Journal of Environmental Chemical Engineering 3 (2015) 179–186

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Journal of Environmental Chemical Engineering

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

Removal of divalent manganese from aqueous solution using glycine

modified chitosan resin
Khaled Z. Al-Wakeel a , H. Abd El Monem b , Mostafa M.H. Khalil c, *
a
Environmental Science Department, Faculty of Science, Port Said University, Port Said, Egypt
b
Nuclear Materials Authority, El Maadi, Cairo, Egypt
c
Chemistry Department, Faculty of Science, Ain Shams University, Cairo, Egypt

A R T I C L E I N F O A B S T R A C T

Article history: Removal of Mn(II) ions from aqueous solution through adsorption on glycine modified chitosan resin
Received 2 July 2014 (G@Chs) has been studied. Experiments were carried out as a function of pH, concentration of metal ion
Accepted 21 November 2014 and contact time. Optimum Mn(II) uptake was observed at pH 6 and most of the Mn(II) were sorbed
Available online 25 November 2014
within 150 min. The isothermal data correlated with Langmuir model better than Freundlich model.
Thermodynamic data indicated that adsorption process is exothermic and spontaneous reaction, while
Keywords: the kinetic data indicated that the adsorption follows the pseudo second order kinetics. The adsorption
Mn(II)
capacity of glycine onto modified chitosan resin was found to be 1.3 mmol/g, at 25
C  1. Due to their
Glycine
Chitosan
outstanding adsorption capacities, G@Chs resin is an excellent adsorbent for the removal of Mn(II) ions.
Adsorption The resin regeneration was greater than 93% with 1.0 M HCl, and G@Chs could be repeatedly utilized for
Kinetics Mn(II) removal with negligible loss in sorption capacity.
Thermodynamics ã 2014 Elsevier Ltd. All rights reserved.

Introduction known that an excess Mn(II) in portable water causes problems in

respiratory system and in the nervous system; it concentrated in
Removal of heavy metal ions from various water resources has brain especially in the basal ganglia, resulting in neurological
been a crucial issue. Heavy metals are generally present as disorders [5], and several reports are available on the effects of
pollutants in a variety of industrial effluents. Industries such as exposure to Mn(II) in water [5–7]. According to the World Health
metal plating, metal finishing, rubber processing, fertilizers, Organization, the maximum acceptable drinking water concentra-
mining as well as agriculture release theses heavy metals into tion in drinking water is 0.05 mg/L for manganese [8]. While the
the surface and ground water [1]. Manganese is one of the Egyptian legislation sets a limit of 0.4 mg/L for manganese [9]. It is
important heavy metals found in groundwater, wastewater etc. therefore, necessary to proceed with the treatment of water
Manganese can impair the quality of water from dual sources, contaminated by excess manganese so as to reduce their impact on
natural and manufactured. Manganese can be present in water as a the environment and to the human health. Different adsorbent
result of mineral dissolution and/or leaching from some rock and have been carried out for adsorption of manganese ions: calcium
soils [2]. It could also be as a result of pollution emanating from silicate [10], clay [11], activated carbon [12], nut shells of
industrial operations such as pyrolusite (MnO2) treatment, steel Tamarindus indica [13], volcanic ashes [14] etc. In recent years,
alloy dry cells, glass and ceramics, paint and vanish, ink and dyes, researchers have extensively focused on research into biosorbent
metal galvanization plant effluents etc. [3]. Heavy metals such as such as chitosan because of its desirable properties like nontoxic,
Mn2+ are not biodegradable and thus tend to mount up in living inexpensive, biocompatible and bio-functionality including antith-
organisms through the use of the heavy metal impaired water, and ermobogeneric, homeostatic, and wound healing properties, anti-
eventually causing various diseases and disorders [4]. Manganese bacterial property and its low cost efficient [15–19]. Chitosan is a
is an oligo-element necessary for human survival but become toxic natural polymer derivative from N-deacetylation of chitin in
when the concentrations become too high in human body. It is alkaline medium [20]. It is the second most abundant amino-
polysaccharide found in nature after cellulose. It is constituted of
both glycosamine and acetylglucosamine moieties. Chitosan has
been widely applied to the fields of food and pharmacy processing
* Corresponding author. Fax: +20 663657601.
E-mail addresses: Khalid_elwakeel@yahoo.com (K.Z. Al-Wakeel), biotechnology and analytical chemistry. Chitosan shows high
hythamawed@gmail.com (H. Abd El Monem), khalil62@yahoo.com (M.M.H. Khalil). affinity for metal ions due to the amine and hydroxyl groups. These

http://dx.doi.org/10.1016/j.jece.2014.11.022
2213-3437/ ã 2014 Elsevier Ltd. All rights reserved.
 180 K.Z. Al-Wakeel et al. / Journal of Environmental Chemical Engineering 3 (2015) 179–186

groups function as the coordination sites for heavy metal ions [21]. FT-IR analysis
The removal of heavy metals (Cu, Ni, Co and Mn) was increased by Infra red spectra were performed using Nicolet IR200 FT-IR
the introduction of amino acids to chitosan, especially for Mn [22]. Spectrometer.
In this work, we synthesized chelating resin possessing glycine
moieties, by using a cross linked chitosan as a base material for Sorption experiments
removal of Mn(II). The influences of the experimental parameters
such as pH, temperature, contact time, initial concentration on Preparation of Mn(II) solutions
adsorption will be studied. The kinetic models used to describe the A stock solution of Mn(II) is prepared by dissolving an accurate
rate data will be discussed. Both Langmuir and Freundlich isotherm quantity of MnSO4H2O (Merck Ltd., Germany). Stock solution
models will be discussed, also the equilibrium isotherm modeling (1 102 M) of Mn(II) was prepared, the range of concentrations
data and thermodynamic parameters will be calculated. Desorp- prepared from stock solutions has been varied from 0.0001 to
tion studies will be carried out using suitable agents to regenerate 0.01 M. Distilled water was used in preparing the stock solutions
the spend adsorbent. and also throughout the experimental analysis. The initial pH
adjustments were carried out either by HCl and NaOH.
Experimental
Batch studies
Bach adsorption was carried out by contact of dry resin (0.1 g) in
Chemicals
100 mL of 5  103 M Mn(II) solution taken in 125 mL Erlenmeyer
flasks and agitated at 200 rpm on a shaking water bath model-1083
Chitosan, glycine, glutaraldehyde, dioxane, epichlorohydren
(Labortechnik mbH, Germany). Samples are withdrawn at periodic
and manganese sulfate monohydrate were Aldrich products. All
intervals and filtered. The concentration of Mn(II) ions remaining
other chemicals were of analytical grade obtained from Merck Ltd.,
in the filtrate is analyzed by spectrophotometer (HANNA-HI
Germany and were used as received.
96709C) at 525 nm [23]. Quality control charts for Mn(II) analysis
were done, and each data point was taken as the average of three
Surface modification and cross-linking of chitosan
measurements with standard deviation of 0.1  0.05%.
Three grams of chitosan was dissolved in 20% aqueous solution
of acetic acid and stirred until the solution became homogenous.
Effect of pH
Then 2 mL of glutaraldehyde solution (25%) was added, the
The uptake of Mn(II) by the investigated resin was studied at
obtained chitosan solution was stirred with heating until gelati-
different pH values (1.0–8). The pH was adjusted using HCl or
nous product was obtained. The gel obtained was washed with
NaOH. 0.1 g of investigated resin was placed in a series of flasks. To
distilled water several times and kept for use.
each flask 100 mL of Mn(II) solution (5  103 M) was added. The
contents of each flask were shaken for 150 min on a shaker at
Synthesis of glycine-type chitosan resin
200 rpm and at temperature 25  1
C at desired pH. The resin was
The modification of chitosan with glycine is schematically
separated from the solution by filtration. Then the residual
described in Scheme 1. A glycine moiety was introduced to the
concentration of Mn(II) was estimated as above (Section Batch
cross-linked chitosan in two steps according to the previously
studies).
reported method [17] as follows:
Step 1: Cross-linked chitosan (5 g) was suspended in a mixture
Adsorption isotherms
of distilled water (50 mL) and ethanol (50 mL), and then
Complete adsorption isotherms were carried out by placing
epichlorohydren (10 g) was added to it. The mixture was then
0.1 g portions of dried resin in a series of flasks containing 100 mL
refluxed for 3 h. The product was filtered and washed with ethanol
of Mn(II) ions at pH 6. The temperature was thermostatically kept
and distilled water to remove any residual reagents.
at 25  1, 35  1 or 45  1
C and equilibrium time 150 min. The
Step 2: 5 g of glycine suspended in dioxane (100 mL) were
residual concentration of Mn(II) was determined. The adsorption
mixed with the produced chitosan, and then 40 mL of 1.0 M NaOH
data were treated according to Langmuir equation [24]:
was added to the mixture. The reaction mixture was refluxed for
12 h, filtered and washed with water followed by acetone. The Q max K L C e
qe ¼ (1)
produced resin was dried in air and kept for use. The resin was 1 þ K L Ce
referred by G@Chs. where qe the adsorbed value of Mn(II) ions at equilibrium
concentration (mmol/g), Qmax is the maximum adsorption capacity

[(Schem_1)TD$FIG]

Scheme 1. Schematical description of the modification of chitosan with glycine.

 K.Z. Al-Wakeel et al. / Journal of Environmental Chemical Engineering 3 (2015) 179–186 181

(mmol/g) and KL is the Langmuir binding constant which is related (ii) Pseudo-second order model [29]:
to the energy of adsorption (L/mmol), Ce is the equilibrium
k2 t
concentration of Mn(II) in solution (mmol/L). qt ¼ (10)
1 þ k2 qe t
After linearization:
Ce Ce 1
¼ þ (2) After linearization:
qe Q max K L Q max
 
t 1 1
¼ 2
þ t (11)
qt k 2 qe qe
The most important multisided adsorption isotherm for hetero-
geneous surfaces is the Freundlich isotherm, characterized by the where k2 is the pseudo second order rate constant of adsorption (g/
heterogeneity factor 1/n. The Freundlich model is described by [25]: mmol/min).
(iii) Fickian diffusion low [30]:
qe ¼ K F C 1=n
e (3)
qt ¼ K i t0:5 þ X (12)
where KF and n are the Freundlich constants related to the
adsorption capacity and intensity, respectively. where qt is the amounts of Mn(II) adsorbed at time t and Ki is
After linearization: intraparticle diffusion rate (mmol/g/min0.5). The Ki is the slope of
straight-line portions of the plot of qt vs t0.5. If the intraparticle
1
logqe ¼ logK F  logC e (4) diffusion is the sole rate-limiting step, it is essential for the plot to
n
go through the origin. However, it is not always the case, and
adsorption kinetics may be controlled by film diffusion and
The degree of suitability of the obtained resin towards Mn(II) intraparticle diffusion simultaneously. Thus, the intercept is not
was estimated from the values of the separation factor (RL) using equal to zero (X). The positive values of X indicate the presence of
the following relation [26]. boundary layer effect on the rate of adsorption.
(iv) Elovich equation [31]:
1
RL ¼ (5)
1 þ K L C0 dqt
¼ aebq (13)
where KL is the Langmuir equilibrium constant and C0 is the initial dt
concentration of Mn(II).
The thermodynamic parameters of adsorption reaction were After linearization:
obtained from the treatment of KL values at different temperature
1 1
according to van’t Hoff equation [27]: qt ¼ blnab þ lnt (14)
b
DH
DS

lnK L ¼ þ (6) where qt is the sorption capacity at time t and a the initial sorption
RT R
rate (mmol/g/min) and b is the desorption constant (g/mmol).
where DH and DS are enthalpy and entropy changes, R is the
o o
Thus, the constants can be obtained from the slope and intercept of
universal gas constant (8.314 J/mol/K) and T is the absolute a straight line plot of qt vs ln t.
temperature (K). Plotting ln KL against 1/T gives a straight line
with slope and intercept equal to – DHo/R and DSo/R, respectively. Resin regeneration
The Gibbs free energy of adsorption (DGo) at different temper- Resin regeneration were performed by placing 0.5 g of resin in
atures was calculated using the following relation: the column and then loaded with Mn(II) solution at initial
concentration of 5  103 M and flow rate of 1 mL/min. After the
DGo ¼ DHo  T DS0 (7)
loading the column, the resin was washed carefully by flowing
distilled water through the column. The resin loaded by Mn(II) was
then subjected for regeneration using 1.0 M HCl. After regeneration
Effect of contact time on the uptake the resin was again carefully washed with distilled water to
The effect of contacting time on the uptake of Mn(II) by resin was become ready for the second run of uptake. The efficiency of
carried out by placing 0.1 g of dry resin in a flask containing 100 mL of regeneration was calculated using the following equation:
Mn(II) solution at initial concentration of 5  103 M and pH 6. The
Regeneration efficiencyð%Þ
contents of the flask were placed on a shaker at 200 rpm and at
temperature 25  1
C. 10 mL of the solution were taken at different Total adsorption capacity in t he second run
¼  100 (15)
time intervals and used to determine the residual concentration of Total adsorption capacity in t he second run
Mn(II). The adsorption data were treated according to the kinetic
models; these models are expressed as follows:
Sorption/desorption process was carried out for three cycles.
(i) Pseudo-first order model [28]:

qt ¼ qe ½1  ek1 t  (8) Results and discussion

FT-IR analysis
After linearization:
 
k1 The IR (infrared) spectra of glycine modified chitosan resin,
logðqe  qt Þ ¼ logqe  t (9) compared with that of the cross-linked chitosan resin, depicted an
2:303
additional band at 1600 cm1 (Fig. 1). These seem to originate from
where k1 is the pseudo first order rate constant (min1) of
the ligand moiety, and are characteristic of carboxylate group
adsorption and qe and qt (mmol/g) are the amounts of Mn(II)
vibration of the glycine moiety; this result confirms the success of
adsorbed at equilibrium and time t, respectively.
the modification.
182 K.Z. Al-Wakeel et al. / Journal of Environmental Chemical Engineering 3 (2015) 179–186
[(Fig._1)TD$IG]

Fig. 1. FT-IR Spectra of (a) cross-linked chitosan and (b) glycine modified chitosan.

Effect of pH on the uptake protons and the surface becomes negatively changed, so the
adsorption of Mn(II) ions increases. The uptake mechanism is the
The pH of the adsorption medium is an important factor for the chelate interaction between Mn(II) and modified adsorbent. The
adsorption of heavy metal ions onto adsorbents, because the adsorption capacity of G@Chs decreases with further increasing of
charge at the adsorbent surface and metal ion speciation changes pH (pH > 6.0), this may be due to the formation of MnOH+ and Mn
with the initial pH [32]. Mn(II) ions being present in the solution as (OH)2 species, which have a lower binding affinity for the active
Mn(H2O)62+. In order to optimize the pH for maximum removal sites on the adsorbent [34].
efficiency of Mn(II), experiments were conducted at 25  1
C over
the initial pH range of 1.0–8.0. This pH range was chosen to avoid Adsorption isotherms
consequent precipitation of Mn(II) ions [33]. From Fig. 2, it will be
seen that the uptake capacity towards Mn(II) ions increased with The adsorption isotherms reveal the specific relation between
increasing solution pH. In acidic solutions, strong competition the concentration of adsorbate and the adsorption capacity of an
exists between the metal ions and protons for chelation with the adsorbent at a constant temperature [35]. The Langmuir and
sorbent active sites and this leads to a decrease in the uptake Freundlich adsorption isotherms are generally used to describe the
capacity of Mn(II) ions. Ionizable functional groups, such as —NH2, adsorption behavior. Fig. 3 show the adsorption isotherms of
COOH or —OH, on the surface of G@Chs may gain or lose protons, Mn(II) by G@Chs at pH 6 and at different temperatures. The
resulting in a surface charge that varies with pH. At low pH, the adsorption capacity of G@Chs for Mn(II) at 25 o C is 1.3 mmol/g, this
surface sites are protonated and the surface becomes positively value is higher than previously published one for the adsorption of
charged; in contrast, at high pH, the ionizable groups lose their
 K.Z. Al-Wakeel et al. / Journal of Environmental Chemical Engineering 3 (2015) 179–186 183
[(Fig._2)TD$IG] [(Fig._4)TD$IG]
1.4 7

6
1.2
5
Uptake, mmol/g

Ce/q e (g/L)
1.0 4

3 Temperature
0.8
25°C
2
35°C
0.6
1 45°C

0.4 0
0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8 9 10
Initial pH Ce (mM)
Fig. 2. Effect of pH on the uptake of Mn(II) by G@Chs resin at initial concentration of Fig. 4. Linear Langmuir isotherms for the adsorption of Mn(II) onto G@Chs at
5  103 M; contact time 150 min at 25
C. different temperatures; pH 6; contact time 150 min.

Fe(III) onto G@Chs (0.9 mmol/g) at pH 2.5 and the same other
The values of KF and n at different temperatures were calculated
adsorption conditions [17].
from linear Freundlich isotherm (Fig. 5) are reported in Table 1. The
The Langmuir sorption model assumes that sorption occurs at
high values of KF and n at elevated temperatures confirms the high
specific homogeneous sites on the sorbent and is the most
adsorption capacity and strong binding of Mn(II) ions on the resin
commonly used model for the monolayer sorption process. The
surface.
Freundlich sorption model describes the multilayer adsorption
The reported values of DHo, DSo and DGo in Table 2 were
isotherm for heterogeneous surfaces. The values of KL and Qmax for
calculated from Fig. 6. The positive value of DHo indicates an
adsorption of Mn(II) on resin was calculated from Langmuir
endothermic adsorption process, and are coherent with chemical
isotherm (Fig. 4) and reported in Table 1. The values of Qmax are
process, which confirm that the complex formation between Mn
comparable with the experimental results, and the values of R2
(II) and amine sits on the resin surface. The negative values of DGo
reported in Table 1, which is a measure of the goodness-of-fit,
(Table 2) indicate that the adsorption reaction is spontaneous, the
confirm the better representation of the experimental data by the
increase in the negativity of DGo with increasing temperature
linear Langmuir model than Freundlich model. This indicates the
confirm that the adsorption is favorable at higher temperatures
homogeneity of active sites on the resin surface. The observed
[36]. The thermodynamic behavior may be attributed to the
increase of both Qmax and KL with increasing temperature may be
increased number of active sites as well as the endothermic nature
related to the increase of the stability of the complex formed
of the reaction between resin active sites and Mn(II) ions, This may
between Mn(II) and glycine moieties on the resin surface. The
also be reflected in the values of KL. The values of KL increase as the
reported values of KL (Table 1) are relatively high in comparison
temperature increases, indicating higher affinity of the resin
with the previously published work for the adsorption of Fe(III)
towards Mn(II) at higher temperature.
onto G@Chs resin [17], this may be due to the lower binding energy
in the later case. The value of KL gives a good idea about the ability
Adsorption kinetics
of the resin for removing Mn(II) from low concentrations indicates
the high removal efficiency of G@Chs for Mn(II) removal from
The equilibrium data to investigate the effect of contact time on
diluted solutions.
the removal of Mn(II) onto G@Chs at pH 6 and 25
C is shown in
Fig. 7. Clearly, the equilibrium time was reached after approxi-
[(Fig._3)TD$IG] mately 150 min. The data in Fig. 7 were treated according to the
pseudo first-order (PFORE) and pseudo-second-order (PSORE)
1.7
equation (Fig. 8). PFORE and PSORE rate constants as well as
1.6 equilibrium sorption capacities are reported in Table 3. The validity
1.5 of each model is checked by comparing the R2 values. Accordingly,
as shown in Table 3, the adsorption of Mn(II) on G@Chs is perfectly
1.4
fit pseudo second order model rather than pseudo first order one. It
qe (mmol/g)

1.3 is also seen that the experimental and theoretical value of qe

1.2 (obtained from pseudo second-order model) are much close,
confirming the validity of that model. This behavior implies that
1.1
the dependence of the reaction rate on the textural properties of
1.0 the resin.
Experimental data at 25°C

0.9 Experimental data at 35°C To know if the intraparticle diffusion is the rate determining
Experimental data at 45°C step or not the uptake/time data were treated according to Fickian
0.8
diffusion low (Fig. 9a). The Ki value obtained from the slope of the
0.7 straight-line portion is 0.050 mmol/g/min0.5. The high value of Ki
0 1 2 3 4 5 6 7 8 9 10 11 12
indicates the fast transfer and the negative value of X (0.668)
Ce (mM) indicate no boundary layer effect on the rate of adsorption.
Elovich equation was also applied to the adsorption of Mn(II) by
Fig. 3. Adsorption isotherms of Mn(II) onto G@Chs at different temperatures; pH 6;
contact time 150 min. the G@Chs resin (Fig. 9b). The value of a for the adsorption of Mn
 184 K.Z. Al-Wakeel et al. / Journal of Environmental Chemical Engineering 3 (2015) 179–186

Table 1
Langmuir and Freundlich constants for adsorption of Mn(II) on G@Chs resin.

Temp. (
C) Langmuir constants Freundlich constants

2
Qmax, exp (mmol/g) Qmax, calc (mmol/g) KL (L/mmol) R n KF R2
25 1.3 1.377 1.25 0.973 6.48 2.59 0.895
35 1.4 1.485 1.39 0.977 6.64 2.75 0.988
45 1.6 1.683 1.44 0.968 4.47 6.49 0.9

[(Fig._5)TD$IG] [(Fig._7)TD$IG]
0.3 1.4

1.3
0.2
1.2

qe (mmol/g)
1.1
0.1
Log qe

1.0

0.0 0.9
Temperature

25°C 0.8
-0.1 35°C
45°C 0.7

-0.2 0.6
-5 -4 -3 -2 -1 0 0 30 60 90 120 150 180 210
Log Ce t (min)
Fig. 7. Uptake of Mn(II) by G@Chs as a function of time at 25
C; pH 6; initial
Fig. 5. Linear Freundlich isotherms for the adsorption of Mn(II) onto G@Chs at
concentration of 5  103 M.
different temperatures; pH 6; contact time 150 min.

reacting with Mn(II) ions. While the values of b (desorption

constant) is found to be 4.74 g/mmol. The observed high desorption
Table 2 constant compared with that of the adsorption of Fe(III) onto
Enthalpy, entropy and free energy changes for adsorption of Mn(II) ions on G@Chs
G@Chs (3.347) [17] may be due to the fast adsorption/desorption
resin.
equilibrium of Mn(II) on G@Chs. The data obtained indicate that
DH
(kJ/mol) DS
(J/mol/K) DG
(kJ/mol) the studied resin is promising for Mn(II) removal.
298 K 303 K 313 K
5.74 78.49 17.65 18.43 19.22 Comparison of the maximum sorption capacities with other sorbents

Table 4 shows a comparison of the maximum sorption

(II) ions on G@Chs resin is 0.0605 mmol/g/min, This value indicates capacities of materials found in the literature; the best operating
that the initial sorption rate of Mn(II) ions is relatively high, in conditions are also presented. G@Chs have a sorption capacity of
comparison with the previously published one (0.031) for the the same order of magnitude as other sorbents; although Pleurotus
adsorption of Fe(III) onto G@Chs [17]. This may be attributed to the ostreatus (nano-particles) [43], pecan nutshell [44] and black
high concentration of active sites on resin surface allowed for carrot residues (acetic acid-ethanol modified) [45] present better
[(Fig._8)TD$IG]
[(Fig._6)TD$IG] 150
7.35

120
(min g/mmol)

7.30

90
ln KL (L/mol)

7.25

60
7.20
t/qt

30
7.15

0
7.10 0 40 80 120 160 200
0.0031 0.0032 0.0033 0.0034 t (min)
1/T (1/K)
Fig. 8. Pseudo second-order kinetics of the uptake of Mn(II) by G@Chs at 25
C; pH
Fig. 6. Van’t Hoff plots for adsorption of Mn(II) onto G@Chs. 6; initial concentration of 5  103 M.
 K.Z. Al-Wakeel et al. / Journal of Environmental Chemical Engineering 3 (2015) 179–186 185

Table 3
Kinetic parameters for the adsorption of Mn(II) on G@Chs resin.

Pseudo-first order Pseudo-second order Fickian diffusion law Elovich equation

k1 (min 1
) qe, calc (mmol/g) R 2
k2 (g/mmol/ min) qe, calc (mmol/g) R 2
Ki (mmol/g/min 0.5
) X R 2
a (mmol/g/min) b (g/mmol) R2
0.057 0.207 0.141 0.045 1.41 0.998 0.05 0.668 0.959 0.605 4.74 0.996

[(Fig._9)TD$IG] Resin regeneration

(a) 1.4
Regeneration of the resin was carried out using 1 M HCl. The
1.3 regeneration process was repeated for four cycles, the regeneration
efficiency for each adsorption/desorption cycle was found to be
1.2 96.4, 94.1, 93.5%. This indicates that resin has good performance for
repeated use up to at least 3 cycles.
qe (mmol/g)

1.1

1.0 Conclusions

0.9 The results obtained in the present study show that the G@Chs
resin may be considered as a potential biosorbent material for the
0.8 removal of Mn(II) ions from aqueous media. The equilibrium
adsorption data were interpreted via the Langmuir and Freundlich
0.7
models, while the kinetic adsorption data were studied using the
0.6 pseudo-first-order, pseudo-second-order and Elovitch models.
0 2 4 6 8 10 12 14 16 Langmuir provided the best fit of the equilibrium adsorption data
t 0.5 (min) 0.5 while the kinetic data were best fitted by the pseudo-second-order
(b) 1.4 kinetic models. Thermodynamic parameters obtained indicated that
the adsorption process is an endothermic spontaneous reaction. The
maximum uptake value was found to be 1.3 mmol/g at pH 6 and
1.3 25
C. Regeneration of the resin was carried out using 1.0 M HCl. The
regeneration process was repeated for three cycles, the regeneration
1.2 efficiency for each adsorption/desorption cycle was found to be 96.4,
qe (mmol/g)

94.1, 93.5%. This indicates that the resin has good durability as well as
1.1 good efficiency for repeated use.

References
1.0
[1] B. Southichak, K. Nakano, M. Nomura, N. Chiba, O. Nishimura, Phragmites
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0.9
solution, Water Res. 40 (12) (2006) 2295–2302, doi:http://dx.doi.org/10.1016/
j.watres.2006.04.027. 16766011.
[2] A.U. Rajapaksha, M. Vithanage, C. Oze, W.M.A.T. Bandara, R. Weerasooriya,
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ln t (min) [3] H.B. Röllin, C.A. Nogueira, Manganese: environmental pollution and health
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Fig. 9. (a) Intraparticle diffusion and (b) Elovich kinetics of the uptake of Mn(II) by [4] A. Takeda, Manganese action in brain function, Brain Res. Brain Res. Rev. 41 (1)
G@Chs at 25
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12505649.
[5] ATSDR, Toxicological Profile for Manganese, Atlanta, GA, United State, De-
partment of Health and Human Services, Public Health Services, Agency for
Toxic Substances and Disease Registry, 2000.
adsorption capacity, G@Chs has an important advantage because of [6] D.G. Barceloux, Manganese, J. Toxicol. Clin. Toxicol. 37 (2) (1999) 293–307, doi:
it’s fast kinetics. http://dx.doi.org/10.1081/CLT-100102427. 10382563.
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Table 4
Comparison of adsorption capacity for Mn(II) ions with various sorbents.

Sorbent Sorption capacity mg/g (mmol/g) Author

Pure chitin 5.43 (0.09) (Robinson-Lora and Brennan, 2010) [37]
Oxalic acid modified maize husk 8.51 (0.15) (Adeogun et al., 2013) [38]
Formaldehyde modified green tomato husk 19.83 (0.36) (García-Mendieta et al., 2012) [39]
Rice husk 7.7 (0.14) (Krishnani et al., 2008) [40]
Vermiculite (a clay mineral) 31.52 (0.57) (Fonseca et al., 2006) [41]
Poly(protoporphyrin-co-vinylpyridine) 5 (0.09) (Oliveira et al., 2013) [42]
Pleurotus ostreatus (nano-particles) 130.6 (2.37) (Ma et al., 2013) [43]
Pecan nutshell 103.8 (1.88) (Vaghetti et al., 2009) [44]
Black carrot residues (acetic acid–ethanol modified) 387 (7.04) (Güzel et al., 2008) [45]
Glycine modified chitosan 71.4 (1.3) (This work)
186 K.Z. Al-Wakeel et al. / Journal of Environmental Chemical Engineering 3 (2015) 179–186

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