Separation Science and Technology

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Chitosan nanoparticles extracted from shrimp

shells, application for removal of Fe(II) and Mn(II)
from aqueous phases

Mohamed Elsayed Abdelfattah Ali, Moustafa Mohamed Saeid Aboelfadl, Atef

Mahmoud Selim, Hazem Fathy Khalil & Gamal Mohamed Elkady

To cite this article: Mohamed Elsayed Abdelfattah Ali, Moustafa Mohamed Saeid Aboelfadl, Atef
Mahmoud Selim, Hazem Fathy Khalil & Gamal Mohamed Elkady (2018): Chitosan nanoparticles
extracted from shrimp shells, application for removal of Fe(II) and Mn(II) from aqueous phases,
Separation Science and Technology, DOI: 10.1080/01496395.2018.1489845

To link to this article: https://doi.org/10.1080/01496395.2018.1489845

Published online: 12 Jul 2018.

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SEPARATION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01496395.2018.1489845

Chitosan nanoparticles extracted from shrimp shells, application for removal of

Fe(II) and Mn(II) from aqueous phases
Mohamed Elsayed Abdelfattah Alia, Moustafa Mohamed Saeid Aboelfadla, Atef Mahmoud Selimb,
Hazem Fathy Khalilb, and Gamal Mohamed Elkadyb
a
Egyptian desalination research Center of excellence (EDRC), Hydrogeochemistry Department, Desert Research Center, Cairo, Egypt;
b
Department of Chemistry, Faculty of Science, Al-Azhar University, Nasr City, Cairo, Egypt

ABSTRACT ARTICLE HISTORY

The present work aims to prepare an ecofriendly and effective material for adsorption of heavy Received 6 March 2018
metals, especially iron and manganese from polluted water. Chitosan nanoparticles were prepared Accepted 13 June 2018
from the extracted chitosan of shrimp shells waste using a traditional ionic gelation method in KEYWORDS
presence of sodium tripolyphosphate as a cross-linker. To confirm the polymer structure and its Shrimp shells; chitosan
characteristics, the prepared nanoparticles were characterized using FT-IR, X-Ray diffraction, TEM nanoparticles; ionic gelation;
and SEM. Molecular weight, the degree of de-acetylation, ash content, particle size and zeta adsorption; heavy metal ions
potential values were 3923 D, 75 %, 4 %, 331 nm and +38 mv, respectively. A batch equilibrium removal
experiments were carried out to evaluate the chitosan nanoparticles as adsorbents of Fe (II) and
Mn (II) ions from aqueous solutions. The removal efficiency and adsorption capacity were studied
at different contact times, pH of the sorption medium, and initial metal ion concentration in the
feed solution. The removal efficiency and maximum adsorption capacity of Fe (II) and Mn (II) were
99.8, 116.2 mg/g and 95.3%, 74.1mg/g, respectively. From the adsorption isotherm and kinetic
studies, it was found that the Langmuir and the pseud-second order models, respectively, were
more fitted in this study.

Introduction widely.[7] Chitosan has the ability to adsorb significant

amounts of metal ions over a wide range.[4,8] Chitosan is
Heavy metals are one of the most important categories of
a polysaccharide which is made from the chitin present in
water pollutants, where they can be leached from their
the exoskeletons of the various crustaceans. Chitosan can
bearing rocks into groundwater. Heavy metals are also
be prepared from shrimps and crabs waste through several
produced during industrial activities and cause soil and
steps involving demineralization with the acid solution,
water contamination.[1] Iron and manganese are metallic
deproteinization with alkaline solution, and deacetylation
elements present in many types of rock. They are mostly
(DA) with a concentrated alkaline solution.[9] However,
present in the soluble reduced divalent form as ferrous Fe
chitin is made up of a linear chain of acetyl glucosamine
(II) and manganous Mn(II) ions. Both iron and manganese
groups while chitosan is obtained by removing enough
impart a strong metallic taste to the water, both cause
acetyl groups (CH3–CO) leaving behind a complete
staining and their accumulation has harmful effects on
amino group (–NH2) in addition to (OH) group which
human body.[2,3] Iron and manganese removal from
are both active sites in many chemical reactions.[10]
water is recommended when the dissolved concentrations
Chitosan is a natural, nontoxic, biodegradable, and bio-
exceed 0.3 mg/l iron Fe(II) and 0.05 mg/l manganese Mn
compatible polymer with antibacterial activity and has a
(II).[3] Despite presence of simple traditional methods for
wide range of applications in different fields such as mem-
removal of heavy metals ions from wastewater filtration,
branes, biomedical, and pharmaceutical (tissue engineer-
chemical precipitation, ion exchange, and membrane
ing-artificial skin, wound healing, drug delivery),[11–13]
technologies,[4,5] the adsorption has been considered as
cosmetic (toothpaste, body creams, and shampoos),[14]
one of the most efficient methods with many advantages
water treatment (flocculating and chelating agents),[15,16]
including low cost, high efficiency, good selectivity, and
agricultural (fertilizers, pesticides, and insecticides),[17]
recyclability with various materials.[6] Recently, low-cost
food processing (packaging, clarification of juices
adsorbents that are produced from wastes have been used

CONTACT Mohamed Elsayed Abdelfattah Ali mohamedea@edrc.gov.eg; m7983ali@gmail.com Egyptian desalination research Center of
excellence (EDRC), Hydrogeochemistry Department, Desert Research Center, Cairo, Egypt
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
© 2018 Taylor & Francis
2 M. E. A. ALI ET AL.
and protein recovery[18]), fuel cells, textile, and paper
industry.[19] The molecular weight (M.wt) and degree of
DA can be modified during its preparation. It is known
that chitosan is a weak base, insoluble in water and organic
solvents; however, it is soluble in dilute aqueous acidic
solution (pH < 6.5), which can convert the glucosamine
units into a soluble form of the protonated amine
(R
NHþ 3 ).
[20]
The adsorption capacity of chitosan or
even natural polymer can be controlled by sorbent particle
size, i.e., preparation of chitosan at the nanoscale, because
of unique size and large surface-to-volume ratio.[21]
Among the variety of methods developed to prepare chit-
osan nanoparticles, ionic gelation technique has attracted
considerable attention due to this process which is non-
toxic, organic solvent free, convenient, and controllable.[22]
Chitosan nanoparticles are formed in the ionic gelation due
to the electrostatic interaction between the positively
charged amine group of chitosan and negatively charge
groups of polyanion such as tripolyphosphate (TPP).[21]
The advantage of the ionic gelation process is that desired
size and surface charge can be modulated by right control
of critical processing parameters such as chitosan-to-TPP
weight ratio, pH, concentration of chitosan and TPP solu-
tions, etc. to fabricate the nanoparticle structure with opti-
mum antimicrobial activity.[23] TPP has also been selected
as a possible crosslinking agent for the preparation of
chitosan nanoparticles because of its coagulation and neu-
tralization effect.
In this work, effective adsorbent chitosan nanopar-
ticles were extracted from shrimp shell waste and using
it in the removal of Fe(II) and Mn(II) ions from waste-
water as there is a few paper-used chitosan nanoparti-
cles as an adsorbent for Fe(II) and Mn(II) removal.
Compared to the other methods, this method is very
economic and environment-friendly as it depends
mainly on waste recycling using no costive chemicals
that have been used for the removal of Fe(II) and Mn
(II) ions. Many of traditional methods are time con-
suming, for example during treatment using oxidation
method more cost and some byproducts (trihalo-
methanes) using chlorination are produced.[24]
Experimental and material
Materials
Local shrimp waste was collected and immediately
washed several times with water and detergent then
allowed to dry in open area under sunlight then
grounded to small particles. The grounded material
was transformed into chitosan via three successive
steps (demineralization, Deproteinization, and DA),
TPP, acetic acid, sodium hydroxide, hydrochloric acid,
glacial acetic acid, ferrous sulfate heptahydrate, and
manganese chloride hydrate brought from El-Nasr
Company for Intermediate Chemicals, Egypt.
Methods
Extraction of chitosan from chitin
First, demineralization and deproteinization to remove
primarily calcium carbonate and disrupt the chemical
bonds between chitin and proteins were generally per-
formed by acid treatment technique using 1 M HCl
(1:10 w/v) and 1 M NaOH (1:10 w/v) for 24 h for
each at room temperature, respectively.[10] After that,
the solution was filtered and the residue was washed
several times with deionized water (DI) until neutral
pH. However, demineralization was easily achieved
because of decomposition of calcium carbonate into
the water-soluble calcium salts with the release of car-
bon dioxide as shown in the following equation.[9,25,26]
2HCl þ CaCo3 ! CaCl2 þ H2 O þ Co2 "
To convert chitin to chitosan, the acetyl groups were
removed during the DA process, where demineralized
chitin was transferred to a 60% sodium hydroxide
solution. Then the solution was boiled for 2 h after
that alkali solution was drained off and washed repeat-
edly with DI till pH was lowered to normal. Finally,
chitosan was further dried at room temperature and
stored for further uses.[27]
Preparation of chitosan nanoparticles
Chitosan nanoparticles were prepared by dissolving at
0.5 g of prepared chitosan in 100 ml of 1% acetic acid
(v/v), and the pH of the solution was adjusted to be 4.6–
4.8 using 1N NaOH. Chitosan nanoparticles were formed
spontaneously upon addition of 3 ml chitosan solution
under vigorous magnetic stirring to 1 ml of an aqueous
TPP solution (0.25% w/v), with a ratio of chitosan to TPP
3:1 at room temperature. Nanoparticles were separated
by centrifugation at 9000×g for 20 min.[28] Chitosan
nanoparticles were extensively rinsed with DI to remove
any NaOH residues and dried at 40°C for 24 h before
further use or analysis.[29,30]
Characterization
Characterization of chitosan
Ash value: to determine the ash value of chitosan, 1.0 g
of chitosan sample is placed and accurately weighed
into clean, dry, pre-weighed porcelain crucible. The
samples are heated in a muffle furnace preheated to
650°C for 4 h. The crucibles are allowed to cool in the

furnace to less than 200°C and then placed into desic-
cators with a vented top. Percentage of ash value is
calculated using the following.[31]
ðW1
W2 Þ
Ash% ¼  100
W1
where W1 and W2 in grams are the weight of chitosan
before and after ignition, respectively.
Determination of degree of DA: the degree of DA
was measured by the acid-base titration method with
modifications. In brief, chitosan (0.1 g) was dissolved in
30 ml HCl aqueous solution (0.1 mol/l) at room tem-
perature with 2–3 drops of methyl orange added. The
red chitosan solution was titrated with 0.1 mol/l NaOH
solution until it turned orange. The DA was calculated
by the formula
C1 V1  C2 V2
DA% ¼  0:016
M  0:0994
where C1 = concentration of standard HCl aqueous solu-
tion (mol/l), C2 = standard NaOH solution (mol/l),
V1 = volume of the standard HCl aqueous solution used
to dissolve chitosan (ml), V2 = volume of standard NaOH
solution consumed during titration (ml), and M = weight
of chitosan (g). The number 0.016 (g) is the equivalent
weight of NH2 group in 1 ml of standard 1 mol/l HCl
aqueous solution and 0.0994 is the proportion of NH2
group by weight of chitosan.[32]Determination of mole-
cular weight was determined using viscosity measurement
method; the viscosity was assessed using a Brookfield
viscometer, Model DV3THBCJ0 (Brookfield
Engineering Labs, made in USA). In brief, 1% chitosan
solution was prepared using 1% acetic acid. The measure-
ment was made using a No. 5 spindle at 50 rpm at 25°C
with values reported in centipoises (cps) units.[33]
Intrinsic viscosity was used to calculate the average mole-
cular weight of the prepared samples using Mark-
Houwink Sakurada equation: η=KMa where K and 'a'
are the constants for a given solute–solvent system is
0.078 and 0.76, respectively.[33,34] FT-IR spectroscopy
(Jasco FT-IR 6100, Japan) was used to compare and con-
firm the chemical conformation of standard chitosan with
that of extracted chitosan. The spectra of chitosan samples
were obtained with a frequency range of λ = 400–
4000 cm.[35] The wide-angle X-ray diffraction (XRD)
analysis was applied to detect the crystallinity of chitosan
and nano-chitosan prepared and their patterns were
recorded using PAN analytical XRD X’pert PRO. The
particle size distribution, the zeta potential, and polydis-
persity index of the chitosan nanoparticles were deter-
mined by dynamic light scattering using a Zetasizer Nano
instrument (Malvern Instruments, UK). Transmission
electron microscopy (TEM) was used to examine size,
SEPARATION SCIENCE AND TECHNOLOGY 3
shape, and morphologies of the nanoparticles prepared
in this study. TEM micrographs of nanoparticle samples
deposited on copper grids were obtained with a JEOL-
2100 Electron Microscope, made in Japan. Scanning elec-
tron microscope (SEM) analysis employed to determine
the morphology of formed nanoparticle using (Quanta
FEG250 SEM FEI company) SEM gives high-resolution
images of the surface of a sample.
Metal ion uptake experiments
Batch adsorption experiments were conducted in two
series of 150 ml beakers with 100 ml of iron and
manganese solution at a certain concentration. The
initial pH of solutions was adjusted using the required
amounts of 0.1 M HCl or 0.1 M NaOH solutions to
study the adsorption at different pH, otherwise it was
constant at 4 and 6 for iron and manganese, respec-
tively. The mixture was equilibrated with nano-chitosan
at a rotation speed of 180 rpm using a mechanical
shaker for 120 min. All experiments were conducted
at room temperature. Samples were taken at fixed time
intervals to determine solution concentration. Iron and
manganese concentrations in the filtrates were analyzed
by ICP (ICAP, 6500 Duo, Thermo Scientific, England).
A series of experiments was conducted to determine the
effect of parameters such as adsorbent dose, pH, initial
concentration, and contact time on equilibrium uptake
of Fe(II)and Mn(II) ions by NCS.[36] Adsorption
experiments for the removal of Fe(II) and Mn(II) ions
were conducted in pH range of (2.5–7), adsorbent
dosage (0.5–15 g/l), contact time from 0 to 120 min,
and metal concentration (10–120 mg/l) at room tem-
perature. The adsorption kinetics and isotherms data
were collected under the optimized condition of adsor-
bent dose, pH, and contact time. After separation by
centrifugation at 5000 rpm, the residual concentration
of the metal ions was determined by ICP. In all of the
above experiments, the adsorption values were calcu-
lated from the change in solution concentration using
the following equation.[37]
V
q ¼ ðCo
Ce Þ 
M
where q is the amount (mg/g) of metal ions adsorbed
by the NCS, Co and Ce (mg/l) are the metal concentra-
tions in the solution initially and after adsorption,
respectively, V is the volume of added solution, and
M (g) is the mass of the adsorbent (dry) used. The
removal efficiency is calculated as
Co
Ce
R% ¼ 100 
Co
4 M. E. A. ALI ET AL.
Result and discussion
Characterization of chitosan and chitosan
nanoparticles
The extracted chitosan from shrimp has been prepared
at three different M.wts, high M.wt (51269.68 D), med-
ium M.wt (32403.67 D), and low M.wt (3923 D). The
difference in M.wt of the obtained chitosan was due to
the difference in heating of the reaction temperature
and time,[25] where the low M.wt was obtained as the
continuous heating of the polymer during the DA
process with NaOH that causes a decrease in the M.
wt with the rising in the DA degree.[34] Based on the
data produced from particle size analyzer, it was found
that the lowest M.wt was chosen to be easier to resize it
in the nano-form, where the produced nanoparticle size
was 331 nm, while the particle size of that produced
from medium and high M.wt was 1562 and 3914 nm,
respectively, where as the M.wt decreased, the particle
size also decreased.[38] Based on the experimental data,
it was found that the DA degree and ash content of
chitosan were found to be 75% and 4%, respectively. It
is known that DA is the most parameter used for
chitosan characterization and is defined as the number
of amines group in relation to the number of amides
group of the polymeric chain formed as a result of
removing –CO–CH3 group from the chitin chain as
shown in Scheme 1. In addition, DA of chitosan affects
the adsorption properties of heavy metals from waste-
water, the obtained medium DA (75%) confirms that
the prepared chitosan can be used as an effective adsor-
bent for some heavy metals.[39]
The structure of the extracted chitosan from chitin
was confirmed by FT-IR, Fig. 1, where the spectrum of
the prepared chitosan shows more broad absorption
bands at 3422 cm−1 than that observed in the spectrum
of chitin. This broad band might be corresponded to –
OH stretching vibrations of water, hydroxyls and NH2
stretching vibrations of free amino groups. The two
bands observed at 2923.56 and 2859.92 cm−1 corre-
spond to asymmetric stretching of CH3 and CH2 in
both chitin and chitosan. The observed band at
2221 cm−1 is attributed to C–N group of C–NH2. The
band observed at 1645.95 cm−1 in chitin spectrum has
been split in the spectrum of chitosan to two bands
with intensity increases, which corresponds to bending
vibration of NH2 and also indicates the occurrence of
DA. In addition, the stretching band of C–O in chit-
osan spectrum was observed at 1038.48 cm−1.[9,40,41]
Figure 2 shows XRD patterns of the extracted chitosan
and chitosan nanoparticles. From the pattern, the two
characteristic peaks at 2 = 10° and 20° of the extracted
chitosan with crystalline structure have been fully
destroyed after crosslinking with TPP during formation
of chitosan nanoparticles, where these two peaks disap-
peared in the pattern of NCS, which indicates the amor-
phous nature, this in agreement with a previous work.[42]
However, according to kinetic studies, the decreasing of
the polymer crystallinity results in an improvement of
metal ion sorption and capacity. The decreasing of crys-
tallinity could be due to that chitosan nanoparticles are
composed of a dense network structure of interpenetrat-
ing counter ions of TPP, where the polymer chains cross-
link with each other by TPP. Thus, the XRD pattern of
chitosan nanoparticles is characteristic of an amorphous
polymer.[28]
The surface charge and stability of the prepared
chitosan nanoparticles were characterized using zeta
potential, it was found that the surface was shown to
be positively charged (+38 mV). However, the positive
zeta potential was because of the hydrogen bonds
formed between the amino and hydroxyl groups of
chitosan with the hydroxyl groups or oxygen atoms of
water.[43] In this work, the optimum preparation con-
ditions were obtained by changing the ratio of chitosan
to TPP as follow; (1:1), (2:1), and (3:1), respectively, at
pH of chitosan solution of 4.6–4.8.[44] The lowest par-
ticle size was obtained from the ratio of chitosan/TPP
(3:1). These nanoparticles of chitosan were confirmed
using TEM at two magnifications of 50 and 100 nm,
Fig. 3 showed roughly spherical in shape.[45] Since the
adsorption process is a surface process, the surface area
of the adsorbent is of great importance for contentious
adsorption.
Figure 4 shows SEM images of NCS, which has a
porous layer composed of pores network. It is known
that surfaces with porosity have a high surface, which
enhancing the adsorption capacity.[46]
Factors affecting on adsorption
Heavy metal ions and surface charge of the adsorbent
depend mainly upon pH of the solution, where Fe(II)
and Mn(II) precipitate at pH 6 and over 7, respectively.
Hence, it is mandatory to study the effect of pH on
adsorption efficiency for sorption studies.[47] However,
pH must be less than that at which metal ions precipi-
tate, i.e., pH 6 for iron and 8 for Mn.[48] The effects of
pH on the removal of Fe(II) and Mn(II) were studied
with the pH range of 2.5 ± 0.2 to 7 ± 0.2 with keeping
other parameters constant (Fig. 5a). From the figure,
the optimum adsorption takes place at pH 4 for Fe(II)
and at pH 6 for Mn(II), where the removal percent was
81.3 and 81.1, respectively. Further increase in pH leads

Scheme 1. Schematic of extraction of chitosan from chitin.
to precipitation of Fe(II) which inhibits the adsorption
process. At low pH values, chitosan became positively
charged with higher H+ ion concentration, which led to
protonation of amino groups that induces an electro-
static repulsion of metal cations that reduces the num-
ber of binding sites available for metallic ions.[42] In
SEPARATION SCIENCE AND TECHNOLOGY 5
general, Fe(II) and Mn(II) ions uptake increases as the
pH increases until to pH 7.
The amount of adsorbent was one of the impor-
tant parameters that strongly affect the sorption
capacity. The dependence of Fe(II) and Mn(II) ions
sorption on nano-chitosan was studied by varying the
6 M. E. A. ALI ET AL.

Figure 1. FTIR spectra of pure chitosan and prepared chitosan nanoparticles.

Figure 2. XRD patterns of pure chitosan, TPP, and prepared chitosan nanoparticles.

amount of the adsorbent dose from 0.5 to 15 g at pH
4.0 ± 0.2 for Fe(II) ions and pH 6 ± 0.2 for Mn(II)
ions. Figure 5b shows that the removal percentage
increases with increasing the adsorbent dose from
92% to 99.8% for Fe(II) and from 37.9% to 95.3%
for Mn(II) ions. These increases were attributed to
increasing the active sites and surface area of the
chitosan nanoparticles.
Figure 5c shows the effect of initial concentration of
Fe(II) and Mn(II) ions onto removal efficiency, where

Figure 3. TEM images of chitosan nanoparticles at two magnifications.
Figure 4. Surface morphology of chitosan nanoparticles at two magnifications.
different concentrations of the metal ions were gently
shaken with 0.5 g of chitosan nanoparticles at pH of the
solution 4 and 6 for Fe(II) and Mn(II), respectively.
The figure shows that the removal efficiency of the
metal ions decreased from 87% to 49% and from
44.9% to 27% for Fe(II) and Mn(II), respectively, as
the initial concentration increased from 20 to 120 mg/l,
where the removal efficiency decreased as initial metal
ions concentration increased. The poor uptake of the
ions at higher concentrations was due to the increased
ratio of the initial number of moles of metal ions to the
vacant sites available in adsorbent sites which resulting
in a decrease in the removal of adsorbate.
The study of contact time between adsorbent and
adsorbate is necessary during adsorption process to
consider the efficiency of desorption and regeneration
of the adsorbent. The effect of contact time on metal
SEPARATION SCIENCE AND TECHNOLOGY 7
ions adsorption efficiency is shown in Fig. 5d. It was
observed that the adsorption rate initially increased
rapidly from 5 to 20 min, and then a steady state was
obtained with optimal removal efficiency within about
100 min that reached 86% and 49% for Fe(II) and Mn
(II), respectively. During the process, the adsorbent
surface is progressively blocked by the adsorbate mole-
cules, becoming covered after some time, where the
adsorbent cannot adsorb any more ions.[49]
Adsorption isotherms
Adsorption isotherms are essential in order to determine
the adsorption potential of the adsorbent. Figure 6 shows
the experimental data of adsorption of Fe(II) and Mn(II)
on NCS at different concentrations. Langmuir and
Freundlich’s equations were used to fit the experimental
8 M. E. A. ALI ET AL.
Figure 5. Effect of (a) pH, (b) adsorbent dose, (c) initial ions concentrations and adsorption time on removal of Fe2+ and Mn2+ using
chitosan nanoparticles.
data. However, the linearized Langmuir adsorption
model is shown by the following equation:
Ce 1 1
¼ þ Ce
qe kL qm qm
where Ce is the equilibrium concentration in the solu-
tion (mg/l), qe the amount of metal ion adsorbed on
adsorbent NCS (mg/g), qm is amount of metal ion for a
formation of a monolayer adsorbate on adsorbent sur-
face (mg/g), kL is Langmuir equilibrium constant that
depends on the absorbed energy (mg/l). The essential
characteristics of the Langmuir isotherm can be
expressed by a dimensionless constant called the
separation factor RL that calculated as follow:
1 (II) and Mn(II) removal fitted well with the Langmuir
RL ¼
1 þ kL Co
where Co is initial concentration of adsorbate (mg/g),
RL values indicate the adsorption to be unfavorable
when RL > 1, linear when RL = 1, favorable when
0 < RL < 1, and irreversible when RL = 0. The
Freundlich isotherm is another popular isotherm that
is used widely to express adsorption equilibrium at
constant temperature.[7]
The linearized Freundlich adsorption model is
shown by the following equation:
1
log qe ¼ log kF þ ðlog CeÞ
n
where kF is Freundlich isotherm constant that shows
adsorption potential and n is Freundlich equilibrium
constant that expresses the binding energy between
the adsorbent and metal ions. The isotherm constants
for these models were found by a linear regression
and the results are shown in Table 1 and Fig. 6. The
data values indicate that the adsorption data for Fe
and the Freundlich isothermal curve for the concen-
tration studied. However, the higher correlation coef-
ficient obtained from Freundlich model (R2 = 0.985,
0.979) for Fe(II) and Mn(II), respectively, compared
to Langmuir curve (R2 = 0.93, 0.95) suggests that the
adsorption was taken place on the heterogeneous
 SEPARATION SCIENCE AND TECHNOLOGY 9

(II) were 2.58 and 1.69 g/l, respectively, which mean

an appropriate adsorption.

Adsorption mechanism
Chitosan has two main reactive groups, hydroxyl and
amine group, which are responsible for metals ion
adsorption through chelation or forming complex.
However, chelation with Fe and Mn is the main process
for removal by forming coordinate covalent bonds with
the metal ions, whereas some hydroxyl groups also
might take part in coordination by release of protons.
The crosslinking of chitosan with TPP reduces its par-
ticle size, increases the surface area, and increases the
stability of the polymer in the acidic solution, which
would translate in adsorption enhancement.

Adsorption kinetics
A suitable adsorbent for water treatment must not only
have a high capacity but also a fast adsorption rate, where
the adsorption rate is one of the important properties of
adsorbent. Kinetic models are used to survey the control-
ling parameters of adsorption processes, such as adsorption
rate, chemical reaction, and diffusion mechanisms.
Figure 7 illustrates the effect of contact time on adsorption
of Fe(II)and Mn(II) using NCS. For kinetics study, the
models of pseudo-first order and pseudo-second order
were used. The pseudo-first-order model equation is
logðqe
qt Þ ¼ log qe
k1 t
Figure 6. Effect of initial concentration on (a) the Langmuir and where qt (mg/g) is amounts of metal ion adsorbed at a
(b) the Freundlich on adsorption of Fe+2 and Mn+2 using time “t,” qe is amounts of metal ion adsorbed at equili-
chitosan nanoparticles. brium, and k1 is the constant coefficient of pseudo-
first-order rate of adsorption (min−1) by the value, k1
Table 1. Parameters for the Langmuir and Freundlich models of is obtained by plotting logðqe
qt Þ against t. The linear
Fe2+ and Mn2+ adsorption. form of pseudo-second-order model is given by the
Parameter Fe(II) Mn(II) following equation:
Langmuir isotherm results qm (mg/g) 133.33 99.3
kL (l/mg) t 1 1
R2
0.064356 0.33665 ¼ þ t
0.93 0.95 qt k2 q2e qe
RL 0.115 0.217
Freundlich isotherm results n 2.58 1.69
kF 3.807 2.442
where k2 is the rate constant of pseudo-second order
R2 0.979 0.985 adsorption, k2 is also obtained by plotting t/qt against
time. The fitted parameters of the two kinetic models are
reported in Table 2. The experimental qe values for both
surface of the adsorbent much better than the mono- metal ions were closer to the calculated qe values obtained
layer adsorption. The value of RL calculated for Fe(II) from the second-order kinetic plots compared to those of
and Mn(II) concentrations was 0.115 and 0.217, the first-order kinetic plots and the values of the correlation
respectively, that means the adsorption of both of coefficient R2 for both metal ions from the linear plots show
metal ions on NCS is a favorable process. For the slightly different (Table 2). These indicated the adsorption
Freundlich constant, the values “n” for Fe(II) and Mn kinetics followed the pseudo-second-order kinetics.
10 M. E. A. ALI ET AL.

methods called demineralization, deproteinization,

and DA with 75% DA and M.wt (3923 D).
Controlling the M.wt was essential, as the lower M.wt
was the easier to convert into nanoparticles. The
extracted chitosan was converted to nanoparticles, to
enhance the adsorption capacity, using ionic gelation
method in presence of sodium TPP as cross-linker.
NCS was characterized using FT-IR, TEM, SEM,
XRD, and particle size analyzer. The factors include
pH, adsorbent dose; initial concentration and contact
time were optimized for removal of Fe(II) and Mn(II)
from aqueous solutions in batch experiments. The
removal efficiency and maximum adsorption capacity
of Fe(II) and Mn(II) were 99.8%, 116.2 mg/g and
95.3%, 74.1 mg/g, respectively. From the adsorption
isotherm and kinetic studies, it was found that the
Langmuir and the pseudo-second-order models,
respectively, were more fitted in this study, where the
sorption capacity of chitosan nanoparticles was high
and the adsorbent favors multilayer adsorption. The
choice of chitosan nanoparticles for removal Fe(II)
and Mn(II) metal ions is considered an effective, inex-
pensive, safe, and environment-friendly substance used
as a chemical adsorbent for water treatment derived
from renewable and very abundant material widely
available in many countries.

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