Carbohydrate Polymers 207 (2019) 663–674

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

A chitosan-thiomer polymer for highly efficacious adsorption of mercury T

⁎
Rahul Bhatt, P Padmaj
Department of Chemistry, Faculty of Science, M. S. University of Baroda, Vadodara, India

A R T I C LE I N FO A B S T R A C T

Keywords: Thiomers have recently attracted attention as effective adsorbents for Hg2+. In the present study a chitosan-
Thiomer thiobarbituric acid based thiomer(CTG) was investigated as a potential adsorbent for elemental mercury (Hg°),
Chitosan inorganic mercury (Hg2+) and methyl mercury (CH3Hg+). CTG was characterized by Fourier transform infrared
Thiobarbituric acid spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray
Elemental mercury
spectroscopy (EDX), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Adsorption
Methyl mercury
Inorganic mercury
experiments were performed to optimize the parameters for maximum removal of Hg°, Hg2+ and CH3Hg+. The
experimental data fitted well to Freundlich isotherm and pseudo second order kinetic models with high R2 and
minimal error function values. The maximum adsorption capacities were determined to be 1367 ± 96.9,
2493 ± 174.6 and 2531 ± 178.4 mg/g for Hg°, Hg2+ and CH3Hg+ respectively. Quantitative desorption of
Hg°, Hg2+ and CH3Hg+ from CTG could be performed using 0.01 N thiourea, 0.01 N HClO4 and 0.2 N NaCl
respectively.

1. Introduction organic mercury species and is ubiquitous in the aquatic environment

Mercury and its related compounds are of serious concern to all
living organisms and the environment when discharged into industrial
waste water and natural water bodies due to their high toxicity, vola-
tility and persistence. Although the use of mercury has decreased in
industry, its overall emission is still a health hazard (Lu, Jiang, Sun,
Wang, & Zhang, 2014). This has resulted in restriction of the con-
centration of mercury in drinking water to 1 μg L−1 and in waste dis-
charge to 5 μg L−1 respectively by regulatory bodies such as The Eur-
opean Union and the US Environmental Protection Agency (EPA). The
World Health Organisation (WHO) has also restricted the concentration
of mercury in drinking water to nil and in waste discharge to
0.0001 ppm respectively (Pillay, Cukrowska, & Coville, 2013).
Hg (II) is the most toxic as it binds to the cysteine residue of protein
chains through the strong Hg–S bond. The waste waters emanating
from electroplating, metal finishing operations, electronic–circuit pro-
duction, steel and nonferrous processes, chemical, pharmaceutical
production industries, chlor-alkali, fertilizer, pulp and paper, plastic,
battery manufacturing, oil refining, paints and electrical components
are the major sources of Hg (II) in the environment. In addition, mer-
cury can be strongly absorbed but slowly eliminated by biological or-
ganisms or tissues, causing serious threat to the health of people and
wildlife. The mercury species can be transformed into methylmercury
by microorganisms under aerobic conditions. Methyl mercury is a toxic
resulting in bioaccumulation in fish and biomagnification in the food
chain (Kolya, Das, & Tripathy, 2014; D. Zhang, Yin, & Liu, 2017).
Several waste water treatment techniques such as chemical pre-
cipitation, coagulation, ion exchange, chemical reduction, membrane
separation, biological treatment, solid phase extraction, and adsorption
(Da̧browski, Hubicki, Podkościelny, & Robens, 2004; Gao, Sun, Zhu, &
Chung, 2014; Meng, Korfiatis, Christodoulatos, & Bang, 2001;
Srivastava & Majumder, 2008)have been adapted in recent years. The
removal of elemental mercury (Hg°) is very difficult because of its high
volatility and low solubility in water (Wang, Liu et al., 2014). State-of-
the-art technologies for elemental mercury abatement mainly focus on
two methods: adsorption and oxidation.
Among these methods, adsorption is an effective and versatile
method that is capable of removing trace levels of heavy metal ions
from dilute solutions (Li et al., 2015). The materials used in adsorption
of Hg° mainly include activated carbon, modified activated carbon, fly
ash and modified fly ash (Zhao, Hao, Zhang, & Zhou, 2014).
According to the HSAB theory, Hg2+is classified as a soft ion. Soft
ions form very strong bonds with -CN, -SR, -SH, -NH2 and imidazole, i.e.
groups containing nitrogen and sulphur atoms. Therefore, chitosan with
-NH2 group shows very high adsorption capacity to mercury ions
(Volesky, 1990). The presence of –NH2 groups on the surface of chit-
osan gives a cationic behavior to the biopolymer which provide ex-
cellent sorption capacities. The adsorption capacity of chitosan can be

⁎
Corresponding author.
E-mail address: padmaja.sudhakar-chem@msubaroda.ac.in (P. P).

https://doi.org/10.1016/j.carbpol.2018.12.018
Received 22 June 2018; Received in revised form 3 December 2018; Accepted 9 December 2018
Available online 12 December 2018
0144-8617/ © 2018 Elsevier Ltd. All rights reserved.
R. Bhatt, P. P
well enhanced by grafting as well as crosslinking using reagents such as
epichlorohydrin with benzaldehyde to protect amino group and in-
crease swelling (Ruiz, Sastre, & Guibal, 2000), glutaraldehyde with
barbituric acid by providing additional active sites for binding
(Kushwaha & Sudhakar, 2011) diepoxy compound [1,2:7,8-diepox-
yoctane (DEO)] (Vakili et al., 2018) by making the adsorbent more
porous and hydrophilic, genepin (Rocha et al., 2016) by increasing the
swelling capacity of chitosan, etc. Thiomers are a new generation of
polymers being used for mucoadhesive drug delivery systems (Kast &
Bernkop-Schnürch, 2001). A chitosan thiomer derived from thiourea
has recently been reported as adsorbent and sensor for mercury
(Chauhan, Singh, & Singhal, 2015).
In this work, glutaraldehyde cross-linked 2-thiobarbituric acid-
grafted chitosan (CTG) has been synthesized, characterized and eval-
uated for the removal of elemental mercury (Hg°), inorganic mercury
(Hg2+) and methyl mercury (CH3Hg+). The experimental parameters
have been optimized for their maximum removal.
2. Materials and methods
2.1. Chemicals
Chitosan (from crab shells) (75∼85% deacetylated) (mean mole-
cular weight ∼ 190,000–310,000 Da reported by viscometric method)
was purchased from Sigma-Aldrich. 2-Thiobarbituric acid (98% and
molecular weight = 144.15 g/mol) and Glutaraldehyde (25% in water
and molecular weight = 100 g/mol) were purchased from
Spectrochem, NaOH (AR grade and molecular weight = 40 g/mol) and
Glacial acetic acid (AR grade and molecular weight = 60.05 g/mol)
were purchased from S D Fine-Chem Limited. Coomassie brilliant blue
G-250 (AR grade and molecular weight = 825.97 g/mol) was pur-
chased from National Chemicals, Vadodara, Phosphoric acid (AR grade
and molecular weight = 97.99 g/mol)was purchased from S D Fine-
Chem Limited, Malonaldehyde bis(dimethyl acetal) (AR grade and
molecular weight = 164.20 g/mol) was purchased from Sigma. All
chemicals were used as received without any further purification.
2.2. Preparation of chitosan-thiobarbituric acid-glutaraldehyde adsorbent
(CTG)
For the preparation of CTG thiomer, a 100 mL solution of 1% chit-
osan in 1% glacial acetic acid was prepared by dissolving 1 g chitosan
flakes in 1% glacial acetic acid. A 100 mL of 1% solution of 2-thio-
barbituric acid in double distilled water was prepared. Both the solu-
tions were mixed in a volume ratio of 1:1 and then stirred for 4 h at
50–55 °C till a yellow coloured solution was obtained. Further, 100 mL
of 0.1% glutaraldehyde solution was added to the yellow coloured so-
lution and the reaction mixture was further allowed to stir for 4 h at
50–55 °C. The solution obtained was injected dropwise into 100 mL
0.4 N NaOH solution for the formation of beads. The obtained beads
were then filtered, washed with double distilled water until neutral,
and then air-dried. The beads were then crushed well and used as such
for mercury uptake studies.
2.3. Adsorbent characterization
The adsorbent CTG was characterized using Ultra-violet Visible
Spectrscopy (UV–vis), Fourier transform infrared spectroscopy (FTIR),
X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-
Dispersive X-ray spectroscopy (EDX), Differential Scanning Calorimetry
(DSC), Thermal Gravimetric Analysis (TGA), Nuclear Magnetic
Resonance (NMR) and Zeta Potential studies.
The UV analysis of the adsorbent was done using JASCO V630
model UV–vis Spectrophotometer within the range 200–1100 nm while
FTIR analyses of CH and CTG were obtained using a Perkin-Elmer RX1
model in the wave number range 500 to 4000 cm−1. The SEM and
664
Carbohydrate Polymers 207 (2019) 663–674
EDAX analyses of the adsorbent and metal loaded adsorbent were done
using JEOL make model no. JSM 5610 L V SEM instrument. The NMR
analysis of the adsorbent was done using Bruker Avance-400 MHz in-
strument and DSC analysis was done using METTLER 822E DSC in-
strument from 30 to 550 °C under nitrogen atmosphere.
Thermogravimetric analysis of CTG was obtained using EXSTAR6000
TG/DTA 6300 instrument from 30 to 550 °C under nitrogen atmo-
sphere. The Zeta Potential measurement of CTG was done using
Zetasizer ZetaPlus 90Plus/BI-MAS BrookHaven instrument within the
range of −150 mV to + 150 mV. The extent of crosslinking was cal-
culated using the Bradford Assay (Abraham, Rajamanickam, &
Srinivasan, 2018) wherein the amount of free amino groups in the
chitosan material before (Ci) and after cross-linking (Cf) was considered
to be proportional to the optical absorbance of the solution. The %
cross-linking index was calculated using the following equation
(Ci − Cf )
% Cross − linking index = × 100 %
Ci (1)
Where:
Ci = Amount of free amino groups in chitosan before cross-linking
Cf = Amount of free amino groups in cross-linked chitosan
The extent of the grafting of thiobarbituric acid onto chitosan was
calculated using the TBARS method.
XRD analyses of the adsorbent and metal loaded adsorbents were
obtained using BRUKER D2 PHASER model. The radiation source used
was Cu-K-alpha-1.5414 Å. The crystallinity index was calculated from
the Eq. (2):
I − Iam ⎤
Crystalline Index (%) = ⎡ 110 * 100
⎣ I110 ⎥
⎢ ⎦ (2)
Where I110 denotes the maximum intensity at ∼ 20° and Iam is the in-
tensity of amorphous diffraction at 14° (Caro León et al., 2017).
2.4. Adsorption studies
2.4.1. Batch adsorption experiments
The adsorption study of Hg°, Hg2+ and CH3Hg+ was carried by
batch process. Stock solutions of mercury were prepared by dissolving
1.379 g (98% pure) and 1.264 g (98% pure) of mercury (II) chloride and
methyl mercuric(II) chloride respectively in double distilled water to
make up 1 L of 1000 ppm of each solutions. Working standards were
prepared by diluting different volumes of the stock solution to obtain
the desired concentration.
The experimental setup for the Elemental mercury uptake is as
shown in the Scheme 1. A 10 mL solution of Hg2+ of known con-
centration was taken in the reaction flask to which 3% NaBH4 solution
in 1% NaOH was added, to obtain Hg° of desired concentration. N2 gas
at a pressure of 25 psig was purged through the reaction vessel at a flow
rate of 0.350 L/min to carry the generated Hg° in the range 13.9 to
1399 mg/m3 into the adsorbent tube containing 0.01 g of CTG for a
predetermined time interval. The unadsorbed mercury that reached the
Quartz Tube Atomizer (QTA) was measured by AAS. The effect of dose
was also studied where the amount of CTG was varied from 0.01-0.05 g.
The Hg° removal efficiency was calculated as follows (Eq. (3)):
Removal Efficiency (%) = (C0 − C /C0)* 100 % (3)
where C0 is the inlet concentration of Hg° and C is the outlet con-
centration of Hg°
The adsorption potential of CTG for Hg° was investigated by passing
the mercury inlet gas through the sorbent bed into the analytical system
for finding the unadsorbed mercury until the inlet mercury concentra-
tion and the unadsorbed mercury was observed to be the same.
The Mercury Mass Balance expression (Eq. (4)) was used to show
that the mass of inflow mercury was equal to sum of mass of mercury
adsorbed plus the mass of mercury in off-gas (P. Sun et al., 2017).
R. Bhatt, P. P Carbohydrate Polymers 207 (2019) 663–674

Scheme 1. Elemental Mercury Uptake Procedure.

Fig. 1. (a) Electronic Absorption Spectra, (b) FTIR of CH and CTG, and (c) XRD analysis.

665
R. Bhatt, P. P Carbohydrate Polymers 207 (2019) 663–674

Fig. 2. a) SEM image of CH; b) SEM image of CTG ; c) EDX image of CTG; d) EDX image of CTG-Hg°; e) EDX image of CTG-Hg2+ and f) EDX image of CTG-CH3Hg+.

t = tf t = tf
m3 ⎤ m3 ⎤ contents of the flask were filtered and the filtrate was analyzed for the
∑ Cin ⎡ mg Hg
3
⎤ * Q⎡ * dt = ∑ Cout ⎡ mg Hg
3
⎤ * Q⎡ * dt presence of unadsorbed Hg2+ by CVAAS technique (AAnalyst 200,
t=0 ⎣ m ⎦ ⎢ min ⎦
⎣ ⎥ t=0 ⎣ m ⎦ ⎢ min ⎦
⎣ ⎥
Perkin Elmer). All the experiments were conducted in triplicate, and the
+ mad * Cad (4) average results are reported. The mercury uptake by CTG was calcu-
lated as follows (Eq. (5)):
where:
Cin, Cout: Initial (mg/m3) and off-gas mercury concentration, re- qe = (Ci − Ce )/ m (5)
spectively.
where Ci is the initial concentration of metal ion (mg/L), Ce is the
Q: Gas flow, (mL/min = m3/min).
equilibrium concentration of metal ion (mg/L), m is the mass of ad-
tf: Time of adsorption experiment, (min).
sorbent (g/L), and qe is the amount of metal ion adsorbed per gram of
mad: Mass of adsorbent, (g).
adsorbent. The experiments performed without adsorbent were treated
Cad: Mercury concentration in adsorbent, (mg Hg/gad).
as blank.
Experiments were performed to study the effect of various para-
Adsorption isotherms were determined by the treatment of 0.01 g of
meters such as pH, dose, temperature and initial concentration of the
adsorbent under study with metal solution having an initial con-
adsorbate for the removal of Hg2+ and CH3Hg+ on CTG. For each ex-
centration varying from 100 to 1000 ppm on a rotary shaker. After
periment, 25 mL of Hg2+ and CH3Hg+ solutions of known initial con-
shaking, the contents of the flasks were filtered. The concentration of
centration and desired pH were taken in a 100 mL stoppered conical
metal remaining in the solution was determined by CV-AAS technique.
flask. A suitable adsorbent dose was added to the solution, and the
Attempts were made to fit the equilibrium metal sorption isotherm
mixture was agitated at constant speed at the desired temperature. The
data to models like Freundlich (Aljeboree, Alshirifi, & Alkaim, 2017),

666
R. Bhatt, P. P
Fig. 3. NMR analysis of CTG (in CD3COOD).
Langmuir (Belhachemi & Addoun, 2011), Temkin (Geethamani,
Ramesh, Gandhimathi, & Nidheesh, 2013) and Halsey (Singha & Das,
2013) for the better understanding of the processes governing adsorp-
tion of metal onto the adsorbent under study. Further the mechanism
underlying the sorption process was investigated by fitting the sorption
data to pseudo-first order(lagergren) (Kumar, 2006), pseudo-second
order (Kakavandi et al., 2015), elovich (Skodras, Diamantopoulou,
Pantoleontos, & Sakellaropoulos, 2008) and Liquid film diffusion
models (Karmaker, Sen, & Saha, 2015) were used as kinetic models.
2.4.2. Determination of degree of cross linking by Bradford technique
For the preparation of Bradford reagent, 5 mg of coomassie brilliant
blue G-250 was dissolved in 2.5 mL of 95% ethanol. To this solution,
5 mL of phosphoric acid was added. The resulting solution was diluted
to 50 mL with distilled water (Abraham, Rajamanickam et al., 2018).
A 1 mL solution of 1% chitosan/ cross-linked chitosan solution in
1% v/v acetic acid was taken to which 9 mL of Bradford reagent was
added and mixed well. The absorbance of the resulting solutions was
measured at 595 nm using UV Visible spectrophotometer (Jasco V-630).
A solution containing 1 mL of 1% v/v acetic acid and 9 mL of Bradford
reagent was taken as blank.
2.4.3. Thiobarbituric acid reactive substance (TBARS) assay for TBA
Standard stock solutions of TBA (1 mM) and malondialdehyde
(MDA) (1 mM) were prepared in 50% glacial acetic acid (Zeb & Ullah,
2016). From the stock solution, different concentrations of 0.2, 0.4, 0.6,
and 0.8 mM TBA were prepared. The calibration curve was constructed
for TBA in the concentration range of 0.2 to 1.0 mM. Standard solutions
(5 mL each) of 0.2–1 mM TBA was mixed with 5 mL standard solution of
1 mM MDA and heated in boiling water bath for 1 h. For the extraction
of TBA from the adsorbent, 0.1 g of adsorbent was taken in 10 mL
glacial acetic acid and heated in boiling water bath for 1 h. About 5 mL
667
Carbohydrate Polymers 207 (2019) 663–674
of the extract was mixed with 5 mL of 1 mM MDA solution and again
heated in boiling water bath for 1 h. The solutions were then cooled,
filtered and made upto definite volume. The absorbance of the resultant
solutions was measured at 530 nm using Jasco V-630 spectro-
photometer. A solution of 50% glacial acetic acid was used as blank.
2.5. Statistical analysis
In order to ensure the reproducibility of results, experiments were
performed in triplicate and data were presented as the mean value from
these independent experiments. The experimental errors were esti-
mated and standard deviations (SD) and error bars were indicated
wherever necessary. SD was calculated using the Eq. (6).
N
1
SD = ∑ (xi − x¯)2
N i=1 (6)
Further, to identify the best fitting adsorption isotherm and kinetic
model error functions such as Chi-square (χ2) (Eq. (7)), Root Mean
Square Error (RMSE) (Eq. (8)), Average Relative Error (ARE) (Eq. (9)),
and Sum of Absolute Errors (SAE) (Eq. (10)) were used to evaluate the
isotherm and kinetic models. The more the agreement between the
experimental and calculated data for a particular model, the lower are
the error function values indicating the goodness of fit of the model.
The error functions used are listed below:
(qe, exp − qe, cal )2
Chi square statistic = x 2 = ∑ qe, cal
(7)
N
1
RMSE = ⎛ ⎞ *∑ (qe, exp − qe, cal )2
⎝ N − 2⎠ 1 (8)
R. Bhatt, P. P Carbohydrate Polymers 207 (2019) 663–674

Fig. 4. a) DSC thermogram of CH, b) DSC thermogram of CTG; c) TG and DTG thermograms of CH, d) TG and DTG thermograms of CTG.

Fig. 5. (a) Adsorption Potential of CTG for different metal ions (Volume - 25 mL; pH - 4; Dose - 0.01 g; Time - 3 h and Temp - 30°C); (b) Adsorption Capacity Curve for
Hg° (Dose - 0.01 g; Time - 10 min. and Temp - 30°C) with ± 5% error bar.

N calculated values and N is the number of observations in the experi-

100
ARE = ⎛ ⎞ * ⎛∑ (|qe, exp − qe, cal|/ qe, exp) ⎞⎟ mental data (El-Zawahry, Abdelghaffar, Abdelghaffar, & Hassabo,
⎝ N ⎠ ⎜⎝ 1 ⎠ (9)
2016; Hamzaoui, Bestani, & Benderdouche, 2017).
N
⎛ ⎞
SAE = ⎜∑ (|qe, exp − qe, cal|) ⎟
⎝ 1 ⎠ (10)

Where the subscripts “exp” and “calc” show the experimental and

668
R. Bhatt, P. P Carbohydrate Polymers 207 (2019) 663–674

Table 1 Table 2
Sorption Isotherms. Sorption Kinetics.
CTG-Hg° CTG-Hg2+ CTG-CH3Hg+ CTG-Hg° CTG-Hg2+ CTG-CH3Hg+

Experimental Experimental
qe (mg g−1) 1379 ± 97.7 2497 ± 176.7 2496 ± 176.6 qe 1379 249.9 249.9
Freundlich Pseudo-First Order
qe (mg g−1) (calc.) 1367 ± 96.9 2493 ± 174.6 2531 ± 178.4 qe 5.44 20.59 181.2
kf (L g−1) 228.6 ± 7.01 2378 ± 90.7 2010 ± 67.2 K 0.68 0.01 0.02
N 1.54 ± 0.05 2.76 ± 0.11 1.47 ± 0.05 R2 0.9981 0.8307 0.9996
R2 0.9974 0.9956 0.9966 SD 0.0205 0.2943 0.0097
SD 0.0051 0.0066 0.0059 x2 1.89 × 106 9.75 × 104 5.87 × 104
x2 0.4904 1.284 1.122 RMSE 1.50 × 103 337.2 283.9
RMSE 14.01 28.23 28.39 ARE 124.9 98.71 98.60
ARE 0.7785 1.041 1.010 SAE 8610 953.6 786.9
SAE 44.58 96.95 102.5 Pseudo-Second Order
Langmuir qe 1370 253.2 296.7
qe (mg g−1) (calc.) 154.8 ± 23.3 6244 ± 407.6 3002 ± 252.8 K −0.12 0.40 9.45 × 10−5
kL (L mmol−1) 19.59 ± 1.23 6.55 ± 0.07 2.07 ± 0.07 R 2
0.9998 0.9997 0.9995
R2 0.9973 0.9889 0.9994 SD 3.397 × 10−5 0.0055 0.0107
SD 1.150 × 10−5 1.570 × 10−4 3.010 × 10−6 x2 0.2162 2.755 0.3955
x2 4.482 × 103 6.710 280.9 RMSE 7.701 18.67 5.677
RMSE 440.7 2493 347.2 ARE 0.6012 4.865 2.147
ARE 71.09 288.1 25.56 SAE 41.45 46.30 15.20
SAE 1519 9346 1094 Elovich
Temkin qe 65.78 512.1 163.8
qe (mg g−1) (calc.) 1351 ± 96.7 4636 ± 326.8 2841 ± 249.5 1.16 0.11 0.016
-ΔH (kJ mol−1) 0.56 ± 0.09 19.27 ± 0.54 5.69 ± 0.10 A 9.06 × 1031 1.782 × 1023 4.99
kT (L mmol−1) 0.44 ± 0.07 18.73 ± 0.53 4.65 ± 0.08 R2 0.9811 0.9417 0.9998
R2 0.9913 0.9984 0.9991 SD 0.0439 2.179 0.7853
SD 23.42 15.55 13.98 x2 1.86 × 105 548.7 310.0
x2 1.344 4633 175.0 RMSE 1.55 × 103 372.1 121.7
RMSE 23.42 1507 285.6 ARE 133.4 109.0 45.17
ARE 1.326 70.28 11.02 SAE 9197 1052 344.1
SAE 77.47 1.030 × 104 1479 Liquid film diffusion model
Halsey qe – −1278 −4782
qe (mg g−1) (calc.) 1.40 ± 0.16 0.66 ± 0.02 0.72 ± 0.05 Klfd – 0.01 0.017
kH (L g−1) 0.36 ± 0.01 0.36 ± 0.01 0.36 ± 0.01 R2 – 0.8307 0.9996
nH −1.54 ± 0.05 −2.76 ± 0.11 −1.47 ± 0.05 SD – 0.2943 0.0224
R2 0.9974 0.9957 0.9967 x2 – 5134 8816
SD 0.0118 0.0153 0.0135 RMSE – 1290 3815
x2 1.48 × 106 7.08 × 106 7.19 × 106 ARE – 319.1 843.4
RMSE 593.2 1069 2618 SAE – 3125 7772
ARE 99.86 99.92 99.93
SAE 2080 3746 3744 qe (mg/g), K2 (g/mg min), K1 (min−1), Kip (mg/g min1/2), β (g/mg), α (mg/g
min).

3. Result and discussion
3.1. Adsorbent material characteristics
3.1.1. Electronic absorption spectra, FTIR and XRD analysis
The UV–vis absorption spectra of CTG and mercury loaded CTG are
shown in Fig. 1(a). CTG shows an intense band at ∼227 and 279 nm
which are characteristic of TBA and can be ascribed to π→π* transitions
while the peaks observed at ∼ 308 and 336 nm can be assigned to n→
π* transitions (Méndez et al., 2007). An absorption peak was further
observed at 547 nm similar to the spectra obtained on reaction of TBA
with pyrimidine compounds (Knight, Pieper, & McClellan, 1988). A
shift and change in intensity of the peaks was observed in the absorp-
tion spectra after adsorption of mercury onto CTG.
The FTIR spectra of CH and CTG and mercury loaded CTG are
shown in Fig. 1(b) and the detailed attributions of the bands are shown
in Table S5 (Supporting Information).
In the FTIR spectra of CH the stretching vibrations of −OH and
-NH2 groups were observed at 3424 cm−1 while the band observed at
2878 cm−1 was assigned to C–H stretching. Further the band at
1658 cm−1 was attributed to amide I and a comparatively less intense
primary amine band at 1597 cm−1.
CTG shows the stretching vibrations of −OH and -NH2 groups at
3430 cm−1, amide band at 1645 cm−1 which is shifted from 1658 cm−1
of chitosan. Other characteristic bands of chitosan did not exhibit much
change but all bands were of reduced intensity (Oliveira, Martins,
Mafra, & Gomes, 2012). Furthermore, the presence of sharp intense
peak at 770 cm-1 assigned to C–S stretching and the presence of a weak
characteristic band at 2314 cm-1 that can be attributed to the stretching
vibration of the -SH group are indicative of the enol-thiol structure of
thiobarbituric acid in CTG (Zaki & Mohamed, 2000).
The XRD pattern (Fig. 1(c)) of CTG exhibited a broad peak at 2θ =
∼20° indexed as 101 plane of crystal form I (Sashikala & Shafi, 2014)
due to the amorphous state of chitosan. Two new peaks at 35° and 38°
not attributed to chitosan were observed in CTG. The crystalline index
was calculated to be 40.89% and the crystallite size calculated using
Scherrer's Formula (Barabás, Czikó, Dékány, Bizo, & Bogya, 2013) was
found out to be 0.81 nm for the peak at 20.33°.
The degree of cross linking in CTG was calculated to be 24% with
incorporation of 0.92 percent TBA.
3.1.2. SEM and EDX analysis
The SEM micrograph images indicated that CTG displayed a com-
pact, rigid and fibrous structure. The EDX spectra showed the presence
of sulphur in CTG indicating the grafting of 2-thiobarbituric acid with
chitosan in the adsorbent. Also, the presence of mercury peaks evi-
dences the mercury uptake by CTG (Fig. 2).
3.1.3. NMR analysis
The 1H-NMR spectrum of CTG (Fig. 3) presented a peak at 2.0 ppm
attributed to CH3 of the N-acetylated glucosamine residue and CH3 of

669
R. Bhatt, P. P
Fig. 6. (a) Desorption Studies with ± 5% error bar (Volume - 25 mL of the desired eluent; Dose - 0.05 g; Time - 3 h and Temp - 30 °C); (b) Adsorption Cycles and (c)
Interference of Different Metals on adsorption of mercury by CTG (Volume - 25 mL; pH - 4; Dose - 0.01 g; Time - 3 h and Temp - 30 °C).
acetic acid (from synthesis and from deutero solvent), a signal at
3.18 ppm due to 2 protons at H2 of glucosamine (Kasaai, 2010), while
the peaks between 3.5 and 4.0 ppm corresponded to the hydrogen
atoms bonded to C3, C4, C5 and C6 anomeric carbons of the gluco-
pyranose ring and methylene protons of thiobarbituric acid. The
anomeric proton of carbon (C1) resulted in a signal at 4.17 ppm while
the signal at 5.029 ppm can be attributed to C5 proton of pyrimidine
ring in thiobarbituric acid and HOD (from synthesis and from deutero
solvent). The weak intensities of the peaks at 3.0–3.8 ppm indicated
that the glucosamine groups were involved in the cross-linking process
with the glutaraldehyde and thiobarbituric acid.
3.1.4. DSC and TGA analysis
DSC analysis (Fig. 4(a)) of CH showed an endothermic peak at
113 °C while CTG exhibited the peak at 136 °C (Fig. 4(b)) attributed to
loss of water and other volatile material. An exothermic peak was ob-
served in CH at 306 °C thermal decomposition of amino and N-acetyl
residues while two exothermic peaks were observed in CTG at 261 and
268 °C due to decomposition of thiobarbituric acid moiety and further
degradation of cross linking of chitosan respectively (Golovnev,
Molokeev, Tarasova, Atuchin, & Vladimirova, 2014).
The TG-DTA analyses of CH and CTG are shown in the figures
(Fig. 4(c) and (d)). The loss in weight upto 200 °C can be attributed to
670
Carbohydrate Polymers 207 (2019) 663–674
loss of water molecules. The 2nd weight loss at 270 °C in CTG as com-
pared to 294 °C in CH could be probably due to degradation of thio-
barbituric acid followed by deacetylation and degradation of chitosan.
The lower overall weight loss in CTG (65%) as compared to CH (72%)
in CH can be attributed to crosslinking of CH (Prakash, Vijayalakshmi,
& Sudha, 2011).
3.2. Batch adsorption experiments
3.2.1. Adsorption potential of CTG
The uptake of different heavy metals such as inorganic mercury,
methyl mercury, copper, cadmium and zinc onto CTG individually was
studied (Fig. 5(a)). CTG (0.01 g) was equilibrated with 100 ppm metal
ion under study at pH 4 in 25 mL solution at pH 4 for 3 h on orbital
shaker at 200 rpm at 30 °C. It was observed that the adsorption of Hg2+
and CH3Hg+ was quantitative and much higher as compared to other
metals. It was observed that as the concentration of Hg° was increased
from 139 to 1395 mg/m3, almost all the vapors were adsorbed onto the
surface of the adsorbent and the residual concentration increased at
high concentrations of Hg° (Fig. 5(b)).
3.2.2. Effect of pH
The effect of pH of solution on the adsorption of mercury onto CTG
R. Bhatt, P. P Carbohydrate Polymers 207 (2019) 663–674

Fig. 7. Proposed structure of CTG and its binding mechanism with mercury species.

was investigated (Fig. S1(a)) (Supporting Information).
It was observed that the adsorption efficiency of CTG was in-
dependent of pH for all species of mercury under study suggesting that
electrostatic attraction was not playing a role in the adsorption process.
The zeta potential values shown in the Fig. S1(b) (Supporting
Information) obtained from the measurement revealed that the ad-
sorption remained almost constant in the pH range of 4-7. Higher pH
values were not studied in order to avoid precipitation (Kyzas &
Deliyanni, 2013).

671
R. Bhatt, P. P
3.2.3. Sorption isotherms
The adsorption data were analyzed using Freundlich, Langmuir,
Temkin and Halsey isotherm models (Fig. S2 (Supporting Information))
and isotherm constants for the adsorption of Hg°, Hg2+ and CH3Hg+
are presented in Table 1. The R2 values were high for all the adsorption
isotherm models under study.
However, from the data, it was observed that the Freundlich model
provided the best fit as the calculated adsorption capacity was close to
the experimental adsorption capacity (Qmax) with high R2 values, low
x 2 (0.4904, 1.284 and 1.122 respectively for Hg°, Hg2+ and CH3Hg+),
RMSE(14.01, 28.23 and 28.39 respectively for Hg°, Hg2+ and
CH3Hg+), ARE(0.7785, 1.041 and 1.010 respectively for Hg°, Hg2+ and
CH3Hg+) and SAE(44.58, 96.95 and 102.5 respectively for Hg°, Hg2+
and CH3Hg+) function values. The n value usually depends on the
nature and strength of the adsorption process as well as the distribution
of active sites. It was observed that the n value was greater than 1 for
Hg°, Hg2+ and CH3Hg+, which represents a favorable adsorption
condition. The high values of kf indicated that the mercury species
could be readily adsorbed onto the surface of the adsorbent.
Furthermore though high regression values were obtained for the
Langmuir and Halsey models, the experimental data deviated sig-
nificantly from the theoretical values suggesting that they were not
good fits to describe the adsorption process. High regression values
were obtained during the fitting of Temkin model but the standard
deviation values obtained were very high for the collected data. Temkin
model is characterized by a uniform distribution of binding energies
(upto some maximum binding energy). The closeness of experimental
data to the theoretical values with low x 2 (1.344), RMSE(23.42), ARE
(1.326) and SAE(77.47) function values for elemental mercury affirms
the fact that Temkin model is excellent for predicting the gas phase
equilibrium (Foo & Hameed, 2010).
The maximum adsorption capacity for CTG was calculated to be
1367 ± 96.9, 2493 ± 174.6 and 2531 ± 178.4 mg/g for Hg°, Hg2+
and CH3Hg+ respectively. Chitosan based adsorbent such as, CTS-I-S-
410 (A. Zhang et al., 2009) has been used for the removal of
Hg°(0.069 mg/g); while Chitosan (Shafaei, Ashtiani, & Kaghazchi,
2007), GLA-chitosan (Vieira & Beppu, 2005), Chitosan-coated magne-
tite nanoparticles (CCMN) (Nadereh Rahbar et al., 2014), Chitosan/
nanohydroxyapatite composites based on scallop shells (CP12) (Hassan
& Hrdina, 2018), Magnetic FeS nanoparticles stabilized with chitosan
(CTO-MFeS) (M. Sun et al., 2018), Magnetic chitosan microspheres
modified with thiourea (TMCS) (Zhou, Wang, Liu, & Huang, 2009),
Thiourea-modified chitosan derivative (TMCD) (Wang et al., 2010),
Glutaraldehyde crosslinked Chitosan Spheres (Vieira & Beppu, 2006)
have been used for the removal of Hg2+with adsorption capacities in
the range 9.34 mg/g to 1127.1 mg/g. Furthermore, to the best of our
knowledge chitosan based adsorbents with good uptake capacity for
CH3Hg+ have not been reported.
Sulfurized adsorbents such as SC-600 (Kumar Reddy, Prabhu, Al
Shoaibi, & Srinivasakannan, 2016), metal sulfide based porous carbons
C/CuS (Reddy, Al Shoaibi, & Srinivasakannan, 2018), Porous sulfur
copolymer foams (Abraham, Kumar, & Alhassan, 2018) and Rattle-type
Fe3O4@CuS (Yang et al., 2018) have been used for the removal of Hg°
with adsorption capacities in the range 0.151 mg/g to 80.73 mg/g while
Thiol functionalized SBA-15 (SBA-15-SH) (Hutchison, Atwood, &
Santilliann-Jiminez, 2008), 2,2-Dithiodisalicylic acid-functionalized
magnetic graphene oxide (Fe3O4@DTSA_GO) (Shen et al., 2018), l-cy-
steine Functionalized nanocellulose (Cys-CNFs) (Bansal, Ram, Chauhan,
& Kaushik, 2018), Activated Carbon (AC–H1.5) (Kazemi, Younesi,
Ghoreyshi, Bahramifar, & Heidari, 2016), Polythiophene modified
chitosan/magnetite nanocomposites (PTh.MCs.NC.) (Morsi, Al-Sabagh,
Moustafa, ElKholy, & Sayed, 2018) have been used for the removal of
Hg2+ with adsorption capacities in the range 13.9 mg/g to 283.5 mg/g
and Polyhedral oligomeric silsesquioxane (POSS-SH) (Wang, Chen,
Chen, & Wang, 2014), has been used for the removal of both Hg2+ and
CH3Hg+ with adsorption capacities 12.90 and 46.73 mg/g respectively.
672
Carbohydrate Polymers 207 (2019) 663–674
It was observed that the adsorption capacity of CTG for Hg°, Hg2+
and CH3Hg+ were very high as compared to the literature reported
adsorbents. Further, the adsorption was efficient over a broad range of
pH from 4 to 7.
3.2.4. Sorption kinetics
The effect of time for adsorption of Hg°, Hg2+ and CH3Hg+ onto
CTG was investigated and the data was fit to Pseudo-first order
(Lagergren), Pseudo-second order, Elovich, and Liquid film diffusion
kinetic models (Fig. S3 (Supporting Information)) and the rate con-
stants for the adsorption of Hg°, Hg2+ and CH3Hg+ are presented in
Table 2. CTG exhibited quantitative adsorption of Hg° in 10 min and 3 h
for Hg2+ and CH3Hg+ respectively.
The calculated Qe values were also closer to those obtained ex-
perimentally for pseudo second order model with good correlation
coefficients(0.9998, 0.9997 and 0.9995 for Hg°, Hg2+ and CH3Hg+
respectively) and low values of error function( x 2 -0.2162, 2.755 and
0.3955 respectively for Hg°, Hg2+ and CH3Hg+, RMSE-7.701, 18.67
and 5.677 for Hg°, Hg2+ and CH3Hg+ respectively, ARE-0.6012, 4.865
and 2.147 for Hg°, Hg2+ and CH3Hg+ respectively and SAE-41.45,
46.30 and 15.20 for Hg°, Hg2+ and CH3Hg+ respectively) indicating
that the adsorption process followed pseudo second order kinetics. This
supported the assumption behind the model that the surface com-
plexation may be the rate-limiting step involving valence forces
through sharing or exchanging of electrons between adsorbent and
adsorbate (Chen, Cai, Zhang, Liu, & Yang, 2014). A high α (elovich
model) value was obtained for inorganic mercury affirming that initial
rate of adsorption was very high.
3.2.5. Desorption studies and reuse of CTG
Desorption studies (Fig. 6(a)) were carried out using different elu-
ents for the recovery of Hg°, Hg2+, and CH3Hg+. A 0.05 g amount of
adsorbent loaded with 692.43 mg/g Hg°, 1249.52 mg/g Hg2+ and
1248.74 mg/g CH3Hg+ was added to 25 mL of eluent solution and the
flasks containing solutions were shaken in a shaker for 180 min.. The
supernatant was separated from the adsorbent by filtration and ana-
lyzed for the presence of desorbed mercury. 20
It was found that the Hg° was eluted quantitatively using 0.01 N
thiourea whereas inorganic mercury was quantitatively desorbed using
0.01 N HClO4 and CH3Hg+ was quantitatively desorbed using 0.2 N
NaCl.
Repeated adsorption cycles (Fig. 6(b)) were performed for CTG with
697 mg/m3 Hg° and 500 ppm Hg2+ / CH3Hg+. It was observed that the
adsorption capacity decreased by about 30%, ∼ 15% and ∼ 20% for
Hg°, Hg2+ and CH3Hg+ respectively after 3 cycles. However there was
no visible change in CTG after three cycles of adsorption and deso-
rption.
Further, to study the interference of different metals on the mercury
uptake (Fig. 6(c)), 25 mL solution containing 25 ppm each of Hg2+,
CH3Hg+, Cu2+, Cd2+, Pb2+ and Zn2+ at pH 4 and was equilibrated
with 0.01 g CTG for 3 h using an orbital shaker. It was observed that
copper, cadmium, lead and zinc did not cause any interference on up-
take of both Hg2+ and CH3Hg+ though there was ∼ 30% uptake of
Cu2+, Cd2+, Pb2+ and Zn2+.
3.2.6. Discussion
The FTIR spectra of the mercury loaded adsorbent depicts the
changes in stretching frequencies or intensities in CTG after adsorption
of different mercury species (Fig. S4-Supporting Information) which
could be attributed to the binding of mercury species to CTG. The ad-
sorption of mercury may be accompanied with substantial charge re-
distribution near the O and S atoms in the TBA structure resulting in
intensity change and frequency shifts of the vibrational peaks of CTG.
This reflects the dipole moment change owing to the formation of O-Hg
(II)- S bonds.
Furthermore, the XRD analysis (Fig. 1(c)) showed that the position
R. Bhatt, P. P
of peak at 20.33° for CTG shifted to 21.28°, 19.98° and 20.20° upon
interaction with Hg°, Hg2+ and CH3Hg+ respectively which may be
well attributed to the interaction of CTG with the elemental mercury
and the mercuric ions (Trimukhe & Varma, 2008). The binding of the
sulfur in CTG with Hg°, Hg2+ and CH3Hg+ respectively was supported
with the generation of new peaks at 44.51°, 44.36° and 42.66° respec-
tively (Marimuthu, Arivanandhan, & Vedhi, 2015).
The lone pair of electrons on nitrogen and oxygen of hydroxyl group
on chitosan and on TBA could enable binding of mercury species by
chelation. Hg(II) forms bonds with deprotonated sulphur of mercapto
group and oxygen of hydroxyl group, which results in the formation of a
stable six membered chelate (log K = 33.20) (Karthikeyan,
Parameshwara, Shetty, & Shetty, 2007). Looking into the high stability
constant this would be the predominant mechanism mercury being a
soft acid. However since pH was observed to be not critical during the
adsorption process the ion exchange mechanism would not be pre-
dominant though the pKa values of chitosan range from 6.2 to 7 sug-
gesting that below a pH of 6 amino groups would be protonated and ion
exchange with protonated amino groups (-NH3+) through proton (H+)
could be possible.
Hg° has high affinity for thiols wherein Hg2+ is formed by ligand-
induced oxidative complexation with thiols (Gu et al., 2011; Skyllberg,
Bloom, Qian, Lin, & Bleam, 2006). The adsorption capacity of Hg° was
observed to be lesser as compared to Hg2+ and CH3Hg+ as the ad-
sorption process is dependent upon the oxidative complexation.
A plausible structure for CTG and the nature of its interaction with
mercury species has been proposed in Fig. 7.
4. Conclusions
A chitosan thiomer(CTG) using thiobarbituric acid was successfully
prepared for removal of Hg°, Hg2+ and CH3Hg+. The adsorption effi-
ciency was unaffected over a wide pH range of 4 to 7 and was complete
within 10 min for Hg° and 180 min for Hg2+ and CH3Hg+. The ad-
sorption data of the mercury species provided the best fit to Freunlich
isotherm model as the calculated adsorption capacity was close to the
experimental adsorption capacity (Qmax) with high R2 and low error
function values( x 2 -0.4904, 1.284 and 1.122 for Hg°, Hg2+ and
CH3Hg+ respectively, RMSE-14.01, 28.23 and 28.39 for Hg°, Hg2+ and
CH3Hg+ respectively, ARE-0.7785, 1.041 and 1.010 for Hg°, Hg2+ and
CH3Hg+ respectively and SAE-44.58, 96.95 and 102.5 for Hg°, Hg2+
and CH3Hg+ respectively). and the kinetics of adsorption followed the
pseudo-second order model with high R2 and minimal error function
values( x 2 -0.2162, 2.755 and 0.3955 respectively for Hg°, Hg2+ and
CH3Hg+, RMSE-7.701, 18.67 and 5.677 for Hg°, Hg2+ and CH3Hg+
respectively, ARE-0.6012, 4.865 and 2.147 for Hg°, Hg2+ and CH3Hg+
respectively and SAE-41.45, 46.30 and 15.20 for Hg°, Hg2+ and
CH3Hg+ respectively). The maximum adsorption capacity was calcu-
lated to be 1367 ± 96.9, 2493 ± 174.6 and 2531 ± 178.4 mg/g for
Hg°, Hg2+ and CH3Hg+ respectively. To the best of our knowledge, it is
for the first time that a single adsorbent is reported to be found effective
in removing Hg°, Hg2+ and CH3Hg+. The adsorption capacities were
found to be higher than all other adsorbents reported in literature. CTG
could be reused as adsorbent for three cycles after eluting Hg°, Hg2+
and CH3Hg+ using 0.01 N thiourea, 0.01 N HClO4 and 0.2 N NaCl re-
spectively. The adsorption desorption cycles suggest that though des-
orption is quantitative, adsorption efficiency decreased in successive
cycles. Copper, cadmium, lead and zinc did not cause any interference
on uptake of both Hg2+ and CH3Hg+. Further, CTG would prove to be
an effective adsorbent to remove Hg° from flue gases without escaping
from the adsorbent. A probable mechanism of adsorption has been
proposed. However further investigations to affirm the mechanism of
binding suggested for mercury species by XPS, understand the loss in
efficiency of the adsorbent by SEM EDX mapping and investigation of
the practical applicability of CTG to remove mercury from flue gases
and waste water samples need to be undertaken.
673
Carbohydrate Polymers 207 (2019) 663–674
Acknowledgements
The authors are thankful to University Grants Commission for fi-
nancial assistance vide UGC-MRP (39-718/2010(SR) dated 13 Jan
2011), Mr. Jagtar Singh from SAIF Chandigarh for XRD studies, Dr.
Vandana Rao, Department of Metallurgy, M. S. University of Baroda,
Vadodara, Dr. S. P. Sahoo from SPARC, Vadodara for DSC studies and
Department of Chemistry, M. S. University of Baroda, Vadodara for
laboratory facilities.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.carbpol.2018.12.018.
References
Abraham, A. M., Kumar, S. V., & Alhassan, S. M. (2018). Porous sulphur copolymer for
gas-phase mercury removal and thermal insulation. Chemical Engineering Journal,
332, 1–7. https://doi.org/10.1016/J.CEJ.2017.09.069.
Abraham, S., Rajamanickam, D., & Srinivasan, B. (2018). Research article Preparation,
Characterization and Cross-linking of Chitosan by Microwave Assisted Synthesis.
Science International, 6(1), 18–30. https://doi.org/10.17311/sciintl.2018.18.30.
Aljeboree, A. M., Alshirifi, A. N., & Alkaim, A. F. (2017). Kinetics and equilibrium study
for the adsorption of textile dyes on coconut shell activated carbon. Arabian Journal of
Chemistry, 10, S3381–S3393. https://doi.org/10.1016/J.ARABJC.2014.01.020.
Bansal, M., Ram, B., Chauhan, G. S., & Kaushik, A. (2018). l-cysteine functionalized ba-
gasse cellulose nanofibers for mercury(II) ions adsorption. International Journal of
Biological Macromolecules, 112, 728–736. https://doi.org/10.1016/J.IJBIOMAC.
2018.01.206.
Barabás, R., Czikó, M., Dékány, I., Bizo, L., & Bogya, E. S. (2013). Comparative study of
particle size analysis of hydroxyapatite-based nanomaterials. Chemical Papers, 67(11),
1414–1423. https://doi.org/10.2478/s11696-013-0409-6.
Belhachemi, M., & Addoun, F. (2011). Comparative adsorption isotherms and modeling of
methylene blue onto activated carbons. Applied Water Science, 1(3), 111–117. https://
doi.org/10.1007/s13201-011-0014-1.
Caro León, F. J., Lizardi-Mendoza, J., Argüelles-Monal, W., Carvajal-Millan, E., López
Franco, Y. L., & Goycoolea, F. M. (2017). Supercritical CO2 dried chitosan nano-
particles: Production and characterization. RSC Advances, 7(49), 30879–30885.
https://doi.org/10.1039/C7RA02555F.
Chauhan, K., Singh, P., & Singhal, R. K. (2015). New chitosan–Thiomer: An efficient
colorimetric sensor and effective sorbent for mercury at ultralow concentration. ACS
Applied Materials & Interfaces, 7(47), 26069–26078. https://doi.org/10.1021/acsami.
5b06078.
Chen, X. J., Cai, J. C., Zhang, Z. H., Liu, L. J., & Yang, G. L. (2014). Investigation of
removal of Pb(II) and Hg(II) by a novel cross-linked chitosan-poly(aspartic acid)
chelating resin containing disulfide bond. Colloid and Polymer Science, 292(9),
2157–2172. https://doi.org/10.1007/s00396-014-3240-x.
Da̧browski, A., Hubicki, Z., Podkościelny, P., & Robens, E. (2004). Selective removal of
the heavy metal ions from waters and industrial wastewaters by ion-exchange
method. Chemosphere, 56(2), 91–106. https://doi.org/10.1016/j.chemosphere.2004.
03.006.
El-Zawahry, M. M., Abdelghaffar, F., Abdelghaffar, R. A., & Hassabo, A. G. (2016).
Equilibrium and kinetic models on the adsorption of Reactive Black 5 from aqueous
solution using Eichhornia crassipes/chitosan composite. Carbohydrate Polymers, 136,
507–515. https://doi.org/10.1016/j.carbpol.2015.09.071.
Foo, K. Y., & Hameed, B. H. (2010). Insights into the modeling of adsorption isotherm
systems. Chemical Engineering Journal, 156(1), 2–10. https://doi.org/10.1016/j.cej.
2009.09.013.
Gao, J., Sun, S.-P., Zhu, W.-P., & Chung, T.-S. (2014). Chelating polymer modified P84
nanofiltration (NF) hollow fiber membranes for high efficient heavy metal removal.
Water Research, 63, 252–261. https://doi.org/10.1016/j.watres.2014.06.006.
Geethamani, C. K., Ramesh, S. T., Gandhimathi, R., & Nidheesh, P. V. (2013). Fluoride
sorption by treated fly ash: Kinetic and isotherm studies. Journal of Material Cycles
and Waste Management, 15(3), 381–392. https://doi.org/10.1007/s10163-013-
0128-7.
Golovnev, N. N., Molokeev, M. S., Tarasova, L. S., Atuchin, V. V., & Vladimirova, N. I.
(2014). The 5-(isopropylidene)-2-thiobarbituric acid: Preparation, crystal structure,
thermal stability and IR-characterization. Journal of Molecular Structure, 1068(1),
216–221. https://doi.org/10.1016/j.molstruc.2014.04.024.
Gu, B., Bian, Y., Miller, C. L., Dong, W., Jiang, X., & Liang, L. (2011). Mercury reduction
and complexation by natural organic matter in anoxic environments. Proceedings of
the National Academy of Sciences, 108(4), 1479–1483. https://doi.org/10.1073/pnas.
1008747108.
Hamzaoui, M., Bestani, B., & Benderdouche, N. (2017). The use of linear and nonlinear
methods for adsorption isotherm optimization of basic green 4-dye onto sawdust-
based activated carbon. Journal of Materials and Environmental Science, 2508(4),
1110–1118.
Hassan, A. F., & Hrdina, R. (2018). Chitosan/nanohydroxyapatite composite based scallop
shells as an efficient adsorbent for mercuric ions: Static and dynamic adsorption
studies. International Journal of Biological Macromolecules, 109, 507–516. https://doi.
org/10.1016/J.IJBIOMAC.2017.12.094.
Hutchison, A., Atwood, D., & Santilliann-Jiminez, Q. E. (2008). The removal of mercury
from water by open chain ligands containing multiple sulfurs. Journal of Hazardous
R. Bhatt, P. P
Materials, 156(1–3), 458–465. https://doi.org/10.1016/J.JHAZMAT.2007.12.042.
Kakavandi, B., Kalantary, R. R., Jafari, A. J., Nasseri, S., Ameri, A., Esrafili, A., ... Azari, A.
(2015). Pb(II) adsorption onto a magnetic composite of activated carbon and su-
perparamagnetic Fe 3 O 4 nanoparticles: Experimental and modeling study. Clean -
Soil, Air, Water, 43(8), 1157–1166. https://doi.org/10.1002/clen.201400568.
Karmaker, S., Sen, T., & Saha, T. K. (2015). Adsorption of reactive yellow 145 onto
chitosan in aqueous solution: Kinetic modeling and thermodynamic analysis. Polymer
Bulletin, 72(8), 1879–1897. https://doi.org/10.1007/s00289-015-1378-4.
Karthikeyan, J., Parameshwara, P., Shetty, N. A., & Shetty, P. (2007). Complexometric
determination of mercury (II) using 2-thiobarbituric acid as a releasing agent. Indian
Journal of Chemical Technology, 14(2), 209–211.
Kasaai, M. R. (2010). Determination of the degree of N-acetylation for chitin and chitosan
by various NMR spectroscopy techniques: A review. Carbohydrate Polymers, 79(4),
801–810. https://doi.org/10.1016/j.carbpol.2009.10.051.
Kast, C. E., & Bernkop-Schnürch, A. (2001). Thiolated polymers - thiomers: Development
and in vitro evaluation of chitosan-thioglycolic acid conjugates. Biomaterials, 22(17),
2345–2352. https://doi.org/10.1016/S0142-9612(00)00421-X.
Kazemi, F., Younesi, H., Ghoreyshi, A. A., Bahramifar, N., & Heidari, A. (2016). Thiol-
incorporated activated carbon derived from fir wood sawdust as an efficient ad-
sorbent for the removal of mercury ion: Batch and fixed-bed column studies. Process
Safety and Environmental Protection, 100, 22–35. https://doi.org/10.1016/J.PSEP.
2015.12.006.
Knight, J. A., Pieper, R. K., & McClellan, L. (1988). Specificity of the thiobarbituric acid
reaction: Its use in studies of lipid peroxidation. Clinical Chemistry, 34(12), 2433 LP-
2438. Retrieved from http://clinchem.aaccjnls.org/content/34/12/2433.abstract.
Kolya, H., Das, S., & Tripathy, T. (2014). Synthesis of Starch-g-Poly-(N-methylacrylamide-
co-acrylic acid) and its application for the removal of mercury (II) from aqueous
solution by adsorption. European Polymer Journal, 58, 1–10. https://doi.org/10.1016/
j.eurpolymj.2014.05.019.
Kumar, K. V. (2006). Linear and non-linear regression analysis for the sorption kinetics of
methylene blue onto activated carbon. Journal of Hazardous Materials, 137(3),
1538–1544. https://doi.org/10.1016/j.jhazmat.2006.04.036.
Kumar Reddy, K. S., Prabhu, A., Al Shoaibi, A., & Srinivasakannan, C. (2016). Application
of sulfonated carbons for mercury removal in gas processing. Energy & Fuels, 30(4),
3227–3232. https://doi.org/10.1021/acs.energyfuels.5b02630.
Kushwaha, S., & Sudhakar, P. P. (2011). Adsorption of mercury(II), methyl mercury(II)
and phenyl mercury(II) on chitosan cross-linked with a barbital derivative.
Carbohydrate Polymers, 86(2), 1055–1062. https://doi.org/10.1016/j.carbpol.2011.
06.028.
Kyzas, Z. G., & Deliyanni, A. E. (2013). Mercury(II) removal with modified magnetic
chitosan adsorbents. Molecules. https://doi.org/10.3390/molecules18066193.
Li, K., Wang, Y., Huang, M., Yan, H., Yang, H., Xiao, S., ... Li, A. (2015). Preparation of
chitosan-graft-polyacrylamide magnetic composite microspheres for enhanced se-
lective removal of mercury ions from water. Journal of Colloid and Interface Science,
455, 261–270. https://doi.org/10.1016/j.jcis.2015.05.043.
Lu, X., Jiang, J., Sun, K., Wang, J., & Zhang, Y. (2014). Influence of the pore structure and
surface chemical properties of activated carbon on the adsorption of mercury from
aqueous solutions. Marine Pollution Bulletin, 78(1–2), 69–76. https://doi.org/10.
1016/j.marpolbul.2013.11.007.
Marimuthu, G., Arivanandhan, M., & Vedhi, C. (2015). Chemical vapor deposition of β-
HgS nanoparticles from a precursor, bis(cinnamylpiperazinedithiocarbamato) mer-
cury(II). Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal
Chemistry, 45(2), 217–224. https://doi.org/10.1080/15533174.2013.831884.
Méndez, E., Cerdá, M. F., Gancheff, J. S., Torres, J., Kremer, C., Castiglioni, J., ... Ventura,
O. N. (2007). Tautomeric forms of 2-thiobarbituric acid As studied in the solid, in
polar solutions, and on gold nanoparticles. The Journal of Physical Chemistry C,
111(8), 3369–3383. https://doi.org/10.1021/jp0628176.
Meng, X., Korfiatis, G. P., Christodoulatos, C., & Bang, S. (2001). Treatment of arsenic in
Bangladesh well water using a household co-precipitation and filtration system.
Water Research, 35(12), 2805–2810. https://doi.org/10.1016/S0043-1354(01)
00007-0.
Morsi, R. E., Al-Sabagh, A. M., Moustafa, Y. M., ElKholy, S. G., & Sayed, M. S. (2018).
Polythiophene modified chitosan/magnetite nanocomposites for heavy metals and
selective mercury removal. Egyptian Journal of Petroleum. https://doi.org/10.1016/J.
EJPE.2018.03.004 In Press, Corrected Proof.
Oliveira, J. R., Martins, M. C. L., Mafra, L., & Gomes, P. (2012). Synthesis of an O-alkynyl-
chitosan and its chemoselective conjugation with a PEG-like amino-azide through
click chemistry. Carbohydrate Polymers, 87(1), 240–249. https://doi.org/10.1016/j.
carbpol.2011.07.043.
Pillay, K., Cukrowska, E. M., & Coville, N. J. (2013). Improved uptake of mercury by
sulphur-containing carbon nanotubes. Microchemical Journal, 108, 124–130. https://
doi.org/10.1016/j.microc.2012.10.014.
Prakash, N., Vijayalakshmi, K., & Sudha, P. N. (2011). Enhancement in the thermal sta-
bility of chitosan/nylon6 polymer blends by crosslinking. International Journal of
Chemistry Research, 2(3), 15–18.
Rahbar, Nadereh, et al. (2014). Mercury removal from aqueous solutions with chitosan-
coated magnetite nanoparticles optimized using the box-behnken design. Jundishapur
Journal of Natural Pharmaceutical Products, 9(2) e15913.
Reddy, K. S. K., Al Shoaibi, A., & Srinivasakannan, C. (2018). Mercury removal using
metal sulfide porous carbon complex. Process Safety and Environmental Protection,
114, 153–158. https://doi.org/10.1016/J.PSEP.2017.12.022.
Rocha, L. S., Almeida, Â., Nunes, C., Henriques, B., Coimbra, M. A., Lopes, C. B., ...
Pereira, E. (2016). Simple and effective chitosan based films for the removal of Hg
from waters: Equilibrium, kinetic and ionic competition. Chemical Engineering Journal,
300, 217–229. https://doi.org/10.1016/J.CEJ.2016.04.054.
674
Carbohydrate Polymers 207 (2019) 663–674
Ruiz, M., Sastre, A. M., & Guibal, E. (2000). Palladium sorption on glutaraldehyde-
crosslinked chitosan. Reactive and Functional Polymers, 45(3), 155–173. https://doi.
org/10.1016/S1381-5148(00)00019-5.
Sashikala, S., & Shafi, S. S. (2014). Synthesis and characterization of chitosan Schiff base
derivatives. Der Pharmacia Lettre, 6(2), 90–97.
Shafaei, A., Ashtiani, F. Z., & Kaghazchi, T. (2007). Equilibrium studies of the sorption of
Hg(II) ions onto chitosan. Chemical Engineering Journal, 133(1–3), 311–316. https://
doi.org/10.1016/J.CEJ.2007.02.016.
Shen, Y., Jiang, N., Liu, S., Zheng, C., Wang, X., Huang, T., ... Bai, R. (2018). Thiol
functionalization of short channel SBA-15 through a safe, mild and facile method and
application for the removal of mercury (II). Journal of Environmental Chemical
Engineering, 6(4), 5420–5433. https://doi.org/10.1016/J.JECE.2018.08.030.
Singha, B., & Das, S. K. (2013). Adsorptive removal of Cu(II) from aqueous solution and
industrial effluent using natural/agricultural wastes. Colloids and Surfaces B:
Biointerfaces, 107, 97–106. https://doi.org/10.1016/j.colsurfb.2013.01.060.
Skodras, G., Diamantopoulou, I., Pantoleontos, G., & Sakellaropoulos, G. P. (2008).
Kinetic studies of elemental mercury adsorption in activated carbon fixed bed re-
actor. Journal of Hazardous Materials, 158(1), 1–13. https://doi.org/10.1016/j.
jhazmat.2008.01.073.
Skyllberg, U., Bloom, P. R., Qian, J., Lin, C.-M., & Bleam, W. F. (2006). Complexation of
mercury(II) in soil organic matter: EXAFS evidence for linear two-coordination with
reduced sulfur groups. Environmental Science & Technology, 40(13), 4174–4180.
https://doi.org/10.1021/es0600577.
Srivastava, N. K., & Majumder, C. B. (2008). Novel biofiltration methods for the treatment
of heavy metals from industrial wastewater. Journal of Hazardous Materials, 151(1),
1–8. https://doi.org/10.1016/j.jhazmat.2007.09.101.
Sun, M., Cheng, G., Ge, X., Chen, M., Wang, C., Lou, L., ... Xu, X. (2018). Aqueous Hg(II)
immobilization by chitosan stabilized magnetic iron sulfide nanoparticles. Science of
The Total Environment, 621, 1074–1083. https://doi.org/10.1016/J.SCITOTENV.
2017.10.119.
Sun, P., Zhang, B., Zeng, X., Luo, G., Li, X., Yao, H., ... Zheng, C. (2017). Deep study on
effects of activated carbon’s oxygen functional groups for elemental mercury ad-
sorption using temperature programmed desorption method. Fuel, 200, 100–106.
https://doi.org/10.1016/j.fuel.2017.03.031.
Trimukhe, K. D., & Varma, A. J. (2008). A morphological study of heavy metal complexes
of chitosan and crosslinked chitosans by SEM and WAXRD. Carbohydrate Polymers,
71(4), 698–702. https://doi.org/10.1016/j.carbpol.2007.07.010.
Vakili, M., Deng, S., Li, T., Wang, W., Wang, W., & Yu, G. (2018). Novel crosslinked
chitosan for enhanced adsorption of hexavalent chromium in acidic solution.
Chemical Engineering Journal, 347, 782–790. https://doi.org/10.1016/J.CEJ.2018.04.
181.
Vieira, R. S., & Beppu, M. M. (2005). Mercury ion recovery using natural and crosslinked
chitosan membranes. Adsorption, 11(1), 731–736. https://doi.org/10.1007/s10450-
005-6015-3.
Vieira, R. S., & Beppu, M. M. (2006). Dynamic and static adsorption and desorption of Hg
(II) ions on chitosan membranes and spheres. Water Research, 40(8), 1726–1734.
https://doi.org/10.1016/j.watres.2006.02.027.
Volesky, B. (1990). Biosorption of heavy metals. Retrieved fromTaylor & Francishttps://
books.google.co.in/books?id=doFlZsR2LQEC.
Wang, L., Xing, R., Liu, S., Cai, S., Yu, H., Feng, J., ... Li, P. (2010). Synthesis and eva-
luation of a thiourea-modified chitosan derivative applied for adsorption of Hg(II)
from synthetic wastewater. International Journal of Biological Macromolecules, 46(5),
524–528. https://doi.org/10.1016/j.ijbiomac.2010.03.003.
Wang, W., Chen, M., Chen, X., & Wang, J. (2014). Thiol-rich polyhedral oligomeric sil-
sesquioxane as a novel adsorbent for mercury adsorption and speciation. Chemical
Engineering Journal, 242, 62–68. https://doi.org/10.1016/j.cej.2013.12.063.
Wang, Q., Liu, Y., Yang, Z., Wang, H., Weng, X., Wang, Y., ... Wu, Z. (2014). Study of
mercury re-emission in a simulated WFGD solution containing thiocyanate and sul-
fide ions. Fuel, 134, 588–594. https://doi.org/10.1016/j.fuel.2014.05.080.
Yang, Z., Li, H., Liao, C., Zhao, J., Feng, S., Li, P., ... Shih, K. (2018). Magnetic rattle-type
Fe3O4@CuS nanoparticles as recyclable sorbents for mercury capture from coal
combustion flue gas. ACS Applied Nano Materials, 1(9), 4726–4736. https://doi.org/
10.1021/acsanm.8b00948.
Zaki, Z. M., & Mohamed, G. G. (2000). Spectral and thermal studies of thiobarbituric acid
complexes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,
56(7), 1245–1250. https://doi.org/10.1016/S1386-1425(99)00225-5.
Zeb, A., & Ullah, F. (2016). A simple spectrophotometric method for the determination of
thiobarbituric acid reactive substances in fried fast foods. Journal of Analytical
Methods in Chemistry, 2016, 1–5. https://doi.org/10.1155/2016/9412767.
Zhang, A., Xiang, J., Sun, L., Hu, S., Li, P., Shi, J., ... Su, S. (2009). Preparation, char-
acterization, and application of modified chitosan sorbents for elemental mercury
removal. Industrial & Engineering Chemistry Research, 48(10), 4980–4989. https://doi.
org/10.1021/ie9000629.
Zhang, D., Yin, Y., & Liu, J. (2017). Removal of Hg2+ and methylmercury in waters by
functionalized multi-walled carbon nanotubes: Adsorption behavior and the impacts
of some environmentally relevant factors. Chemical Speciation & Bioavailability, 29(1),
161–169. https://doi.org/10.1080/09542299.2017.1378596.
Zhao, Y., Hao, R., Zhang, P., & Zhou, S. (2014). An integrative process for Hg0 removal
using vaporized H 2O2/Na2S2O8. Fuel, 136, 113–121. https://doi.org/10.1016/j.
fuel.2014.07.046.
Zhou, L., Wang, Y., Liu, Z., & Huang, Q. (2009). Characteristics of equilibrium, kinetics
studies for adsorption of Hg(II), Cu(II), and Ni(II) ions by thiourea-modified magnetic
chitosan microspheres. Journal of Hazardous Materials, 161(2), 995–1002. https://
doi.org/10.1016/j.jhazmat.2008.04.078.