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Article history:
Received 22 November 2014
Received in revised form 10 January 2015
Accepted 27 January 2015
Available online 3 February 2015
Keywords:
Chitosan
Sporopollenin
Heavy metal
a b s t r a c t
Use of natural polymers as biosorbents for heavy metal removal is advantageous. This paper reports a
study aiming to design a novel biosorbent from two biomacromolecules; chitosan, a versatile derivative
of chitin, and sporopollenin, a biopolymer with excellent mechanical properties and great resistance to
chemical and biological attack. Chitosan/sporopollenin microcapsules were prepared via cross-linking
and characterised by employing scanning electron microscopy, Fourier transform infrared spectroscopy
and thermogravimetric analysis. Sorption performance of the microcapsules and the plain chitosan beads
were tested for Cu(II), Cd(II), Cr(III), Ni(II) and Zn(II) ions at different metal ion concentration, pH, amount
of sorbent, temperature and sorption time. The adsorption pattern followed Langmuir isotherm model
and the sorption capacity of the chitosan/sporopollenin microcapsules was found to be Cu(II): 1.34,
Cd(II): 0.77, Cr(III): 0.99, Ni(II): 0.58 and Zn(II): 0.71 mmol g1 . Plain chitosan beads showed higher
afnity for the ions; Cu(II): 1.46, Cr(III): 1.16 and Ni(II): 0.81 mmol g1 but lower for Cd(II): 0.15 and
Zn(II): 0.25 mmol g1 . Sporopollenin enhanced Cd(II) and Zn(II) ions sorption capacity of the chitosan
microcapsules. Chitosan/sporopollenin microcapsules can be used in Cd(II) and Zn(II) metal removal.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Water bodies are contaminated with heavy metal ions through
discharge of waste from many industries such as metal plating,
mining, textile and electric/electronic devices manufacturing [1,2].
The waste efuents from these industrial operations, untreated or
even treated, can have signicant amounts of heavy metal ions.
Heavy metal ions in aquatic systems and ground water pose risks
to the living organisms by accumulating in food chain due to their
mobility, stability and non-biodegradability [3]. When their detrimental effects and toxicity are considered, it is critical to remove
heavy metal ions to save diminishing water resources.
There have been increasing interest and efforts to improve conventional techniques to treat the metal contaminated efuents
efciently. Among the conventional physicochemical methods,
adsorption has been extensively employed because of its ease of
use, effectiveness and feasibility [1,4].
Selection of sorbent is a key parameter when sorbents for
heavy metal removal are designed. In addition to physicochemical
Corresponding author: Tel.: +90 332 223 3852; fax: +90 332 241 2499.
E-mail address: idrissargin@hotmail.com (I . Sargn).
http://dx.doi.org/10.1016/j.ijbiomac.2015.01.039
0141-8130/ 2015 Elsevier B.V. All rights reserved.
2. Experimental
2.1. Materials
Medium molecular weight chitosan was obtained from
SigmaAldrich. Sporopollenin from L. clavatum with 20 m particle size was purchased from Fluka Chemicals. Metal salts
(Cu(NO3 )2 3H2 O, Cr(NO3 )3 9H2 O, Ni(NO3 )2 6H2 O, Zn(NO3 )2 4H2 O)
were purchased from Merck, Cd(NO3 )2 4H2 O was obtained from
SigmaAldrich. Glutaraldehyde (25% in water, v:v) was obtained
from Merck. Double distilled water puried with Barnstead
(Dubuque, IA) ROpure LP reverse osmosis system was used in the
experiments.
231
(Ci Ce )V
W
(1)
232
and asymmetric modes of CH2 group vibration) appeared in spectrum of cross-linked chitosan/sporopollenin microcapsules. These
two peaks were also observed in the presence of metal ions but
with some alterations. These observations demonstrated that the
interaction of metal ions with the microcapsules occurred mainly
via amino, hydroxyl and phenolic groups. Earlier workers studied
interactions of metal ions with raw and modied sporopollenin.
These workers reported that sporopollenin itself had an afnity for
the metal ions due to the functional hydroxyl, carbonyl/carboxyl
and ether moieties on it. Based on ndings reported [34,35] and
the analysis of FT-IR spectra of pristine and treated sporopollenin
(Fig. 2) in this study, it can be commented that functional groups
on sporopollenin particles could also contribute to the sorption of
the metal ions.
3.1.3. Thermogravimetric analysis
The thermal stability of the microcapsules and the beads was
evaluated by TGA (Fig. 4). In the thermogram of the microcapsules,
three decomposition steps were observed. The rst decomposition
step could be resulted from the evaporation of water molecules
[36]; the others can be ascribed to the degradation of the chitosan polymer and the sporopollenin grains within the matrice.
The microcapsules exhibited two maximum decomposition temperatures (DTGmax ) (272.4 and 278.8 C); whereas the chitosan
beads one at lower temperature 269.3 C. In a recent paper by
Fraser et al. (2014) [21], it has been reported that the sporopollenin grains are heat-resistant and the grains start to decompose
at around 300 C. Therefore, the higher DTGmax (278.8 C) could be
corresponded to the degradation of sporopollenin grains. It appears
that sporopollenin grains contributed to the thermal stability of the
microcapsules.
3.2. Effect of the adsorbent dosage on metal uptake
The effect of the amount of chitosan/sporopollenin microcapsules and the chitosan beads on metal sorption was investigated
for each metal ion (Fig. 5). As the sorbent dose was increased, so
did the amount of metal ions sorbed by the microcapsules to a certain extent. Sorption saturation point, where increase in sorbent
dosage did not contribute much to the metal sorption, was different for all the metal ions studied. As seen, such saturation point was
reached at about 0.1500 g of microcapsules or the beads.
3.3. Effect of contact time
Contact time determining studies were conducted for each
metal ion for 6 h (Fig. 6). Initial adsorption rate of Cu(II) ions onto
the microcapsules was relatively higher than the rest; demonstrating rapid uptake process in rst 120 min. Sorption equilibrium for
Cr(III), Zn(II), Cd(II) and Ni ions was attained nearly at 240 min.
3.4. Effect of solution pH on metal sorption
Changes in pH of the metal solution can affect both metal ion
speciation in the solution and the nature of the sorbent especially
through protonation/deprotonation of the functional moieties.
Lower sorption percentage observed in more acidic conditions
(Fig. 7) may be explained by the competition between hydrogen
ions and cationic species for the same binding sites. Presence of
excessive hydrogen ions could lead to protonation of the amino
and hydroxyl groups of chitosan, lowering electron-donating ability of N and O atoms. Additionally, metal binding ability of hydroxyl,
carbonyl and carboxyl groups on sporopollenin [35] could be weakened at lower pH values.
The enhancement observed in sorption capacity of chitosan/sporopollenin microcapsules at higher pHs may be attributed
233
Fig. 1. SEM images of the sporopollenin grains (ad) (magnication: a: 1000, b: 3000, c: 5000 and d: 10000) and chitosan/sporopollenin microcapsules (eh):
(magnication: e: 80, f: 250, g: 1000 and h: 5000).
G = RT lnKC
(2)
G = H T S
(3)
changes (H ) conrming the endothermic nature of the sorption of metal ions onto the microcapsules, the negative values
of G indicated that the sorption process was spontaneous and
thermodynamically feasible at studied temperatures. Additionally,
regarding the high enthalpy changes, particularly in case of Cu(II)
and Cd(II) ions, it appeared that metal sorption primarily occurred
on the surface of the microcapsules rather than within the pores
[39]. Sorption of the metal ions onto the cross-linked chitosan beads
was endothermic. On the other hand, after the incorporation of
sporopollenin grains into the chitosan microcapsules, Cu(II) and
Cd(II) sorption occurred exothermically. The sorption of Cd(II) and
Zn(II) onto the beads were nonspontaneous, but onto the microcapsules the sorption was opposite in nature. Also, considering the
increase in negative values of G with increasing temperature for
the ions other than Ni(II) ions, it can be suggested that metal ion
sorption on the microcapsules was more efcient at higher temperatures. The standard entropy changes were found to be positive,
indicating the increase in the entropy during the adsorption of the
ions onto the chitosan/sporopollenin microcapsules. Similar trend
was observed for the Cu(II), Cd(II) and Cr(III) ions onto the chitosan beads with exception Ni(II) and Zn(II) ions. The entropy of the
equilibrium system decreased upon sorption of these ions onto the
cross-linked chitosan beads. This complex thermodynamic nature
of the different ions onto the same sorbent has been dealt with in
a recent paper by Liu and Lee [40]. The authors performed metaanalysis to critically assess these phenomena and concluded that
the thermodynamic assessment of any metal or dye-sorbent system
dees simple explanations and needs clarifying by more elaborate
experimental study.
(4)
logKC =
S H
2.303R
2.303RT
1
n
log Ce
(5)
234
Fig. 2. FT-IR spectra of sporopollenin (a), methanol-NaOH treated sporopollenin (b), chitosan (c) and chitosan/sporopollenin microcapsules (c).
Table 1
Thermodynamic parameters for the adsorption of Cu(II), Cd(II), Cr(III), Ni(II) and Zn(II) on sporopollenin/chitosan microcapsules and chitosan beads.
Metals
Sorbents
H (J mol1 )
S (J K1 mol1 )
G (J mol1 )
T = 298.15 (K)
T = 308.15 (K)
T = 318.15 (K)
Cu(II)
Microcapsules
Beads
3626.650
2364.790
14.112
15.835
7834.190
2356.560
7975.310
2514.910
8116.430
2673.270
Cd(II)
Microcapsules
Beads
1748.600
6933.527
3.676
7.927
2844.730
4569.999
2881.500
4490.725
2918.260
4411.452
Cr(III)
Microcapsules
Beads
2115.865
275.924
10.397
1.762
984.125
249.304
1088.100
266.921
1192.070
284.573
Ni(II)
Microcapsules
Beads
5323.172
385.834
16.027
8.578
544.734
2943.469
368.464
3029.252
224.195
3115.036
Zn(II)
Microcapsules
Beads
5736.771
2814.771
19.512
2.068
80.706
3431.343
275.826
3452.023
470.945
3472.703
235
Fig. 3. FT-IR spectra of chitosan/sporopollenin microcapsules loaded with copper(II) (a), zinc(II) (b), cadmium(II) (c), chromium(III) (d), nickel(II) (e).
with qe , amount of solute adsorbed in mmol g1 , Ce , the equilibrium concentration of the adsorbate in mM L1 and KF
(mmol g1 ) and n Freundlich constants denoting adsorption
capacity and intensity of adsorption, respectively.
ii. The Langmuir model:
Ce
1
Ce
= 0 + 0
qe
Q
Q b
(6)
with qe , amount of solute adsorbed in mmol g1 , Ce , the equilibrium concentration of the adsorbate in mmol L1 , Q0 (in
mmol g1 ) and b (in L mmol1 ) Langmuir constants related to
adsorption capacity and energy of adsorption.
iii. The DR model:
ln qe = lnXm K2
(7)
(8)
(9)
236
Fig. 4. TG-DTG curves of chitosan/sporopollenin microcapsules (a) and chitosan beads (b).
Fig. 5. Effect of the adsorbent dosage on metal uptake; chitosan/sporopollenin microcapsules and chitosan beads (at initial pH; metal concentration 10 mg L1 ; volume of
solution 25 mL; temperature 25 C; contact time 4 h).
Fig. 6. Effect of contact time on metal uptake; chitosan/sporopollenin microcapsules and chitosan beads (at initial pH; metal concentration 10 mg L1 ; volume of solution
25 mL; temperature 25 C; adsorbent dosage 0.15 g).
Fig. 7. Effect of pH on metal uptake; chitosan/sporopollenin microcapsules and chitosan beads (metal concentration 10 mg L1 ; volume of solution 25 mL; temperature 25 C;
contact time 4 h; adsorbent dosage 0.15 g).
0.866
0.942
7.906
10.000
0.008
0.005
0.954
0.340
0.571
0.811
0.853
0.296
60.000
460.900
0.940
0.954
0.707
0.246
1.028
1.153
2.113
0.552
Microcapsules
Beads
Microcapsules
Beads
Ni(II)
Zn(II)
2.421
3.205
0.823
0.890
50.480
10.690
0.831
0.861
10.000
5.000
0.005
0.020
0.728
0.444
0.816
0.234
0.649
0.874
108.500
3.449
0.991
0.949
0.583
0.813
1.667
2.723
microcapsules
Beads
Cr(III)
4.274
1.362
0.739
0.910
72.886
2.398
0.965
0.979
7.906
6.455
0.008
0.012
1.084
1.359
0.904
0.948
0.983
1.222
51.190
25.090
0.991
0.988
0.993
1.164
12.050
0.321
Microcapsules
Beads
Cd(II)
3.300
2.198
0.937
0.941
47.288
38.805
0.931
0.954
6.455
6.455
0.012
0.012
1.902
0.187
0.379
0.848
1.367
0.170
40.710
25.880
0.944
0.959
0.773
0.152
14.388
5.888
Microcapsules
Beads
Cu(II)
1.406
2.119
0.878
0.917
85.930
0.827
0.973
0.972
11.180
7.906
0.004
0.008
1.935
1.191
0.799
0.717
1.157
1.621
1156.000
23.340
0.955
0.916
1344.086
60.650
1.344
1.456
0.833
0.990
R
Qs (mmol/g)
Ks (L/mmol)
R
b (L/mmol)
Q0 (mmol/g)
R
n
KF (mmol/g)
Sorbents
Metal ions
2.105
1.706
Xm (mmol/g)
DR
Scatchard
Langmuir
Freundlich
Isotherms
Table 2
The parameters of Freundlich, Langmuir, Scatchard and DR isotherms for sorption of Cu(II), Cd(II), Cr(III), Ni(II) and Zn(II) on chitosan beads and sporopollenin/chitosan microcapsules.
K (mol2 /kJ2 )
E (kJ/mol)
R2
237
238
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