Journal of the Taiwan Institute of Chemical Engineers 119 (2021) 204
212

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Journal of the Taiwan Institute of Chemical Engineers

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Sorption/desorption of aqueous mercury ions [Hg2+] onto/from sulfur-

impregnated attapulgite: Process optimization, co-existing anions and
regeneration studies
Qicheng Qiaoa, Seema Singhb,c,*, Shang
Lien Lob,*, Vimal Chandra Srivastavad, Jierong Jina,
Yongchang Yua, Lizhang Wange
a
School of Environment and Biological Engineering, Nantong College of Science and Technology, Nantong City, Jiangsu 226007, P R China
b
Graduate Institute of Environmental Engineering, National Taiwan University, 71, Chou-Shan Rd., Taipei 106, Taiwan
c
Omvati Devi Degree College Bhalaswagaj, Haridwar, Uttarakhand, India
d
Department of Chemical Engineering, Indian Institute of Technology, Roorkee, Roorkee, Uttarakhand 247667, India
e
School of Environment Science and Spatial Informatics, China University of Mining and Technology Xuzhou City, Jiangsu 221116, P R China

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

Article History: Present study proposed a sorption and desorption approach of aqueous mercury ion (Hg2+) on sulfur impreg-
Received 26 October 2020 nated attapulgite (ATPS) adsorbent. Morphological characterization of natural and impregnated ATP con-
Revised 29 January 2021 firmed the mesoporous nature of ATPS-adsorbents. The presence of various types of functional groups on the
Accepted 11 February 2021
surface of ATPS was confirmed by using the zeta-potential measurement, X-ray fluorescence (XRF), and FT-IR
Available online 20 February 2021
analysis. Batch adsorption tests were carried out to detect the optimum condition of temperature for sulfur
Keywords: impregnation, and the results illustrated that the best adsorbent (ATPS-500) produced via the impregnation
Mercury (Hg2+) at 500 °C, with the highest equilibrium uptake of Hg2+ at initial pH 7. Different parameters like solution pHo,
Attapulgite (ATP) initial concentration of mercury (Co), temperature (T), contact time (t) and the effect of co-existing ions were
Sulphur impregnated attapulgite (ATPS) optimized. Optimum pH and equilibrium contact time at the optimum dose of adsorbent (m) = 0.02 g in
Sorption-desorption 50 mL and Co = 2.0 mg L
1 were found to be pH~5 and 24 h at T = 313 K for ATPS-500.The best representation
Kinetics and isotherm of adsorption kinetic was followed by the pseudo-first order kinetic model. The adsorption of Hg2+ions onto
ATPS-500 was found to be endothermic. The heat of adsorption and changes in the entropy of Hg2+ions sorp-
tion on ATPS-500 were determined as 10.35 kJ mol
1 and 0.16 kJ mol
1 K
1, respectively. Thermal regenera-
tion represented that ATPS-500 was used for five desorption
sorption cycles with excellent efficiency of Hg2
+
in each cycle.
© 2021 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction elemental mercury. It can form covalent bonds with organometallic

Water pollution with heavy metal ions like as mercury, cadmium,
lead, arsenic, etc., presents environmental issues because of the toxic-
ity, carcinogenicity, and non-biodegradability of the metals [1]. The
occurrence of mercury in the environment can arise from both
human activities and natural resources, which results in severe eco-
logical threats and damages of the environment. The carcinogenicity
and toxicity of mercury depend on its oxidation states and its signifi-
cant vapor pressure. Mercury can be easily reduced to elemental Hg
or converted to soluble Hg2+ compounds. Due to the high water solu-
bility of Hg2+ and the high mobility of the mercury vapor, mercury
can be observed as a mobile pollutant [2]. Hg2+ is the highly reactive
form of mercury, and also has the possibility to be transformed in
* Corresponding authors.
E-mail addresses: singh80seema@gmail.com (S. Singh), sllo@ntu.edu.tw (S. Lo).
compounds, for example, mono-methyl mercury [CH3Hg] and dime-
thylmercury (CH3)2 Hg [3].
However, it is well known that CH3Hg and (CH3)2 Hg are more
dangerous than inorganic mercury compounds such as HgCl2 and
metallic Hg itself. These methylated mercury compounds are further
readily absorbed in the gastrointestinal tract due to the superior abil-
ity to penetrate biomembranes. These compounds concentrate in the
bloodstream and have an instant and permanent effect on both the
central nervous system and brain due to their strong binding affinity
to the thiol (
SH) group of the cysteine residue of proteins [4]. The
USEPA has included mercury in the priority list of hazardous pollu-
tants, and prescribed limit of 10 mg L
1 of total Hg discharge limit in
wastewater, while 2 mg L
1 is the maximum limit for the drinking
water [5].
Various treatment approaches like as coagulation, co-precipita-
tion [6], membrane filtration [7], reverse osmosis [8], ion exchange

https://doi.org/10.1016/j.jtice.2021.02.015
1876-1070/© 2021 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 Q. Qiao et al. / Journal of the Taiwan Institute of Chemical Engineers 119 (2021) 204
212
[9], and adsorption [2, 10] have been reported for the removal of
mercury from waters, however, they generally shows several disad-
vantages as low adsorption capacity, high cost, and slow kinetics
[11
16]. These features related to the high level of mercury toxicity
and its incessant discharging into the environment through human
being activities have offered various studies including Hg2+ and dif-
ferent sorbents, like as hyperbranched polyethylenimine functional-
ized carboxymethyl chitosan [17], chitosan/cellulose biocomposite
sponge [18], chitosan-lignin composite functionalized with sponge
polyethyleneimine [19], Zeolite W [14] and clay minerals [20
22].
In addition, clay as cost-effective and natural adsorbents has been
significantly used for the removal of many heavy metal ions from
wasters and wastewaters particularly from developing countries [20,
22]. Adsorption of Hg2+ with clay minerals such as montmorillonite
(MMT) and vermiculite has been investigated as before explained [2,
20
22]. In addition, palygorskite or attapulgite (ATP), a silicate con-
taining crystalline mineral with a fibrous morphology has been stud-
ied with excellent adsorption capacity of various categories of metal
ions and other pollutants from waters [2, 23
28]. Table S1 shows a
comparative assessment of others from of natural ATP and its appli-
cations.
Despite a number of studies focused on the surface modification
of ATP for the Hg2+ removal from waters, they are generally sup-
ported the clay mineral surface modification for the use of removing
comparatively high concentrations of Hg2+. Thus, the main purpose
of present study was to examine the use of sulfur impregnation on
ATP surface. Modified ATP surface was characterized by using the FT-
IR, Brunauer-Emmett-Teller (BET), XRF, XRD, SEM, TEM, and zeta
potential measurement. The effect of initial mercury concentration (1

Co
14 mg L
1), contact time (t) (0
t
24 h), initial pH (pHo) (2

pHo
10), temperature (T) (293
T
313 K), and co-existing (0

salt concentration
10 mmol L
1) for the adsorption of mercury
onto ATPS has been examined. Adsorption kinetics and modeling of
equilibrium isotherm have been investigated to know the best fitting
of experimental data with different models. To know the effect of
temperature on mercury adsorption, the thermodynamic studies
have been performed. A desorption study was also used to investi-
gate the possible regeneration of ATPS.
2. Materials and methods
2.1. Chemicals
The natural clay ATP with a 320 mesh screen was purchased from
Jiangsu Anhalt Ltd. All chemicals of analytical grades, such as
hydrated mercury nitrate, elemental sulfur, HNO3, and NaOH were
acquired from Sinopharm Chemical Ltd. (Shanghai, China). Millipore
water was used to prepare all solutions. During this study, Na2CO3,
NaCl, NaHCO3 NaH2PO4, NaNO3, and Na2SO4 were used to alter the
ionic strength, and NaOH and HNO3 were used to adjust the solution
pH.
2.2. Adsorbent preparation
Sulfur-impregnation on the ATP surface was done by using the
previously reported method with a small alteration [29]. ATP was
first treated with 4 M HCl for 3 h with a solid/liquid ratio of 1:10 (g
L
1) at 70 °C, followed by washing with Millipore water up to the
complete removal of free chloride ions. After that, it was dried at
100 °C for 7 h before use. Later 2:1 mass ratio of ATP/elemental sulfur
was completely mixed in a ceramic boat to get a mixture of ATPS.
Later ATPS containing boat was shifted in a tubular furnace for 3 h
and heated at a constant temperature under N2 atmosphere. The
adsorption capacity of ATPS was examined at constant temperature
ranges from 200
600 °C to obtain four additional ATPS-x (x = 300,
205
400, 500, and 600 °C) sorbents. Prior to use, the resulting adsorbents
were kept in the desiccators.
2.3. Characterization of adsorbents
The N2 adsorption-desorption isotherms were used to calculate
the Brunauer- Emmett-Teller (BET) surface areas of the adsorbents
by using a Micromeritics ASAP 2020 analyzer at 77 K using a 10 s
equilibrium interval. The sulfur concentration of adsorbent was
detected by using a CHN

O-Rapid an elemental analyzer (Heraeus,
Germany) with a 0.3% sulfur detection limit. SEM and TEM analysis
was used to estimate the surface morphological alterations. The sam-
ple compositions were measure by using the X-ray fluorescence
(XRF) analysis. XRD pattern was selected on a SW, X'PERT 2400 kV
diffraction unit by using copper and nickel as a target and as a filter

media (40 kV, λ = 1.5406 A, 120 mA), respectively within the 2u range
of 10 to 80° with a 5°/min scan speed. FT-IR spectrum was recorded
by a Nicolet NEXUS 870 spectrometer with KBr pellet method over
the range of 400 to 4000 cm
1. Zeta potential measurement (Broo-
khaven Zeta PALS) was used to detect the electrophoretic mobility of
selected samples at a different range of pH. Atomic fluorescence spec-
trophotometer (AFS-610, Beijing, China) was used to determine the
mercury concentration. The initial and residual concentrations
change of samples was detected in a double beam spectrophotometer
(HACH, DR. 5000, USA).
2.4. Batch adsorption study
The adsorption performance of Hg2+ ions on ATPS-500 was done
by using a series of batch experiments. For this purpose, 50 mL of
known mercury concentration (4.0 mg L
1) solution was taken in
100 mL conical flask with 0.02 g L
1 adsorbent at an initial pH of 7.
The suspension was shaken in a thermal controlled orbital shaker
keeping specific temperatures such as 293, 303, and 313 K at a con-
stant speed of 150 rpm for 24 h. After an appropriate time, the sam-
ples were collected from shaker.
To determine the changes in concentration after each experiment,
the samples were centrifuged and analyzed. Simultaneously, at the
parallel conditions, blank experimental runs were performed without
mercury in a 50 mL of pure water. In addition, the adsorbate stability
was detected by shaking blank solutions of adsorbate in the absence
of any adsorbent. It was observed that adsorbate was stable in the
experimental runs. The effect of pH changes on mercury removal was
determined over the pH range varies from 2
10.The solution pHo
was altered by adding of 0.1 mol L
1 NaOH or HNO3. Effect of initial
mercury concentration (Co) was determined over the range of
1
14 mg L
1 till equilibrium was reached. The effect of co-existing
anions including carbonate (CO32
), bicarbonates (HCO3
), phosphate
(H2PO4
), sulfate (SO42
), chloride (Cl
) and nitrate (NO3
) on Hg2
+
adsorption at the surface of ATPS-500 was studied. The co-existing
anion solutions were prepared by dissolving NaNO3, NaH2PO4,
Na2SO4,NaCl, NaHCO3, and Na2CO3, to obtain concentrations of 5, 1,
0.5, 0.25, 0.1, 0 mmol L
1, respectively. The adsorption experiments
were conducted to identify their respective adsorption capacity.
The value of qe in mg g
1 (equilibrium adsorption uptake) and
percentage removal of adsorbate was determined by using the
eqns. (1) and 2:
ðC0
Ce Þ ¢ V
qe ¼ ð1Þ
w
ðC0
Ce Þ
Percentage removal ¼  100 ð2Þ
C0
where Co and Ce are the concentration changes (mg L
1) from initial
to an equilibrium level, V is the solution volume (L) and w is the
adsorbent mass (g).
206 Q. Qiao et al. / Journal of the Taiwan Institute of Chemical Engineers 119 (2021) 204
212
2.5. Desorption studies
The batch desorption study of Hg2+ removal was performed by
using solvent and thermal desorption methods, as reported by Srivas-
tava et al. [15] and Hiwarkar et al. [30]. During solvent desorption
study, mercury loaded adsorbent (mercury = 2 mg L
1 and ATPS-
500 = 0.02 g in 50 mL) was agitated in an orbital shaker at 150 rpm
with 50 mL known concentration solution of HNO3, H2SO4, HCl,
C2H5OH, CH3COCH3, NaOH, and CH3COOH at 303 K for 24 h. In the
thermal desorption method, Hg2+ loaded ATPS-500 was dried for 2 h
at 373 K in an oven; after that, it was heated at 623 K for 3 h in a fur-
nace. Thereafter, samples were collected from the furnace and kept
in the desiccators. This ATPS-500 was further used for the mercury
adsorption, and this method was repeated five times.
3. Results and discussion
3.1. Optimization of impregnation temperature
The maximum qe for Hg2+ was used to optimize the sulfur impreg-
nation at different temperatures. Batch experimental runs were con-
ducted to collect the adsorption isotherms for each as-prepared
sample at pH=7 and 0.2 M ionic strength (Table S2). A Langmuir fit-
ting of the adsorption isotherms was used to derive the qe values for
as-prepared ATPS samples. Fig. 1 shows the qe values with BET sur-
face areas and their own total sulfur contents. The qe value of ATPS
was found to be four times more than raw ATP. The adsorption capac-
ities were further improved after the heat treatment of ATPS-x at dif-
ferent temperatures (x = 300, 400, 500, 600 °C), whereas 500 °C
produced the best adsorbent (ATPS-500) with a higher qe. Fig. 1
shows that the sulfur content increased from 0 to 28% (mass ratio),
and surface area decreased from 115 to 1 to72 cm2 g
1 due to the
physically mixing of elemental sulfur with ATP. When ATPS was
treated at 300 °C (ATPS-300), the total sulfur content increased up
from 22% to 28%, along with decreased in area from 115 to 68 cm2
g
1. However, the total surface area increased around 93 cm2 g
1
with increasing the sulfur load temperature at 500 °C (ATPS-500).
However, the temperature at 600 °C has a limited effect on both sur-
face area and sulfur content.
A comparative study between qe and sample properties (total sul-
fur content and surface area) (Fig. 1) proves that there is no separate
correlation between qe and total sulfur content. Accordingly, Hsi
et al. [29] also reported parallel results of mercury adsorption in the
gaseous phase. The sulfur contents during mercury adsorption first
increased as the impregnation temperature increased till it reached
the highest value at 500 °C, and then decreased. Overall, the sulfur
content increased on the surface of ATPS and can effectively increase
the adsorption capacity of mercury [31]. This may happen due to the
polymeric network formation on the macropores and transitional
Fig. 1. Correlation of qe with BET surface area and sulfur content of ATP and ATPS sam-
ples for the adsorption of Hg2+ at time 24 h, Co: 2.0 mg L
1, m: 0.02 g, V: 50 mL, pH: 7
and 303 K.
pores channels of adsorbent. These channels help in entering of
adsorbates between the micropores and could affect the overall
adsorptive capacity of ATPS. Wang et al. [32] and Etienne and Walcar-
ius [32] described that active sulfur groups of the ATPS could effec-
tively work together with hydrolyzed head groups and hydroxyl
groups of channels. Thus, a multilayer network can potentially be
formed on ATP surface by impregnation, leading to the influence of
the adsorptive capacity.
3.2. Characterization of adsorbents
SEM and TEM results illustrate that modification altered not only
the BET surface area but the morphology of attapulgite. Fig. 2.a
d
presents the SEM and TEM analysis of raw ATP and ATPS-500. It is
evidently examined that impregnation changed the morphology of
the raw ATP surface. Fig. 2a and 2c show that raw ATP has loose
aggregates (Fig. 2a) and an apparent hairy morphology with a diame-
ter near about 26 nm (Fig. 2c). After impregnation, the ATPS illus-
trates dense aggregates (Fig. 2b) with a higher diameter of nearly
about 45 nm (Fig. 2d), which could be recognized to the obedience of
ATP based on silane coupling agent.
To know the chemical compositions of raw ATP and ATPS, XRF
analysis was performed. Table S3 illustrates the results of chemical
composition; samples are shown as wt.% of oxides. The result shows
the major quantities of silica oxide attained, which eventually
increased after impregnation than alumina. This analysis confirmed
the evidence about the silane coupling agent interface caused by the
complex reactions at the attapulgite surfaces. The samples relatively
contain a higher quantity of magnesium and potassium. The alkalis
content (K2O + Na2O) is higher. The major effect of alkalis in clays is
to diminish their refractory characteristics and, as a result; they are
fluxes [33]. Fig. 3 shows the XRD spectra of both raw ATP and ATPS.
As shown in Fig. 3, raw ATP and ATPS usually demonstrate a crystal-
lite nature. However, crystalline behavior of ATPS decreased than the
raw ATP, signifying some of the complex reactions take place at the
raw ATP surface. Moreover, the chemical composition of raw ATP
shows almost identical patterns as red mud [34].The main phases of
ATP are K2O, Na2O, MgO, Fe2O3, Al2O3, and SiO2. In addition, other
components SO3, TiO2, and CaO might exist in small amounts con-
firmed from the XRF results (Table S3). As expected, a pattern of the
multi-component arrangements is formed, which is similar to the
various types of clays reported in the literature [24]. However, it is
possible that different phase combination could be formed due to the
complex phase pattern. Thus, herein the main phases have been cho-
sen the position of quartz, dolomite, kaolinite, phyllosilicate, hema-
tite, and feldspar.
Fig. S1 shows the FTIR spectra of raw ATP, ATPS-500, and ATPS-
Hg2+. The raw ATP shows stretching and bending peaks at
3652
3664 cm
1 and 920 cm
1, respectively, owing to the Al
OH
presence. Additionally, a bending peak of Al-OH at 695
710 cm
1
indicates the characteristic of kaolinite [23]. Quartz in non-clay min-
erals was identified by a doublet at 795 and 810 cm
1 [23]. However,
illite detection, mainly by FTIR is quite difficult. Broad band at
1033
1044 cm
1 signifies the presence of Si
O stretching vibration,
whereas, the peaks at 545
555 cm
1 and 420
435 cm
1 were
formed due to the Si
O
Al and Si
O
Si bending mode of vibration
[24]. Comparison of these spectra shows several peaks disappeared
on ATPS-500 and ATPS-Hg2+ surface. The stretching vibrations bands
at 3610
3626 cm
1 and 3435
3420 cm
1and bending vibrations at
1652 cm
1 and 1448 cm
1correspond to free Al-OH, intra-molecular
hydrogen bonding (-OH), free H2O, respectively. Carbonates bands
get slightly disappeared from ATP to ATPS-500 and ATPS-Hg2+,
respectively [24]. These results confirmed that impregnation and
adsorption change the surface of raw ATP [23].
Fig. 4 demonstrates the result of zeta-potential versus pH of raw
ATP, ATPS-500, and ATPS-Hg2+. It is observed that the raw ATP is fully
 Q. Qiao et al. / Journal of the Taiwan Institute of Chemical Engineers 119 (2021) 204
212 207

Fig. 2. SEM and TEM analysis: (a) & (c) raw ATP and (b) & (d) ATPS-500.

negatively charged with no isoelectric point (IEP), whereas the IEP of complex (Hg
S) formation. Wang et al. [31] reported that the sulfur
ATPS-500 was found at pH ~3 with the surface being negatively and sulfoxide species would be a major constituent of binding sites
charged and the surface of ATPS changed in positively charged above on impregnated ATPS for the Hg2+ adsorption.The shifting of pHPZC at
and below the IEP. This is because at pH above IEP; ATPS surface is higher pH after Hg2+ adsorption onto ATPS-500 further supports the
protonated, leading to the formation of positively charged ATPS, inner-sphere complex formation (Fig. 4).
whereas, at pH lower than IEP deprotonation occurred and the sur-
face of ATPS becomes negative due to the ionization of -OH groups
3.3. Effect of pH
on the surface of without impregnated ATP. The IEP of ATPS-Hg2+
was found to be positively charged than ATPS-500. It could be
The effect of solution pH on Hg2+sorption at ATPS-500 surface was
attained due to the specific adsorption of Hg2+ onto the binding sites
determined from the pH range of 2 to 10 and the results were illus-
of ATPS and altering its surface charge. In addition, the interaction
trated in the Fig.S2. Usually, pH can influence the stability of metal
between the ionic constituents of adsorbent with different pH ranges
complexes, conformation of molecular structure, and surface charge
have been affected the adsorption ability because adsorption by
outer-sphere complex mechanism is more impacted than inner-
sphere depending on ionic strength of solution [23], this implies that
Hg2+ removal by ATPS-500 could be elucidated by the inner-sphere

Fig. 3. XRD spectra of the raw ATP and ATPS-500. Fig. 4. Zeta potential of (a) ATP (b) ATPS-500 and (c) ATPS-Hg2+.
208 Q. Qiao et al. / Journal of the Taiwan Institute of Chemical Engineers 119 (2021) 204
212

of an adsorbent in the aqueous phase [35]. The H+ and HO
ions are
relatively adsorbed, and hence, the adsorption of other ions has an
effect on solution pH. Acidic and basic electrolytes are going to be
split into separate smaller negative and positive ions at pH > pKa
and/or pKa > pH, respectively. A parallel phenomenon occurs on the
ATPS surface since of its amphoteric nature. If pHZPC > pH, then ATPS
surface became positively charged, while the opposite charge formed
at pHZPC h pH [1, 36]. Thus, anions adsorption is recommended at pH
< pHZPC, whereas pH i pHZPC is more favored than the cations adsorp-
tion. At low pH, ATPS became negatively charged due to the donor/
acceptor interaction between the different metal oxide layers and the
hydronium ions. The pHZPC for ATPS-500 was found to be ~3.1 (Fig. 4)
[37].
Fig.S2 shows the results of mercury adsorption capacity, which
usually increased with decreasing the pHo from 10 to 2 when a 50 mL
solution is treated with keeping all other parameters constant. Hg2
+
adsorption onto ATPS-500 was found to be higher at pH ~5, and
thereafter, scarcity was attained at pH ~10. This is because surface
charges were changed with changing the solution pH [38]. At pHo~5,
the zeta potential of both ATPS-500 and Hg2+was found to be oppo-
site to each other (Fig. 4). Thus, the electrostatic attractive interaction
Fig. 5. Effect of initial concentration and temperature ( °C) on the adsorption of Hg2+
between ATPS and Hg2+significantly leads the adsorption of Hg2+onto by ATPS-500 at t: 24 h, m: 0.02 g, V: 50 mL, pH: 5.
the ATPS-500, which is opposite in nature at higher pH since at highly
acidic solution (pH < 2) the positively charged species (Hg2+ ions)
exists predominantly as hydrated Hg2+(aq), while pH range between initial concentrations, signifying that the adsorbent would be effi-
2 and 5, positively charged and neutral metal
hydroxyl of Hg such as cient for the bulk of water supplies.
(HgOH)+ and Hg(OH)2 were formed via the hydrolyze of Hg2+(aq)
[39]. These metal
hydroxyl species have a greater affinity towards 3.5. Effect of contact time and adsorption kinetics
the binding sites than hydrated Hg2+(aq) since soft Lewis acidic nature
or smaller hydrated sizes [40]. Fig. 6 illustrates the effect of t on mercury adsorption by using
This phenomenon is also corroborating via the hard
soft acid- ATPS-500. During the first 30 min, Hg2+adsorption were found to be
base (HSAB) principle. The Hg2+ ions strongly interact with sulfur- very fast at all temperatures (293, 303 and 313 K), and subsequently,
bonded ATPS-500 because sulfur impregnation on ATP surface would the adsorption rate steadily increased with rise in the temperature.
significantly generate the soft-soft interaction between sulfur-immo- Fig. 6a shows quick uptake of mercury onto the mesopores surface of
bilized Lewis basic center and hydrated metal
hydroxyl and/or Hg2+ ATPS in the initial stages of treatment at different temperatures. This
ions as Lewis acidic. Wang et al. [31] reported that sulfur effectively is due to the fact that accessibility of larger vacant surface of adsor-
impregnated at the surface of activated carbon and improved its bent subsequently; adsorbates have a long-range of diffusion onto
adsorption ability towards heavy metal ions. Other earlier reports the inner pores of the adsorbents, which were increased with
suggested that active sulfur groups could effectively work together increasing the temperature. It is obvious from Fig. 6a that a wide tem-
with hydrolyzed and hydroxyl groups of ATP to form a complex net- perature range is limited by the rate of uptakes. If the treatment tem-
work [41, 42]. Thus, the sulfur impregnation may also change the sur- perature was increased, the interaction between the adsorbent and
face OH groups to thiol groups, providing a synergetic grouping mercury would be increased due to increasing the driving force. In
between adsorbent and mercury ions. addition, the rate of uptake is restricted and depends on the following
factors: (i) the adsorbent pore size distribution, (ii) distribution coef-
3.4. Effect of initial concentration and temperature ficient of adsorbate in solid phases and the bulk of the solution, (iii)
solution components affinity to the adsorbent, and (iv) the strength
The effect of Co on Hg2+removal was varied from 1 to 14 mg L
1 of mixing [44
46].
at different temperature. Fig. 5 illustrates the Co and temperature Pseudo-first and second-order kinetic models were employed to
effect on mercury adsorption. The mercury removal increased with examine the mercury adsorption on ATPS-500. The equations of
increasing the initial concentration of Hg2+and treatment tempera- these two kinetics models are represented as eqns. (3) and 4:
ture due to increased the availability of free reactive sites at ATPS-
lgðqe
qt Þ ¼ lg qe
k1 t ð3Þ
500 surface for the adsorption of Hg2+ions till saturation was com-
pleted. The amount of qe was found to be higher since the larger the
t 1 1
driving force for mass transfer at higher concentration. These forces ¼ þ t ð4Þ
qt k2 q2e qe
improved the loading capacity of sulfur onto the ATPS-500 [23, 42].
However, the adsorption capacity increased with increasing both Co where qe and qt (mg g
1) are the amounts of adsorbate at equilibrium
and temperatures, but after an optimum level of concentration at dif- and after time t, respectively. The rate constants k1 (h
1) and k2 (g
ferent temperatures, the value of qe becomes constant. This could be mg
1 h
1) are denoted the rate constants of pseudo-first and
related to the fact that at higher temperature collision frequencies pseudo-second order kinetic equations. These kinetic models have
increased till the saturation of the surface adsorption sites, which is been applied to examine their strength using the experimental data
favored by a higher concentration of Hg2+ions adsorption [43]. More- of adsorption kinetic with non-linear regression. To know the best fit-
over, decreasing in adsorption at relatively high concentrations is ting of the kinetic models to signify the experimental data, the Mar-
recommended to decrease the competitive binding of the proton at quardt's percent standard deviation (MPSD) error function was used
the surface of sorbent material parallel with decreasing HgOH+ and [8]. The best fit values of kinetic parameters are illustrated in Table 1.
Hg[OH]2 concentrations. In this study, a considerable reduce in The values of qe,cal and qe,exp of both kinetic models, are given in
adsorption capacity of mercury is only observed at relatively high Table 1. The best fitting of pseudo-first-order kinetic models onto
 Q. Qiao et al. / Journal of the Taiwan Institute of Chemical Engineers 119 (2021) 204
212 209

ATPS confirmed by the calculated Adj R2 and MPSD values. Moreover,

the values of qe,cal, and the qe,exp were found to be very close to each
other for the first-order kinetic model. Fig. 6a shows the best fitting
with solid lines for the pseudo-first-order-model of mercury
removal.

3.6. Intra-particle diffusion model

The rate-controlling of Hg2+ions adsorption onto ATPS may possi-

bly be associated with intra-particle diffusion (IPD). This model was
used to explore the possibility of IPD [36]. Weber and Morris were
recommended the IPD model. The equation of this is represented by
the eqn. (5) [30].

Fig. 6. (a) Effect of contact time and T on the adsorption of Hg2+ by ATPS-500. Experi-
mental data points given by the symbols and the lines predicted by the kinetic model
of pesudo-first-order (dash line) and pesudo-second-order (solid line). (b) Weber-Mor-
ris plot for the treatment of Hg2+by ATPS-500 at different temperature keeping other
conditions are same (Co: 2 mg L
1, m: 0.02 g, V: 50 mL, pH: 5).
Table 1
Kinetic parameters for the adsorption of Hg2+by
ATPS-500 at different temperatures.
qt ¼ kp t 1=2 þ C ð5Þ

1
0.5
Where kp (mg g min ) is the rate constant of IPD, and C illus-
trates the thickness of the boundary layer.
If adsorption processes followed by IPD, the Weber
Morris plot
(qt vs. t1/2) should be linear, and IPD acts as the rate-determining step
if these lines pass through the origin [30]. However, if the data shows
the multi-linear plots, the two or more than two steps may affect the
adsorption procedure. Fig. 6b shows the qt vs. t1/2 plot at different
temperatures of Hg2+ adsorption onto ATPS. This plot is a multilayer
representation of more than one method managing the adsorption
procedure. Boundary layer diffusion or adsorbate diffusion from solu-
tion to the outer surface of adsorbent gives by the first portion (line
not shown in Fig. 6b) [11]. Moreover, IPD shows by the two-linear
portions. The second linear portion (first linear line in Fig. 6b) is
ascribed to the dominating nature of intra-particle diffusion with a
gradual equilibrium stage. Slowing down of IPD, a final equilibrium
stage occurs owing to the very small concentration of adsorbate left
in the solution is depicted by the third portion (second linear line in
Fig. 6b) [43]. The rate parameters (kid,1 and kid,2) are defined by the
slope of the linear portions when the rate is controlled via the intra
particle diffusion. It seems from the first portion that the rate-limiting
step depends upon IPD of adsorbate into micro-pores and the fast
adsorption of mercury, while second linear portion showed the final
equilibrium stage of adsorption occurs by slows down the intra-parti-
cle diffusion since the very low concentration of adsorbate left in the
solution at a higher temperature [36]. The values of Kid,1 and Kid,2
increased with raise in the temperature because of the driving force
and adsorption via meso‑and micro-pores surface of ATPS-500
increased. Also, the lines passing through the origin illustrates that
intra-particle transport within the pores is the main rate-controlling
step of Hg2+ adsorption.

Equations Temperature (K)

3.7. Adsorption isotherms
293 303 313

Pseudo-first-order The qe value of ATPS for Hg2+ was also found to be increased with
kf(min
1) 0.06 0.07 0.11
increasing the temperature from 293, 303, and 313 K (See in Fig. S3).
qe,exp(mgg
1) 8.04 8.53 9.62
qe,cal(mgg
1) 7.82 8.18 9.57 Thus, Hg2+ adsorption on ATPS is an endothermic process. The degree
Adj.R2 0.99 0.97 0.99 of adsorption was improved with temperature, which suggests that
MPSD 0.28 0.15 0.04 both physical and chemical adsorption takes part in the sorption of
Pseudo-second-order
Hg2+on ATPS. The results of enhanced qe value of Hg2+ions on ATPS
ks(gmg
1 g
1) 0.01 0.01 0.02
qe,exp(mgg
1) 8.04 8.53 9.69
surface at elevated temperature may be owing to the activation on its
qe,cal(mgg
1) 8.33 8.68 9.95 surface or the formation of several original active sites on the adsor-
Adj.R2 0.95 0.96 0.95 bent surface. This could be the reason that the degree of diffusion
MPSD 0.40 0.23 0.15 onto the ATPS surface, enhancing the rate of IPD and conquering the
Weber Morris
activation energy barrier. Higher the treatment temperature
kid1 (mg g
1 min
1/2) 1.04 1.08 1.82
I1 0.09 0.39 0.19 increased in mobility of Hg2+ from the bulk solution to the adsorbent
R2 0.86 0.87 0.93 surface [47]. It is essential to set up a highly suitable connection in
kid2 (mg g
1 min
1/2) 0.01 0.02 0.03 support of equilibrium curves to design the optimization of the
I2 7.57 7.79 9.49
adsorption system of Hg2+onto ATPS-500. A relationship between the
R2 0.74 0.90 0.96
concentration of dissolved adsorbate in the liquid and the amount of
210 Q. Qiao et al. / Journal of the Taiwan Institute of Chemical Engineers 119 (2021) 204
212

adsorbate adsorbed on the adsorbent surface at equilibrium
explained via the adsorption isotherm.
The three isotherms namely Langmuir, Freundlich, and Temkin
models were fitted to the experimental results by non-linear regres-
sion [44]. The R2 values and other thermodynamic parameters of
these three isotherms are summarized in Table 2. For ATPS, the com-
parison of R2 values confirmed that the Langmuir isotherm has best
fitting for the experimental results at all temperatures (Fig.S3). The
value of qe of Langmuir model was enhanced from 9.51 to 13.16 mg
g
1 for ATPS-500 as temperature increased from 293 to 313 K. As a
result, ATPS has a higher affinity for Hg2+ removal. In addition, the
adsorption capacity of adsorbent is considered by the KF value. At
higher temperatures, the value of KF is higher for ATPS adsorbent
which is representing the endothermic nature of the adsorption pro-
cess (Table S4). The results of Freundlich isotherm indicates that the
values of 1/n were set up not less than 1 for ATPS adsorbent, which
illustrates that this adsorption is less favorable.
3.8. Thermodynamic study
To determine the nature of mercury adsorption onto ATPS, the
removal process was tested in terms of thermodynamic nature. To
attain this study, three parameters of thermodynamic, including DG°,
DH° and DS° are the Gibbs free energy change, heat of adsorption or
enthalpy change and entropy change, respectively were determined
in following sequences [11, 16, 36].
Change in the DG° shows the spontaneity of the process. To obtain
considerable adsorption, DGo must be negative and calculated by
using the eqn. (6).
DG ¼
RT ln K
According to thermodynamics, change in DG associated with DH° o chloride > nitrates [47].
and DSo at constant temperature via the subsequent
equation (eqn. (7)):
DGB ¼ DHB
T DSB
where DG° (kJ mol ) is the Gibbs free energy change, DS° (J mol
1

1
K
1) is the entropy change, DHo (kJ mol
1) is the heat of adsorption
and T is the absolute temperature.
The van't Hoff equation (eqn. (8)) was used to determine the effect
of T on equilibrium constant (K).
DH DS
ln K ¼
þ ð8Þ
RT R adsorption capacity, while desorption rates are related to the radius
where R is gas constant and KL is the Langmuir equilibrium constant
with units of liters per mole [10, 20]. Table S4 shows the results of
thermodynamic parameters. The positive value of DHo demonstrated
the endothermic behavior of Hg2+adsorption and strong interactions
between Hg2+ and ATPS. Similar results were reported by Eloussaief
and Benzina [38] during the removal of Pb2+ from aqueous solution
with natural and acid-activated Tunisian clays. The negative value of
DG° illustrates adsorption is a spontaneous process; while the
positive value of DS° is represented the randomness at the interface
of solid/solution increased due to increasing the structural changes
on adsorbent and adsorbate surface in the bulk of solution [45].
3.9. Effect of co-existing ions
In addition of Hg2+, the industrial effluents often contain various
salts like as Na2CO3, NaCl, NaHCO3, and Na2SO4. The ions of these slats
powerfully take part in a competition of active adsorption sites of
adsorbent to the adsorption of adsorbate. Thus, it is essential to know
the effect of co-existing anions on adsorption capacity [15, 48]. For
this reason, we further analyzed the break via the behavior of Hg2+ in
simulated wastewater having carbonate, chloride, bicarbonate, phos-
phate, sulfate, and nitrate at a confirmed level of concentrations.
Fig. 7 illustrates a noticeably different between the co-existing anions
and Hg2+adsorption. It is clear to be noted that adsorption capacities
of mercury decreased to some extent when co-existing ions concen-
trations increased. The anions of carbonate and bicarbonate (bicar-
bonate has a lesser effect) considerably affect the adsorption capacity
by reducing the amount of 5
12%. This is due to CO32
or HCO3
hav-
ing an excellent affinity for ATPS-500 [31]. In the case of phosphate
and sulfate, phosphate is a highly significant anion with reducing
adsorption capacity of 5
15% than sulfate (10
25%). This difference
between these two anions is related to their ionic radii (sulfate >
phosphate). The comparative study of anions that have a similar con-
figuration, confirmed the strong bonding between the basic layer and
the divalent ions than monovalent anion [47]. The chloride and
nitrate shows a comparatively small effect on the adsorption of Hg2+,
chloride ion has the most effect (10
25%) than the nitrate (10
28%),
ð6Þ which is reliable with the relative choice of anions for ATPS-500 as
In summary, ATPS-500 has weaker interaction forces between
interlayer, strong covalent bond, and the adsorbate and adsorbent
combine through the hydrogen bond, vander Waals's force of attrac-
ð7Þ tion, electrostatic interaction, etc. [23]. The Hg2+adsorption on ATPS-
500 can be spread via inner or outer surface adsorption and the inter-
layer exchange of anions which belong to weaker forces of interac-
tion. The covalent bond is independent of the effect of co-existing
anions due to its selective and non-reversible nature; however, outer
surface adsorption and interlayer anions exchange adsorption are
not reversible and selective for the co-existing anions. Moreover, the
differences between the nature of co-existing anions control the
ratio of divalent cations. Smaller the radius and higher the ionic
charge density leads to the stronger ionic attraction.

Table 2
Isotherm parameters of Hg2+ adsorption by ATPS-500 at different temperatures.

Isotherms Parameters Temperature (K)

293 303 313

qm KL Ce
Langmuir:qe ¼ 1þK L Ce
KL (L mg
1) 13.14 15.43 17.23
qm (mg g
1) 9.51 10.63 13.19
R2 0.99 0.99 0.99
1
Freundlich: qe ¼ KF Ce n KF (mg(1
1/n)g
1L1/n) 7.46 8.39 10.48
1/n 6.06 6.17 5.39
R2 0.87 0.92 0.92
Temkin : KT (Lmg
1) 3282.47 5883.35 3588.95
qe ¼ RT lnKT þ RT lnCe b (J mol
1) 2518.35 2484.36 1941.42
b b Fig. 7. Effect of coexisted anions on Hg2+ removal by ATPS-500 at Co: 2 mg L
1, t: 24 h,
R2 0.96 0.98 0.98
pH: 5 and m: 0.02 g in 50 mL solution.
 Q. Qiao et al. / Journal of the Taiwan Institute of Chemical Engineers 119 (2021) 204
212
3.10. Desorption study
Fig.S4 shows the results of various eluents stirred with Hg2+
loaded ATPS in 50 ml solution. Very low desorption is obtained for
Hg2+ with the alkali (NaOH), pure water and mineral acids (HCl,
HNO3 and H2SO4) compared with the removal percentage obtained
with organic solvents such as acetic acid (CH3COOH) and acetone
(CH3COCH3). The low desorption results show that bond formation
may take place between the adsorbates and the active sites of ATPS.
Cui et al. [23] reported a desorption study of Hg2+ from spent adsorb-
ents for the thermal desorption analysis. During the thermal desorp-
tion testing of spent ATPS, the mercury loaded ATPS first kept in hot
air oven for 2 h at 373 K and after that kept it in a furnace at 623 K for
4 h. After thermal desorption of mercury, unloaded ATPS was further
used for the adsorption of mercury at optimum condition, after that
loaded adsorbent was again thermally desorbed through the same
method as given above. Fig. S4 shows the results of removal percent
of mercury in five successive experiments for repeating the adsorp-
tion-desorption (A-D) cycle. It is observed that the spent ATPS can be
reused for five successive A-D cycles till it reduced the adsorption
capacity by nearly half of its first cycle capacity. It may obtain due to
the additional complex attachment of mercury with sulfur impreg-
nated ATP. This could be recognized as the strong chemical bonding
between ATPS and adsorbed mercury, which prohibits the adsorbed
mercury from being successfully washed by the thermal desorption,
and this is the reason for the decrease in removal efficiency after
every cycle [48,49].
Conclusions
In this study, surface characterization techniques established the
grafting of sulfur atoms on the ATP surface. The results of zeta-poten-
tial confirmed the availability of active binding sites on ATP-500 sur-
face to enhance the adsorption capacity of Hg2+ ions and Langmuir
sorption isotherms model was well fitted with experimental equilib-
rium data. The adsorption properties of Hg2+in aqueous medium on
porous ATPS-500 were examined the well-fitting of the pseudo-first-
order kinetic model. It can conclude that chemisorption (intra-parti-
cle transportation within the pores) generally contributes in Hg2+
adsorption which depends on intra-molecular Hg2+complex forma-
tion. Co-existing anions have diverse controls on Hg2+adsorption
capacity due to the relative preference of anions and competitive
adsorption on the surface. The effect of co-existing anions was found
in the following sequence: NO3
< Cl
< H2PO4
< SO42
< HCO3
<
CO32
. The regeneration of ATPS-500 was tested by using different
solvents, and the solvent assisted regeneration of ATPS-500 was
established to be incredibly smaller with higher desorption efficiency
confirmed by acetone. However, thermal regeneration of ATPS-500
demonstrated the excellent efficiency in Hg2+removal during five
successive A-D cycles.
Declaration of Competing Interest
This authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was equally supported by the Nantong Planned Projects
for Basic Science Research (Grant No. JC2019153), the National Natu-
ral Science Foundation of China (Grant No. 51978654), and the Qing
Lan Project of Jiangsu Province.
211
Supplementary materials
Supplementary material associated with this article can be found,
in the online version, at doi:10.1016/j.jtice.2021.02.015.
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