing vibration in the CS ring, respectively. In addition, a broadening
of the 3000–3500 cm−1 peaks, attributed to OH of molecular
water along with 1640 cm−1 attributed to H O H bending mode
of water molecule, in the nanoparticles structure is in evidence.
The peak at about 1380 cm−1 is attributed to C O stretching of
the primary alcohol group in the CS ring. The last peak at about
1080 cm−1 is attributed to the C O C stretching of the glycosidic
linkage between chitosan monomers. On the contrary, the peak
at about 1580 cm−1 , related to the NH2 bending vibration in the
CS ring, disappeared in the FT-IR spectra of CS–CA nanoparticles.
The peak at 1750 cm−1 is due to the stretching of C O from the
carbonyl group remaining from CA, which was formerly effective
in the adsorption of Cr (VI). However, the main peaks in the ring
1530–1640 cm−1 are attributed to amide I in the CS–CA nanoparti-
cles.
The X-ray powder diffraction patterns of CS and CS–CA nanopar-
ticles are shown in Fig. 4. Three major peaks in in the XRD pattern of
chitosan were observed at 2 = 8.58◦ , 11.61◦ and 19.21◦ , indicating
the low degree of crystallinity of chitosan. CA was crosslinked with
CS that may be the cause of the increase in the degree of crystallinity
of the CA–CS nanoparticles, shown on XRD results (Fig. 4). Further-
more, the XRD pattern of CS particles in the same figure shows that
there is a broad peak low intensity at 2 = 22.62◦ , which indicates an
amorphous nature of the CS particles. However, the XRD pattern of
the CS–CA particles in Fig. 4 shows that, as CA was crosslinked with
CS, peak appear both at 2 — о ◦
— 20·12 and 2 = 29.48 . The absence of
a peak at 2 = 22.62◦ for CS–CA nanoparticles may be due to their
crystallinity structure.
As seen in Fig. 5a, C1s spectra corresponding to N C O, O C O,
C O and C N present also in CS were identified and quantified with
percentages 6.66, 20, 20 and 53.33%, respectively. From the analy-
sis of C1s, taken from CS–CA–NP, the contribution of O C O was
 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444 435

Size distribution(s) Size distribution(s)

% in class

% in class
15 15

10 10

5 5

5 10 50 100 500 1000 5 10 50 100 500 1000

Diameter (nm) Diameter (nm)

(a) (b)
Size distribution(s) Size distribution(s)
% in class

% in class
60

60

40

40

20
20

5 10 50 100 500 1000 5 10 50 100 500 1000

Diameter (nm) Diameter (nm)

(c) (d)
Size distribution(s)

80
% in class

60

40

20

5 10 50 100 500 1000

Diameter (nm)

(e)
Fig. 1. Effect of chitosan (CS) to citric acid (CA) ratio on particle size of CS–CA nanoparticles; (a) 1:1 (dave. = 554.2 nm), (b) 1:2 (dave. = 403.6 nm), (c) 1:3 (dave. = 1084 nm), (d)
1:4 (dave. = 749 nm), and (e) 2:1 (dave. = 1037 nm).
436 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444

Fig. 2. Scanning electronic microscopy (SEM) images of as-prepared CS–CA nanoparticles with (a) 1:1, (b) 1:2, (c) 1:3, (d) 1:4, (e) 2:1 ratios of chitosan (CS) to citric acid (CA).
 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444 437

(a)

(b)

(c)

(d)
Transmittance, %

(e)

(f)

4000 3600 3200 2800 2400 2000 1600 1200 800 400

Wavenumber, cm-1
Fig. 3. FT-IR spectra of (a) chitosan, as-prepared CS–CA nanoparticles with (b) 1:1, (c) 1:2, (d) 1:3, (e) 1:4, (f) 2:1 ratios of chitosan (CS) to citric acid (CA).

verified in addition to all above mentioned components, confirming
the formation of CS–CA–NP, as seen in Fig. 5b. The contribution
percentages of O C O, N C O, O C O, C O and C N were found
to be 8.58, 14.24, 17.15, 42.88 and 17.15%, respectively, which are
consistent to the chemical structure of CS–CA–NP. A similar trend
was applied for the analysis of the peaks in N1, which showed
the presence of O C NH and C NH2 in both materials studied
(Fig. 5); in percentages of 33.33, 66.66 and 83.33, 16.67 for CS, and
CS–CA–NP, respectively. This variation is another quantitative con-
firmation on the formation of CS–CA–NP. Furthermore, as seen in
Fig. 5, the deconvolutions of O1 peaks in the spectra taken from
CS and CS–CA–NP represent the components involved correspond-
ing to C OH (57.14% for CS and 54.54% for CS–CA–NP), C O C
(35.71% for CS and 27.27% for CS–CA–NP) and O C (7.14% for CS
and 18.18% for CS–CA–NP). The increase in the percentage of O C
bonds present in the nanoparticles is in good agreement with what
is expected to be observed.
3.2. Effect of weight ratio CS–CA on adsorption
The effect of the weight ratio was examined at constant tem-
perature of 25 ◦ C and pH 4, with Cr (VI) concentration at 50 mg/l,
438 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444
500
400 (b)
Intensity, a.u.
300
200
(a)
100
0
5 10 15 20 25 30 35 40 45
2Theta, degree
Fig. 4. X-ray diffraction patterns of (a) chitosan and (b) as-prepared CS–CA nanopar-
ticles with 1:1 ratio of chitosan–citric acid.
CS–CA nanoparticle dose of 2 g/l, contact time 60 min including
various weight ratios of CS–CA nanoparticles (1:1, 1:2, 1:3, 1:4
and 2:1) and CS in order to choose the best candidate for as-
prepared nanoparticle on the basis of the maximum Cr (VI) uptake
capacity and removal efficiency (figure not shown). The results
revealed that the removal percentage of Cr (VI) reached was 71.28,
76.35, 83.54, 82.30, 76.35 and 61.75 for weight ratios of 1:1, 1:2,
1:3, 1:4, 2:1 and CS, respectively, after 60 min contact time. The
weight ratio study showed that the best ratio for Cr (VI) adsorp-
tion on CS–CA nanparticle is 1:3. The Cr (VI) appears to adsorb
onto CS even when CA was not crosslinked with CS. However, the
removal efficiency of Cr (VI) by CS–CA nanoparticle was observed
to be about 10–20%. This indicates that the more positively charged
nanoparticles on the surface may interact with Cr (VI) ions by elec-
trostatic force and also providing evidence for the possibility of
forming a Cr (VI)/CS–CA surface complex on the CS–CA nanoparti-
cles.
3.3. Effect of contact time on adsorption
For designing an efficient filtration system that is economically
affordable, determining the required time to reach equilibrium on
chromium adsorption process is critical. Therefore, the effect of
contact time was carried out at constant temperature of 25 ◦ C and
pH 4, with Cr (VI) concentration of 25 mg/l, CS and CS–CA nanopar-
ticle dose of 2 g/l (in 1:3 weight ratio) and at various time intervals
(0, 10, 20, 40, 60, 110 and 120 min), in order to determine the opti-
mal time for the maximum removal efficiency (figure not shown).
The removal efficiency rate was very rapid in the first 10 min of
contact time, but with increasing contact time the removal effi-
ciency of Cr (VI) increased slowly until the equilibrium time for
both the CS and CS–CA nanoparticle was 60 min, while there was
no significant change in adsorption removal efficiency from 60 to
120 min of contact time. At the equilibrium situation, the max-
imum removal efficiency of 83.54 and 61.75% for CS and CS–CA
nanoparticles, respectively, was attained. This finding is in accor-
dance with previous research [16]. In general, the time required to
reach equilibrium was less in this research as compared to previous
studies.
3.4. Effect of pH on adsorption
Fig. 6 shows the effect of initial pH of the solution on the adsorp-
tion of Cr (VI) was studied in the pH range of 2–6. With an increase
in the pH from 2 to 3, the removal percentage increased from 52.89
to 86.83% and then it decreased from 82.24 to 73.95% by an fur-
ther increase in pH from 4 to 6, respectively. The changes in the
adsorption rate were proportional to pH changes, so the pH impact
on adsorption is due to its impact on the speciation and surface
charge of both the adsorbate and the adsorbent. From a thermo-
dynamic standpoint, pH determines the stability of chromium in
aqueous solution and is considered an outstanding and effective
parameter in the adsorption process.
In aqueous solution, Cr (VI) occurs mainly as chromate
(CrO4 2− ), dichromate (Cr2 O7 2− ), hydrogen chromate (HCrO4 − ),
chromic acid (H2 CrO7 ), hydrogen dichromate (HCr2 O7 − ), trichro-
mate (Cr3 O10 2− ) or tetrachromate (Cr4 O13 2 ). However, these
species depend on both the pH and the analytical concentration
of chromium; for example, when the concentration of Cr (VI) in
surface waters is less than 5 ␮g/l, only HCrO4 − and CrO4 2− can be
50 55 60
found, while HCr2 O7 − is predominant at pH < 6, while CrO4 2− ion is
predominant at pH > 7. Both HCrO4 − and H2 CrO7 are the predomi-
nant species in acidic conditions, while the formation of Cr3 O10 2− ,
and Cr4 O13 2− species of chromium can occur in a strongly acidic
solution. Because of the importance of stability and formation
of chromium species in various pH conditions, our investigation
demonstrated that the adsorption of Cr (VI) at lower pH value was
more favorable, being more efficient. As shown in Fig. 6, the maxi-
mum adsorption capacity and removal percentage of Cr (VI) occurs
at pH 3. This could be due to the fact that Cr (VI) in acidic pH is found
in two forms, in HCrO4 −1 and Cr2 O2 −2 ions that are in equilibrium.
Acidic pH also causes a protonation of the NH− and COO functional
groups on the surface of nanochitosan, and as a result make the
adsorbent surface positively charged. Therefore, these two ions can
be adsorbed on oppositely charged adsorbent surfaces and adsor-
bates at low pH. This means that due to the negatively charged
HCrO4 −1 and Cr2 O2 −2 ions and the protonated surface functional
groups of the adsorbent and the electrostatic tension between pos-
itive and negative ions, the maximum adsorption occurred at pH
3; so this observed fact was used for the rest of the study. At pH
lower than 3, nanochitosan dissolution occurs slowly and the bulky
natured predominant species of Cr3 O10 2− , and Cr4 O13 2− thus have
a negative effect on the efficiency of adsorption. At pH higher than
3, because ion HCrO4 −1 turns into ion CrO4 −2 and the adsorbent
surface is deprotonated, adsorption of CrO4 −2 is restricted due to
the presence of negatively charged ions and competitive − OH, the
low positive surface charge density of the adsorbent and the weak-
ening of the electrostatic forces of attraction between the parallelly
charged adsorbate and adsorbent. The results of the study are con-
sistent with results obtained in previous researches [17,18].
3.5. Effects of adsorbent dose on adsorption
The adsorbent dose is an important parameter that strongly
affects the adsorption capacity. Fig. 7 shows the effect of Cr (VI)
adsorption onto CS–CA nanoparticles (with 1:3 weight ratio) per-
formed with various doses of adsorbent (0.5, 1, 1.5, 2, 2.5, 3,
3.5 g/l) while holding other operating parameters constant dur-
ing 60 min contact time, pH 3 and 50 mg/l concentration of Cr
(VI), 25 ◦ C temperature and 150 rpm agitation speed. Experiments
showed that by increasing the adsorbent dose form 0.5 to 3 g/l,
the removal efficiency increased from 38.51 to 83.33%. But by con-
tinuing to increase the adsorbent dose to 3.5 g/l, the percentage
of removal efficiency remains constant and no change is observed
(Fig. 7).
With increasing the dose of adsorbent, the active sites on the
adsorbent surface increases over the number of constant metal
ions, resulting in increasing the metal removal percentage [19]. But
after a 3 g/l dose of adsorbent, the removal percentage decreases
due to the fact that the increase in adsorbent doses enhances
 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444 439

Fig. 5. X-ray photoelectron spectroscopy characterization: C1s of CS (a) and CS–CA nanoparticles (b), N1s of CS (c) and CS–CA nanoparticles (d), and O1s of CS (e) and CS–CA
nanoparticles (f) as-prepared CS–CA nanoparticles with 1:1 ratio of chitosan to citric acid.

the chances of collision between the adsorbent nanoparticles,
leading to an aggregation of the adsorbent nanoparticles, besides
decreasing the surface area of the adsorbent [20]. Unlike the per-
centage of removal, the adsorption capacity decreases from 38.51 to
3.88 mg/g. In this case the amount of Cr (VI) adsorbed per unit mass
of adsorbent decreases as the adsorbent dose increases (Fig. 7). This
means that the Cr (VI) concentration in solution drops to a lower
value at higher adsorbent dose and the adsorption system reaches
an equilibrium state at a lower value of qe , indicating that the active
sites remain unsaturated.
440 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444

40 50
100

Removal efficiency, %
80 40

60
30
Adsorption capacity, mg/g

30

q e, mg/g
40

20 20 Experimental data
Langmuir
20 0 Freundlich
2 3 4 5 6 10 Redlich-Peterson
pH
0
10 0 10 20 30 40 50 60

C e, mg/l

0
2 3
Fig. 6. Effect of pH on adsorption capacity and removal percentage (inside) of Cr (VI)
adsorption onto CS–CA nanoparticles with 1:1 ratio of chitosan to citric acid and at
dose of 0.15 g/50 ml, initial Cr (VI) concentration of 50 mg/l, contact time of 60 min,
agitation speed of 150 rpm, and temperature of 25 ◦ C.
3.6. Effect of initial concentration of Cr (VI) on adsorption rate
Effect of initial concentration of Cr (VI) was investigated with
fixed pH 3, contact time of 60 min, adsorbent dose of 3 g/l and tem-
perature of 25 ◦ C over a concentration range of 100–110 mg/l. The
results indicate that the removal percentage decreases as the initial
concentration of Cr (VI) is decreased (figure not shown). The Cr (VI)
50
100
Removal efficiency, %
Fig. 8. Langmuir, Freundlich and Redlich–Peterson isotherm models for the Cr (VI)
adsorption onto CS–CA nanoparticles and at dose 0.15 g/50 ml, pH 4, contact time of
contact time of 60 min, agitation speed of 150 rpm and temperature of 25 ◦ C.
4 5 6
removal increases dramatically in the range from 53.42 to 94.46%
pH
at the initial Cr (VI) concentration of 10–70 mg/l. However, the Cr
(VI) removal percentage reaches 90.13 and 88.93 with the initial Cr
(VI) concentration of 90 and 110 mg/l, respectively, going through
a slight decrease compared with the 70 mg/l. The explanation lies
in the response of the removal percentage, which increased with
an increase in the Cr (VI) concentration and decreased after satura-
tion above a certain concentration. This means that by increasing
the amount of available Cr (VI) in the solution, the collision rate of
metal ions with available functional groups on the adsorbent sur-
face, responsible for adsorption, increase which causes an increase
of effective diffusion and in the number of bonds in order to form
the complex with metal ions. At higher Cr (VI) concentrations,
adsorption sites on the adsorbent surface are occupied by Cr (VI)
and also the adsorbent has a limited number of active sites, thereby,
consequently leading to a decrease in the removal percentage [21].
3.7. Adsorption isotherms

80 In order to investigate different isotherms and their capability to

40 compare with equilibrium data, a theoretical graph is plotted in the
60 form of the amount of Cr (VI) adsorbed onto CS–CA per unit mass of
CS–CA (qe ) against the equilibrium concentration of Cr (VI) in the
40
solution (Ce ). Fig. 8 shows the experimental equilibrium data using
30 Langmuir, Freundlich and Redlich–Peterson and also the calculated
20
qe, mg/g

isotherm parameters by nonlinear models are shown in Table 1,

0
according to which the correlation coefficients for Langmuir and
Redlich–Peterson isotherm are higher (R2 > 0.99) than those of the
0.025
0.05
0.075
0.1

0.15
0.125

0.175

20 Freundlich, indicating them to be suitable isotherms for the data.

The maximum adsorption capacity was obtained with 106.15 mg/g
CS-CA nanop article, g/50 ml using the Langmuir model. Based on the data in Table 1, KF
and n values are 16.29 (mg/g)(L/mg)1/n and 2.30, respectively. KF
10
Table 1
Langmuir and Frendlich and Redlich–Peterson parameters of Cr (VI) adsorption onto
CS–CA nanoparticles.

0 Models Parameters
0.025 0.05 0.075 0.1 0.125 0.15 0.175 Langmuir qm (mg/g) b (L/mg) R2
106.15 0.081 0.9932
CS-CA nanoparticle dose, g/50 ml
Freundlich KF (mg/g)(L/mg)1/n n R2
Fig. 7. Effect of adsorbent dose on uptake capacity and removal efficiency onto 16.29 2.30 0.9740
CS–CA nanoparticles with 1:1 ratio of chitosan to citric acid at initial pH of 4, initial
Redlich–Peterson A (L/g) B (L/mg)ˇ g R2
Cr (VI) concentration of 50 mg/l, contact time of 60 min, agitation speed of 150 rpm,
8.65 0.084 0.992 0.9933
and temperature of 25 ◦ C.
 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444
represents the adsorption capacity of adsorbed Cr (VI) and 1/n
shows the effect of concentration on the adsorption capacity
representing adsorption intensity. In order for adsorption to be rec-
ognized as the best, the values of n in range 2–10 indicate good,
1–2 moderately difficult, and <1 poor separation. Table 1 shows
that the n value is found between 2 and 10, showing good sep-
aration of Cr (VI) from the CS–CA nanoparticles [22]. In addition,
Table 1 shows that the value of ˇ is close to unity, indicating homo-
geneity of the adsorbent surface and that the Redlich–Peterson
isotherm approaches the Langmuir adsorption and not the Freund-
lich isotherm [23].
3.8. Adsorption kinetics
The kinetics of adsorption is the most important factor for
any adsorption system design in predicting the adsorption rates
at which adsorption takes place in a given system. The adsorp-
tion kinetics depends on type and surface concentration of the
active sites and the surface area of an absorbent that controls the
adsorption mechanism [24]. In order to investigate the controlling
mechanism and adsorption consistency data, experimental data
were applied with pseudo-first-order and pseudo-second-order
adsorption kinetic models [25]. It was found that the regression
coefficient of the pseudo-first-order equation was small (figure
not shown), so the kinetics of Cr (VI) adsorption onto CS–CA did
not fit the pseudo-first-order model and hence was not charac-
terized by the diffusion-controlled phenomenon. In this case, the
pseudo-second-order model was used for analyzing the experi-
mental data in this study, wherein it is assumed that chemical
adsorption may be the rate-controlling step in the adsorption pro-
cess (with no involvement of mass transfer in solution) and the
adsorption site occupancy rate is proportional to the square of the
number of unoccupied sites and the analyte can be bound to differ-
ent binding sites. The kinetic studies indicated that the adsorption
process was rapid during the initial 30 min, reaching equilibrium
within 60 min, following the pseudo-second-order rate model. The
values of qe and k2 were calculated, when the curve of t/qt as func-
tion of t gave a straight line. A good relationship between t/qt and
t for the pseudo-second-order equation makes possible to confirm
that the adsorption process is of chemical nature. The plots of t/qt
against time for adsorption of Cr (VI) onto CS–CA for the pseudo-
second-order equation is shown in Fig. 9 and the kinetic parameters
8 The negative S◦ value of 365.33 J mol−1 K−1 suggests a decrease
30 mg/l
50 mg/l
70 mg/l
6 90 mg/l
110 mg/l
Pseudo-secon-order kinetic
t/qt
4 ness of the boundary layer decreases with increasing temperature,
2
0
0 20 40
Time, min
Fig. 9. Pseudo-second-order model plot of Cr (VI) adsorption onto CS–CA nanopar-
ticle at pH 3.0, contact time 60 min, dosage of 1.5 g/L, temperature of 25 ◦ C and
agitation speed of 150 rpm.
441
Table 2
Pseudo-second-order parameters of Cr (VI) adsorption onto CS–CA nanoparticles.
exp.
Concentration, qe (mg/g) qe2 (mg/g) k2 (g mg−1 min−1 ) R2
mg/L
30 8.69 8.61 0.076 0.9908
50 13.60 13.26 0.057 0.9919
70 22.04 21.80 0.046 0.9938
90 27.40 27.15 0.068 0.9973
110 28.68 28.94 0.072 0.9998
obtained from the plot of the pseudo-first-order-equation, Eq. (7),
are presented in Table 2. The pseudo-second-order equation, Eq.
(8), shows good agreement between the calculated and experi-
mental equilibrium adsorption capacities, revealed by the very high
correlation coefficients obtained (R2 > 0.99), as the values show in
Table 2. The increase in the value of qe is linearly proportional to the
increase in the initial concentration. The equilibrium rate constant
of the pseudo-second-order model, k2 , decreases with an increase
in the initial Cr (VI) concentrations of 30, 50, and 70 mg/L, but then
the k2 increases at higher initial concentrations of 90 and 110 mg/L,
indicating a tendency for the Cr (VI) ion from bulk liquid to the
adsorbent surface with an increase in the initial concentration.
3.9. Adsorption thermodynamics
In order to describe the thermodynamic behavior of the adsorp-
tion of Cr (VI) onto CS–CA nanoparticles, the thermodynamic
parameters, including the changes in G◦ , H◦ and S◦ were cal-
culated at different temperatures (from 298 to 318 K) The results
showed that the adsorption capacity decreased with increasing of
temperature, indicating that a lower temperature promoted the Cr
(VI) adsorption onto CS–CA nanoparticles. Fig. 10a shows the van’t
Hoff plot, considering a satisfactory correlation coefficient value
of 0.9830. The values of the thermodynamic parameters for the
adsorption of Cr (VI) onto CS–CA nanoparticles were calculated
from the Eqs. (10) and (11), listed in Table 3. The chemisorption
usually has the heat value in the range of −80 to −800 kJ/mol, while
heat values between −5 and −40 kJ/mol refer to a physisorption of
adsorption process [26]. The negative H◦ value of −110.29 kJ/mol
indicates that Cr (VI) adsorption onto CS–CA nanoparticles is
exothermic in nature. Hence, it seems that there is chemisorption
involved. Furthermore, an exothermic nature of adsorption is prob-
ably related to the large number of the active sites on the surface of
CS–CA nanoparticles, which may improve the adsorption capacity.
in the disorder at the solid/solution interface during the adsorption
of Cr (VI) onto CS–CA nanoparticles. The observed negative G◦
value of −1.42 kJ/mol at lower temperature confirms the feasibility
of the process and the spontaneous nature of adsorption processes.
Likewise, the increasing G◦ values with increasing temperature
explains a decrease in feasibility of nonspontaneous adsorption at
higher temperature. The results validate the theory that the thick-
due to the increased tendency of the Cr (VI) ions to escape from
the adsorbent surface to the solution phase, which results in a
decrease in the adsorption capacity as the temperature increases
[27]. Similar results were previously reported by Shahbazi et al.
[15]. Fig. 10b shows the Arrhenius equation, considering a satisfac-
tory correlation coefficient value of 0.9880. Table 3 shows that the
adsorption processes have an adsorption activation energy value
60
of 66.51 kJ/mol for Cr (VI) onto CS–CA nanoparticles. If the value of
activation energy of adsorption is between 20 and 80 kJ/mol, it sug-
gests chemical adsorption, when the adsorption energy is between
8 and 16 kJ/mol, the adsorption type can be explained by ion-
exchange; and when the adsorption energy is lower than 8 kJ/mol,
the type of adsorption can be considered as diffusion-controlled
442 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444

4 to 69.4% in the second and to 56.0% in the third one. However,

the adsorption capacity of Cr (VI) removal after three cycles was
2 8.5%, whereas the results of adsorption and desorption of Cr (VI)
Experimental data
Van't Hoff equation
in 2 M NaCl decreased from 94.7% in the first cycle to 83.5% in the
third one, which showed reasonable regeneration capacity for the
0
adsorbent. The desorption mechanisms proposed were (i) electro-
lnKd, L/g

static interactions or van der Waals forces (physical adsorption)

-2 or (ii) covalent bonds (chemical adsorption containing chelating
and ion exchange) [28]. The using of NaCl to desorb Cr (VI) can
-4 be explained by the presence of Cl− ions with high electronegativ-
ity causing a competition to be created between Cl− and HCrO4 −
-6 ions and Cr2 O2 −2 in establishing links with the adsorbent that has
been protonated at pH 3 and is positively charged. This eventu-
ally weakens the Cr (VI) binding and pushes back the metal species
-8
(HCrO4 − and Cr2 O2 −2 ) mentioned above, causing Cl− to be replaced
3.10 3.15 3.20 3.25 3.30 3.35 3.40
in connection with CS–CA nanoparticles.
-1
1000/T, K
(a) 3.11. Comparison of CS–CA nanoparticles with other sorbents

In the present study, the effect of five parameters namely ini-

-1.2
tial solution pH, initial Cr (VI) ion concentration, contact time,
-1.4 adsorbent dose and temperature on adsorption were considered.
Experimental data
-1.6 Arrhenius equation Studies of the removal and recovery of Cr (VI) from aqueous
solution by different adsorbent have recently gained significant
-1

-1.8
lnK2, g.mg .min

attention. Although, difficult is inherent in direct comparisons

-2.0 with other literature data because of the different experimen-
-1

-2.2 tal conditions used in each study, it is important for readers

to consider the applicability of the research results to practice
-2.4
and that the design and methodology are consistent with the
-2.6 study purpose. Table 4 shows a comparison experimental study
-2.8 of maximum removal efficiency and uptake capacity and desorp-
tion efficiency of Cr (VI) ions by various adsorbents with respect
-3.0
to different initial solution pH, initial ion concentration, and
-3.2 absorbent concentration dose reported in the literatures. The
3.10 3.15 3.20 3.25 3.30 3.35 3.40 results exhibit that the maximum removal efficiency and uptake
-1 capacity and desorption efficiency of CS–CA nanoparticles for Cr
1000/T, K
(VI) ions were comparable to other corresponding adsorbents
(b) reported in the literatures. As can be seen from Table 4, varia-
Fig. 10. (a) van’t Hoff and (b) Arrhenius plots of Cr (VI) adsorption onto CS–CA
tions in removal efficiency and uptake capacity and desorption
nanoparticles at adsorbent dose of 1.5 g/L, pH 3.0, initial concentration of 70 mg/L, efficiency on different kinds adsorbents are associated with adsor-
contact time of 60 min and agitation speed of 150 rpm. bent properties, such as physical and chemical structure of the
adsorbents, metal-bonding functional groups, initial pH of the solu-
tion and initial Cr (VI) concentration, Cr (VI) species (i.e., CrO4 2− ,
transport, thus a physical adsorption process. The value of the Cr2 O7 2− , HCrO4 − , H2 CrO7 , HCr2 O7 − , Cr3 O10 2− , Cr4 O13 2− ) and
activation energy was positive and greater than 40 kJ/mol, indicat- adsorbent dose. Several nano-adsorbent such as polyacrylonitrile
ing the feasibility of the adsorption process being predominantly (PAN) nanofibers functionalized with amine groups (PAN-NH2)
chemical in nature. In fact, the values of H◦ , G◦ and Ea indi- [29], manganese oxide nanofibers (MONFs) [30], guar gum–nano
cated that the adsorption of Cr (VI) by CS–CA nanoparticles was a zinc oxide (GG/nZnO) [31], polypyrrole-titanium(IV) phosphate
chemisorption process. (PPy-TiP) nanocomposite [32], polyaniline/zeolite (PANI/zeolite)
nanocomposite [33], nano-hydrotalcite supported on supported
3.10. Desorption on silica (nano-HT/SiO2 ) [34], and maghemite/polydopamine
core/shell nanoparticles (MNP@PDA) [35] have been investigated
The results of desorption in successive adsorption–desorption for their Cr (VI) adsorption capacity. As can be seen from Table 4,
cycles were obtained by repeating three times using the same hydrotalcite [34], magnetotactic bacteria [36] and wheat bran (WB)
adsorbent. The adsorption capacity of Cr (VI) removal after three [37] and polyacrylonitrile nanofibers functionalized with amine
cycles was 22.7 mg/g, whereas the recovery of Cr (VI) in 1 M NaCl groups (PAN-NH2 ) [29] were used for Cr (VI) removal from aque-
solution it was observed as 82.3% in the first cycle, decreasing ous solution and the results showed that the removal efficiency

Table 3
Thermodynamic parameters of Cr (VI) adsorption onto CS–CA nanoparticles.

T (K) kd (L/g) van’t Hoff equation Arrhenius equation

G◦ (kJ/mol) H◦ (kJ/mol) S◦ (J mol−1 K−1 ) R2 Ea (kJ/mol) R2

298 5.68 −3.95 −303.19 −1004 0.9956 66.51 0.9880

308 0.069 6.09
318 0.0026 16.13
 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444 443

Table 4
Comparison of maximum removal efficiencies of Cr (VI) ion by various adsorbent with respect to various initial solution pH, initial Cr (VI) concentration, and adsorbent dose
reported in the literature.

Adsorbent pH Initial Cr (VI) Adsorbent Temperature Uptake Removal Desorption Ref.

concentration dose (g/l) (◦ C) capacity efficiency (%) efficiency (%)
(mg/l) (mg/g)

Polyacrylonitrile nanofibers 2 100 0.02 23 156 (>90) 10 [29]

functionalized with amine
groups
Magnenese oxide nanofibers 2 40 0.02 25 14.6 99.8 n.d. [30]
Wheat bran 2 200 50 23 4.53 51 n.d. [37]
Modified wheat bran 2 200 50 23 5.28 90 n.d. [37]
Guar gum-nano zinc oxide 7 25 1 25 55.56 98.63 n.d. [31]
Polypyrrole-titanium(IV) 2 200 0.2 n.d. 31.64 99 88 [32]
phosphate nanocomposite
Magnetotactic bacteria 6 50 30 (g wet cell l−1 ) 29 70.42 77 n.d. [36]
PANI/zeolite nanocomposite 2 50 0.2 30 24 100 n.d. [33]
Nano-hydrotalcite/SiO2 n.d. 4 1.0 n.d. n.a. 94.6 n.d. [34]
Hydrotalcite n.d. 4 1.0 n.d. n.a. 84.5 n.d. [34]
Shell of Swietenia mahagoni 2 250 0.08 59.87 47.61 99.9 17.44 [40]
Gelatin-impregnated-yeast 1–2 500 0.005 n.d. 500 100 n.d. [39]
Graphene 2 50 0.5 45 666.67 100 n.d. [38]
oxide-␣CD-polypyrrole
Maghemite/polydopamine 3 100 0.1 25 n.a. 97 90 [35]
core/shell nanoparticles
CS–CA nanoparticles 3 70 3 25 22.4 94.46 82.23 This study

n.d.: not determine, n.a.: not available.

were 84.5, 77, 51 and >90%, respectively, that they are in lower
than CS–CA nanoparticles efficiency removal by 94.46%. Mean-
while, other adsorbents showed higher removal efficiency. For
example, Graphene oxide–␣CD-polypyrrole (GO–␣CD NC) [38],
gelatin-impregnated-yeast [39] and PANI/zeolite nanocomposite
[33] was used for the removal of Cr (VI) from aqueous solution,
and the removal efficiency were found to be 100%. Based on data
presented in Table 4, CS–CA nanoparticles can remove Cr (VI) ions
from water also it is obvious that CS–CA nanoparticles showed
a good affinity for binding Cr (VI) ions and desorption. This out-
come showed that CS–CA nanoparticles will be competitively and
efficiently adsorbent for the removal of Cr (VI) ions from aqueous
solutions.
4. Conclusions
The adsorption potential of CS–CA nanoparticles to remove Cr
(VI) from aqueous solution was investigated in a batch system.
CS–CA nanoparticles were prepared by polymerizing citric acid
(CA) in chitosan (CS) solution. The effect of pH, adsorbent dose,
type of CS–CA nanparticles, Cr (VI) concentration, contact time and
temperature was found to play a significant role in controlling the
adsorption process. The results showed that the adsorption process
follows the pseudo-second-order rate reaction. The equilibrium
data was modeled and estimated using three isotherm models,
the Langmuir and Redlich–Peterson isotherm models yielding the
best fit to the experimental data. Thermodynamic parameters
derived from the van’t Hoff and Arrhenius equations showed the
exothermic, spontaneous and chemical nature of Cr (VI) adsorption.
Consequently, the potential is promising for using CS–CA nanopar-
ticles as clean-up material for Cr (VI) contaminated wastewaters.
Acknowledgements
The authors wish to thank the Islamic Azad University, Science
and Research Branch, for their financial support, which funding
and a research grant made this study possible, and Ellen Vuosalo
Tavakoli (University of Mazandaran) for final editing of the English
text.
References
[1] M. Amini, H. Younesi, N. Bahramifar, Statistical modeling and optimization of
the cadmium biosorption process in an aqueous solution using Aspergillus
niger, Colloids Surf. Physicochem. Eng. Aspects 337 (2009) 67–73.
[2] S. Sadeghi, E. Sheikhzadeh, Solid phase extraction using silica gel modified
with murexide for preconcentration of uranium (VI) ions from water samples,
J. Hazard. Mater. 163 (2009) 861–868.
[3] T.A. Kurniawan, M.E.T. Sillanpää, M. Sillanpää, Nanoadsorbents for
remediation of aquatic environment: local and practical solutions for global
water pollution problems, Crit. Rev. Environ. Sci. Technol. 42 (2011)
1233–1295.
[4] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters: a review, J.
Environ. Manag. 92 (2011) 407–418.
[5] D.H.K. Reddy, S.-M. Lee, Application of magnetic chitosan composites for the
removal of toxic metal and dyes from aqueous solutions, Adv. Colloid
Interface Sci. 201–202 (2013) 68–93.
[6] P. Chassary, T. Vincent, E. Guibal, Metal anion sorption on chitosan and
derivative materials: a strategy for polymer modification and optimum use,
React. Funct. Polym. 60 (2004) 137–149.
[7] A. Heidari, H. Younesi, Z. Mehraban, H. Heikkinen, Selective adsorption of
Pb(II), Cd(II), and Ni(II) ions from aqueous solution using chitosan–MAA
nanoparticles, Int. J. Biol. Macromol. 61 (2013) 251–263.
[8] S. Hajati, S. Tougaard, J. Walton, N. Fairley, Noise reduction procedures
applied to XPS imaging of depth distribution of atoms on the nanoscale, Surf.
Sci. 602 (2008) 3064–3070.
[9] A. Savitzky, M.J.E. Golay, Smoothing and differentiation of data by simplified
least squares procedures, Anal. Chem. 36 (1964) 1627–1639.
[10] A. Shahbazi, H. Younesi, A. Badiei, Functionalized nanostructured silica by
tetradentate-amine chelating ligand as efficient heavy metals adsorbent:
applications to industrial effluent treatment, Korean J. Chem. Eng. 31 (2014)
1598–1607.
[11] O. Redlich, D.L. Peterson, A useful adsorption isotherm, J. Phys. Chem. 63
(1959), 1024-1024.
[12] H.M.F. Freundlich, Über die Adsorption in Lösungen, Z. Phys. Chem. (Leipzig)
57 (1906) 385–470.
[13] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and
platinum, J. Am. Chem. Soc. 40 (1918) 1361–1403.
[14] H. Khakpour, H. Younesi, M. Mohammadhosseini, Two-stage biosorption of
selenium from aqueous solution using dried biomass of the baker’s yeast
Saccharomyces cerevisiae, J. Environ. Chem. Eng. 2 (2014) 532–542.
[15] A. Shahbazi, H. Younesi, A. Badiei, Functionalized SBA-15 mesoporous silica
by melamine-based dendrimer amines for adsorptive characteristics of Pb(II),
Cu(II) and Cd(II) heavy metal ions in batch and fixed bed column, Chem. Eng.
J. 168 (2011) 505–518.
[16] S. Hussain, S. Gul, S. Khan, H.-u. Rehman, M. Ishaq, A. khan, F.A. Jan, Z.U. Din,
Removal of Cr (VI) from aqueous solution using brick kiln chimney waste as
adsorbent, Desalin. Water Treat. (2013) 1–9.
[17] D. Chauhan, M. Jaiswal, N. Sankararamakrishnan, Removal of cadmium and
hexavalent chromium from electroplating waste water using thiocarbamoyl
chitosan, Carbohydr. Polym. 88 (2012) 670–675.
444 M. Bagheri et al. / International Journal of Biological Macromolecules 80 (2015) 431–444
[18] L. Panda, B. Das, D.S. Rao, B.K. Mishra, Application of dolochar in the removal
of cadmium and hexavalent chromium ions from aqueous solutions, J.
Hazard. Mater. 192 (2011) 822–831.
[19] K.G. Bhattacharyya, A. Sharma, Adsorption of Pb(II) from aqueous solution by
Azadirachta indica (Neem) leaf powder, J. Hazard. Mater. 113 (2004) 97–109.
[20] M. Özacar, İ.A. Şengil, Adsorption of metal complex dyes from aqueous
solutions by pine sawdust, Bioresour. Technol. 96 (2005) 791–795.
[21] A. Sarı, M. Tuzen, Ö.D. Uluözlü, M. Soylak, Biosorption of Pb(II) and Ni(II) from
aqueous solution by lichen (Cladonia furcata) biomass, Biochem. Eng. J. 37
(2007) 151–158.
[22] J. Febrianto, A.N. Kosasih, J. Sunarso, Y.-H. Ju, N. Indraswati, S. Ismadji,
Equilibrium and kinetic studies in adsorption of heavy metals using
biosorbent: a summary of recent studies, J. Hazard. Mater. 162 (2009)
616–645.
[23] N.K. Amin, Removal of reactive dye from aqueous solutions by adsorption
onto activated carbons prepared from sugarcane bagasse pith, Desalination
223 (2008) 152–161.
[24] M. Arshadi, M.J. Amiri, S. Mousavi, Kinetic, equilibrium and thermodynamic
investigations of Ni(II), Cd(II), Cu(II) and Co(II) adsorption on barley straw ash,
Water Resour. Ind. 6 (2014) 1–17.
[25] A.E. Ofomaja, Intraparticle diffusion process for lead(II) biosorption onto
mansonia wood sawdust, Bioresour. Technol. 101 (2010) 5868–5876.
[26] I.N. Levine, Physical Chemistry, McGraw-Hill, Boston, MA, 2008.
[27] G. Akkaya, F. Güzel, Application of some domestic wastes as new low-cost
biosorbents for removal of methylene blue: kinetic and equilibrium studies,
Chem. Eng. Commun. 201 (2013) 557–578.
[28] H.Y. Aghdas Heidari, Z. Mehraban, H. Heikkinen, Selective adsorption of Pb(II),
Cd(II), and Ni(II) ions from aqueous solution chitosan–MAA nanoparticles, Int.
J. Biol. Macromol. (2013) 251–263.
[29] M. Avila, T. Burks, F. Akhtar, M. Göthelid, P.C. Lansåker, M.S. Toprak, M.
Muhammed, A. Uheida, Surface functionalized nanofibers for the removal of
chromium (VI) from aqueous solutions, Chem. Eng. J. 245 (2014)
201–209.
[30] A.H. Qusti, Removal of chromium (VI) from aqueous solution using
manganese oxide nanofibers, J. Ind. Eng. Chem. 20 (2014) 3394–3399.
[31] T.A. Khan, M. Nazir, I. Ali, A. Kumar, Removal of chromium (VI) from aqueous
solution using guar gum–nano zinc oxide biocomposite adsorbent, Arabian J.
Chem. (2013), http://dx.doi.org/10.1016/j.arabjc.2013.08.019, in press.
[32] U. Baig, R.A.K. Rao, A.A. Khan, M.M. Sanagi, M.A. Gondal, Removal of
carcinogenic hexavalent chromium from aqueous solutions using newly
synthesized and characterized polypyrrole-titanium(IV)phosphate
nanocomposite, Chem. Eng. J. 280 (2015) 494–504.
[33] A.A. Shyaa, O.A. Hasan, A.M. Abbas, Synthesis and characterization of
polyaniline/zeolite nanocomposite for the removal of chromium (VI) from
aqueous solution, J. Saudi Chem. Soc. 19 (2015) 101–107.
[34] E. Pérez, L. Ayele, G. Getachew, G. Fetter, P. Bosch, A. Mayoral, I. Díaz, Removal
of chromium (VI) using nano-hydrotalcite/SiO2 composite, J. Environ. Chem.
Eng. 3 (2015) 1555–1561.
[35] A. Nematollahzadeh, S. Seraj, B. Mirzayi, Catecholamine coated maghemite
nanoparticles for the environmental remediation: hexavalent chromium ions
removal, Chem. Eng. J. 277 (2015) 21–29.
[36] Y. Qu, X. Zhang, J. Xu, W. Zhang, Y. Guo, Removal of hexavalent chromium
from wastewater using magnetotactic bacteria, Sep. Purif. Technol. 136
(2014) 10–17.
[37] K. Kaya, E. Pehlivan, C. Schmidt, M. Bahadir, Use of modified wheat bran for
the removal of chromium (VI) from aqueous solutions, Food Chem. 158
(2014) 112–117.
[38] V.P. Chauke, A. Maity, A. Chetty, High-performance towards removal of toxic
hexavalent chromium from aqueous solution using graphene oxide-alpha
cyclodextrin-polypyrrole nanocomposites, J. Mol. Liq. 211 (2015) 71–77.
[39] M.E. Mahmoud, Water treatment of hexavalent chromium by
gelatin–impregnated-yeast (Gel–Yst) biosorbent, J. Environ. Manag. 147
(2015) 264–270.
[40] S. Rangabhashiyam, N. Selvaraju, Efficacy of unmodified and chemically
modified Swietenia mahagoni shells for the removal of hexavalent chromium
from simulated wastewater, J. Mol. Liq. 209 (2015) 487–497.