Journal of Environmental Management 211 (2018) 323e333

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Journal of Environmental Management

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Research article

Polyamide magnetic palygorskite for the simultaneous removal of

Hg(II) and methyl mercury; with factorial design analysis
Tawfik A. Saleh a, *, 1, Mustafa Tuzen b, c, Ahmet Sarı d, e
a
Department of Chemistry, King Fahd University of Petroleum and Mineral, Dhahran, 31261, Saudi Arabia
b
Gaziosmanpasa University, Faculty of Science and Arts, Chemistry Department, 60250, Tokat, Turkey
c
King Fahd University of Petroleum and Minerals, Research Institute, Center for Environment and Water, Dhahran, 31261, Saudi Arabia
d
Department of Metallurgical and Material Engineering, Karadeniz Technical University, 61080, Trabzon, Turkey
e
King Fahd University of Petroleum and Minerals, Centers of Research Excellence, Renewable Energy Research Institute, Dhahran, 31261, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: A novel efficient adsorbent was prepared by the modification of magnetic palygorskite (MPG) by poly-
Received 18 October 2017 amide via the interfacial polymerization of trimesoyl chloride with m-phenylenediamine. The prepared
Received in revised form magnetic palygorskite modified with polyamide (MPGP) material was appraised for its removal of the
12 January 2018
Hg(II) and CH3Hg species from aqueous solutions. The developed adsorbent was characterized using
Accepted 15 January 2018
spectroscopic techniques. The adsorption ability of the MPGP sorbent was systematically investigated by
Available online 6 February 2018
using the batch method. Factorial design analysis was applied to study the effect of different batch pa-
rameters on the adsorption yield of both mercury species. These factors include mercury concentration,
Keywords:
Mercury
initial pH, sorbent amount and contact time. The equilibrium data coincided with the Langmuir
CH3Hg adsorption isotherm indicating the maximum adsorption capacity of the MPGP was determined as
Palygorskite 211.93 mg/g for Hg(II) and 159.73 mg/g for CH3Hg. The kinetic mechanism of the adsorption of both
Adsorption magnetic mercury species was well defined by the pseudo-second-order while the adsorption processes
Polyamide demonstrated spontaneity and an exothermic character at the studied temperatures. The cycling
Factorial design adsorption/desorption tests made by using a 1 mol/L HCl solution demonstrated that the MPGP had good
reusable performance up to seven cycles. Based on the results it can be suggested that the synthesized
MPGP sorbent can be handled for the elimination of Hg(II) and CH3Hg from wastewater effluents.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction The conventional techniques used to extract mercury ions from

Mercury, a well-known heavy metal toxic pollutant, represents a
risk to the environment and is capable of causing lethal damage
(Wang et al., 2014). In water, mercury mainly exists in its divalent
mercury (Hg2þ), form which is transformed by water organisms to
other more toxic species such as methyl mercury (Liu et al., 2017).
The World Health Organization (WHO) has set a limit of a
maximum Hg uptake of 0.3 mg per week for human consumption
and has also recommended that the maximum acceptable level of
Hg ions in drinking water should be lower than 0.002 mg/L or 2 ppb
(EPA, 2017). Therefore, it is necessary to have highly efficient
methods for the removal of mercury from industrial wastewaters.
* Corresponding author.
E-mail addresses: tawfik@kfupm.edu.sa, tawfikas@hotmail.com (T.A. Saleh).
1 the other hand, clay minerals are both readily available and
Home Page: http://faculty.kfupm.edu.sa/CHEM/tawfik/.
waste include chemical precipitation, physical process, phytoex-
traction, ion exchange, ultrafiltration, reverse osmosis, and both
electrodialysis and electrochemical recovery. However, these
techniques and processes can be unsuccessful at low levels, in
addition to being costly due to the disposal of toxic sludge, the use
of chemical reagents for toxic metal recovery, adsorbent regener-
ation, and high-energy requirements.
Indeed, the most effective technique for mercury removal is
adsorption. However, for this process, it is necessary to have effi-
cient and cost-effective materials. In this regard, some adsorbents
including activated carbon, coal fly ash, natural zeolites, and syn-
thetic zeolites have been suggested for the adsorption of pollutants
from aqueous solutions (Saleh et al., 2017a; Cai et al., 2014; Sani
et al., 2017; Saleh, 2018). Other functionalized materials were also
reported including ceramic, poly(methyl methacrylate), SiO2, and
Al2O3 (Ho, 1975; He et al., 2012; Tuzen et al., 2018; Saleh, 2016). On

https://doi.org/10.1016/j.jenvman.2018.01.050
0301-4797/© 2018 Elsevier Ltd. All rights reserved.
324 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333
reasonably priced materials, which are also an alternative to the
conventional treatment of polluted waste streams (Uddin, 2017;
Saleh, 2015a,b). Palygorskite clay (attapulgite clay) is a promising
adsorbent due to its low cost and advantageous surface properties
(Potgieter et al., 2006; Saleh et al., 2016; Saleh et al., 2017b).
Moreover, to increase the adsorption selectivity of attapulgite clay,
it was supported by different polymers such as melamine formal-
dehyde (Al-Bayati, 2015), poly(acrylic acid) (Liu et al., 2014) and
polyaniline (Kong et al., 2011).
In this work, we proposed the modification of palygorskite by
changing the magnetic properties for easy separation and modifi-
cation of its surface by polymers to enhance its functionality and its
active sites, and thus, its efficiency. In situ interfacial polymeriza-
tion of trimesoyl chloride in n-hexane solution and m-phenyl-
enediamine in water was performed on palygorskite. The magnetic
palygorskite modified with polyamide (MPGP) composite was
synthesized as a novel adsorbent for the simultaneous removal of
Hg(II) and CH3Hg ions from an aqueous solution. The chemical/
morphological structures and surface properties of the synthesized
composite sorbent were analyzed by FTIR, XRD, SEM/EDS, and BET
analysis methods. The batch adsorption conditions were optimized
by designing experiments with a 95% confidence limit. The suit-
ability of the experimental data with different isotherm models was
investigated. Furthermore, the kinetic models and thermodynamic
equations were applied to discuss the adsorption mechanism of
Hg(II) and CH3Hg on the MPGP sorbent.
2. Experimental procedures
2.1. Reagents and equipment
Hg(II) and CH3Hg solutions were prepared from (Merck).
1000 mg/L stock solution was prepared from HgCl2 and CH3HgCl.
NaBH4 (1.5w/v %) in NaOH (0.5w/v %) was applied as a reducing
reagent. Ferric chloride (FeCl3$6H₂O), Ferrous chloride
(FeCl2$4H2O), trimesoylchloride, n-hexane, m-phenylenediamine
and thionyl chloride were purchased from Sigma Aldrich.
2.2. Preparation of the MPGP adsorbent
The magnetic palygorskite modified with polyamide (MPGP)
was prepared in two stages as shown in Fig. 1. The palygorskite
gained magnetic properties by using the following procedure:7.0 g
of palygorskite was dispersed in 150 mL of distilled water and
100 mL ethanol by a sonicator then stirred for 5 h. Then, a 1 mL
solution containing 5.06 g of FeCl₃$6H₂O and 3.5 g of FeCl2$4H2O
was put into the dispersed palygorskite to prepare a 1 M solution.
This optimum magnetization of the magnetic sorbent was added
according to the literature (Yang et al., 2014). 20 mL of ethylene
glycol was introduced followed by stirring for 2 h. This solution was
adjusted with pH of 8e9 and then was heated to 80  C for 6 h (Yang
et al., 2016; Sani et al., 2016). The filtered precipitate was washed
and dried at 110  C overnight. The obtained material was treated
with thionyl chloride, then dried and used for the next step.
The magnetic palygorskite was modified with polyamide by
interfacial polymerization of about 0.1% (w/v) of trimesoyl chloride
in n-hexane and 2% (w/v) solution of m-phenylenediamine in wa-
ter, where magnetic palygorskite was properly dispersed. The ob-
tained mixture was stirred for 3 h to achieve complete
polymerization. The obtained materials were separated, washed
and then dried.
2.3. Characterization
Scanning Electron Microscope SEM (TESCAN, LYRA 3) was
utilized to study the morphology of the prepared material using
secondary electron (SE) and backscattered electron (BSE) mode
with 20 kV accelerating voltage. Energy dispersive X-ray spec-
trometer (EDS, Oxford Inc.) was attached to the SEM. Powder X-ray
diffraction pattern (XRD) of the dried composites was recorded on
Rigaku miniflex II X-ray diffractometer in step scan mode between
0 and 80 2q (scan rate 0.02 2qs1) using CuKa radiation
(l ¼ 1.5414 Å). A peak is characterized by 2q position and intensity.
The surface structure parameters were determined from the N2
adsorption/desorption isotherms, which were measured by an
automated surface area analyzer; micromeritics ASAP 2020 using
N2 adsorption-desorption at - 196  C. Samples were degassed prior
to measurement at 300  C for 4 h to remove impurities. The surface
area of composites was calculated by BET method whereas pore
volume and average pore diameters were determined using BJH
method.
2.4. Batch adsorption procedure
Hg(II) and CH3Hg sample solutions (50 mL of 10 mg/L) were
buffered pH 5 by using acetate buffer solutions. 200 mg MPGP as
adsorbent was added to this solution. This mixture was shaken at
120 rpm for 30 min by a temperature controlled shaker. The
adsorbent was taken from the aqueous solution by using a neo-
dymium magnet. The concentrations of Hg(II) and CH3Hg in the
solution were determined by using cold vapour atomic absorption
spectrometry (CVAAS). Measurements were performed using high
purity argon and peak height was used. This procedure was carried
out under different batch conditions: contact time 15e45 min, pH
3e7, initial metal concentration 10e400 mg/L, adsorbent concen-
tration 1e20 g/L and temperature 24e60  C. To ensure the repro-
ducibility of the method, all experiments were repeated in
triplicate. The adsorption (%) of Hg(II) and CH3Hg were calculated
as follows:
ðCi  Ct Þ
Adsorption ð%Þ ¼ x100 (1)
Ci
where Ci (mg/L) is the initial concentration of the mercury species
in the solution while Ct (mg/L) is its concentration at any t time.
2.5. Cycling adsorption/desorption process
The desorption process of the Hg(II) and CH3Hg species from the
adsorbent was evaluated as a function of HCl concentration by
mechanical shaking. 5 mL of HCl solutions with concentrations of
0.10 mol/L, 0.25 mol/L, 0.5 mol/L and 1.0 mol/L was used as an
eluent. The cycling adsorption/desorption process was repeated ten
times. The adsorbent was rinsed with distilled water after each
cycle, for the removal of the excess acid and then dried.
2.6. Design of experiments
The one-variable-at-a-time technique does not provide enough
information about the interaction between the adsorption factors.
Thus, to gain more insight into the interaction between the factors
affecting the adsorption, a design of experiments (DOE) was carried
out (confidence limit ¼ 95%). In this study, factors of pH, adsorbent
dosage, contact time and the initial concentration of mercury were
optimized. The low, mid and high levels (1, 0, 1) for the parame-
ters are shown in Table 1. Table 1 summarizes the generated data.
The experiments were performed and the response was inserted
for analysis.
 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333 325

Fig. 1. Preparation steps of MPGP adsorbent.

3. Results and discussion

Table 1 3.1. MPGP characterization

Design matrix of the factorial design (DOE).

Variable Low() Central point (0) High(þ) The prepared MPGP was characterized by morphology, XRD, and
(A)pH 3 5 7 a surface area analyzer. Fig. 2(a) depicts the elemental analysis of
(D)Dosage of adsorbent (mg) 50 200 400
(T)Contact time (min) 15 30 45
the prepared MPGP. The EDX spectrum indicates that the sample
(C) Initial concentration (ppm) 1 10 40 consists of silicon (at 1.739 keV), magnesium (at 1.253 keV),
aluminum (at 1.486 keV), oxygen (at 0.525 keV) from the paly-
Experiment A D T
gorskite and carbon (at 0.277 keV) and oxygen with trace amounts
1 1 1 1 of nitrogen (at 0.392 keV) from the polymer. In addition, the iron
2 1 1 1
3 1 1 1
was detected at 0.7, 6.4 and 6.9 keV. Table 2 also listed the
4 1 1 1 elemental analysis of the synthesized MPGP. The SEM image in
5 1 1 1 Fig. 2(b) indicates the chains on the surface of the materials which
6 1 1 1 are due to the formation of polyamide chains on the palygorskite.
7 1 1 1
As seen from the XRD patterns in Fig. 3, the palygorskite compo-
8 1 1 1
9 1 1 1 nent of MPGP has the largest peak. The main peaks in the XRD
10 1 1 1 pattern look similar to those of the original palygorskite, indicating
11 1 1 1 that its crystal structure was maintained after the formation of the
12 1 1 1 polymer chain on its surface (JCPDS-ICCD 00-031-0783) (Jeffrey
13 1 1 1
14 1 1 1
and Heaney, 2008). The main diffraction peaks at 2q ¼ 8.6, 14.1,
15 1 1 1 16.5, 19.9, 21.5, 27.9, 28.8, 35.1, 42.6 and 55.6 were assigned to
16 1 1 1 (110), (200), (130), (040), (221), (400), (221), (061), (371), (602)
17 0 0 0 planes. The peaks at 2q ¼ 26.6 and 30.9 can be assigned to the
18 0 0 0
(011) plane of quartz and the (104) plane of dolomite (Zhu et al.,
19 0 0 0
20 0 0 0 2016).
21 0 0 0 The textural parameters of the prepared MPGP, as determined
by the nitrogen adsorption-desorption method, are listed in Table 3.
326 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333

It is clearly shown in this table that prepared MPGP is a kind of Table 2

typical microporous adsorbent with a BET surface area of 380 m2/g. EDX elemental analysis of the prepared MPGP adsorbent.

The BET isotherm is shown in Fig. 4. It can be clearly seen that the Element Apparent concentration k Ratio Wt% Wt% Sigma
plot of the MPGP isotherm is of type IV. O 3.70 0.01245 31.00 1.65
C 2.30 0.27890 8.01 1.05
Mg 0.08 0.00055 1.72 0.31
3.2. Optimization of the adsorption efficiency by MPGP Al 0.39 0.00283 8.07 0.55
Si 0.90 0.00714 18.94 0.93
Statistical analyses of the adsorption efficiency of MPGP for Fe 1.22 0.01216 32.26 2.64
Hg(II) and CH3Hg removal were examined according to the exper- Total: 100
imental design results. The full factorial design was established to
investigate the crucial factors with their interactions in the sorp-
tion. The main effects of Hg adsorption were identified with a adsorption of Hg(II) by increasing the dosage and contact time,
confidence level of >95% (Ozbay and Yargic, 2017). The removal although the increase is not as significant as that in the case of pH.
efficacy rises by varying the factor from low level to high level when The contact time required to reach equilibrium is affected by the
the influence of a factor is toward the positive side. However, the features of the adsorbent and its available adsorption sites. As seen
negative effect causes a reduction in the removal efficiency when a in the main effect plots, the removal efficiencies improved with the
factor is changed from a low level to higher. contact time. On the other hand, there is a decrease in adsorption
In Hg(II) removal, pH, dosage, and contact time have positive by increasing the concentration from 1 to 40 ppm. A similar trend
effects while the initial concentration of Hg(II) has a negative effect, can be seen in the case of CH3Hg as depicted in Fig. 6(a).
as shown in Fig. 5(a). The slope of the effect indicates the sign of the The normal probability plots of standardized effects for Hg(II)
main effect. For instance, the adsorption of Hg(II) on MPGP and CH3Hg adsorption, applied to judge the normality of data, is
increased by increasing the pH between 3 and 7. The increase in the depicted in Figs. 5(b) and 6(b). Each point on the plot refers to one

Fig. 2. (a) EDX spectrum (b) SEM image of MPGP adsorbent.

 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333
Fig. 3. XRD pattern of MPGP adsorbent.
Table 3
The BET properties of MPGP adsorbent.
Single point surface area at p/p ¼ 0.300000000:
BET Surface Area:
Langmuir Surface Area:
t-Plot Micropore Area:
t-Plot External Surface Area:
BJH Desorption cumulative surface area of pores
between 17.000 Å and 3000.000 Å width:
Single point adsorption total pore volume
less than 403.122 Å width at p/p ¼ 0.95:
Adsorption average pore diameter (4V/A by BET):
Desorption average pore diameter (4V/A by BET):
BJH Adsorption average pore width (4V/A):
BJH Desorption average pore width (4V/A):
D-H Adsorption average pore width (4V/A):
D-H Desorption average pore width (4V/A):
Freundlich Qm$C:
Freundlich m:
Temkin q$alpha/Qm:
Temkin A:
Average Particle Size
Median pore width:
Dubinin-Astakhov Micropore surface area:
Limiting micropore volume:
Fig. 4. N2 adsorption/desorption isotherms BET plot of MPGP adsorbent.
327
effect. From the graph, the factors and interactions can be seen in
two zones; negative and positive. The value of the negative coef-
ficient is seen <50%, while values on the opposite side are for fac-
tors with positive coefficients. The nonsignificant effects, as
symbolized by circles, are close to the fitted line, while factors with
significant effects (which are represented as a square) are situated
away from the fitted line.
Pareto plots, depicted in Figs. 5(c) and 6(c), are used to prove the
observation from the normal plots. The values positioned to the
right of the vertical line (2.78) were significant. The vertical line
indicated the minimum effect degree for a 95% confidence level.
Consequently, the pH of the solution was a more significant effect in
the case of Hg(II) than in the case of CH3Hg. The interaction effect
plots, Figs. 5(d) and 6(d), are significant when two factors are
interacted to each other by altering from a lower level to a higher
level without representing non-parallel lines. The interactions be-
tween the pH and dosage were more significant than the other
interactions.
3.3. Modeling evaluation results
The adsorption isotherm was used to describe the interaction of
379 m2/g Hg(II) and CH3Hg with the developed MPGP composite sorbent.
380 m2/g The isotherm indicates the association between the concentrations
1722 m2/g
of these species in the aqueous solution and their adsorbed
125 m2/g
253 m2/g amounts by the sorbent at equilibrium.
The adsorption isotherms for both mercury species were ob-
211 m2/g tained using the Langmuir and Freundlich model equations. The
Langmuir model suggests monolayer adsorption which has taken
0.57 mL/g
61 Å
place on a homogeneous surface with no transmigration in the
72 Å plane of the surface. During the adsorption, it is assumed that there
120 Å is no interaction between the adsorbed ions and uniform adsorp-
118 Å tion. The isotherm parameters are usually determined by linear
121 Å
regression of the model equations. However, in this work, the
119 Å
7.14.105 mol/g isotherm parameters were calculated using nonlinear equations of
3.3983 these isotherm models because the use of the nonlinear method
0.338942 kJ/mol$(mmol/g) would be better for selecting the best isotherm model (Ho, 2006;
0.6598 mm Hg Yaneva et al., 2013). The coefficient of the coefficient (R2) value
159.271 Å
6.034 Å
was determined from the regression analysis to recognize the best-
306.4076 m2/g fitted model with a higher R2 value. The equilibrium data were
0.136071 mL/g plotted for isotherm fitting based on the following nonlinear
Langmuir equation (I. Langmuir, 1918);
qm KL Ce
qe ¼ (2)
1 þ KL Ce
where the adsorbed amount (mg) of the mercury species per unit
mass (g) of the MPGP composite sorbent is denoted with qe (mg/g)
as the concentration of the species remained in solution at equi-
librium. This is symbolized by Ce (mg/L). The affinity of the active
sites of the modified composite sorbent with the mercury species is
represented by the KL (L/mg) constant while the maximum
adsorption capacity is shown by qm (mg/g).
Fig. 7 shows the Langmuir isotherm plots regarding the
adsorption of Hg(II) and CH3Hg by the MPGP adsorbent. By
regression analysis of these plots, the R2 value was found to be
0.996 and 0.997 for the adsorption of the Hg(II) and CH3Hg ions.
The high R2 value showed that the adsorption type could be well
characterized by the Langmuir model which assumes monolayer
adsorption of the Hg(II) and CH3Hg ions by homogeneous sites of
the MPGP sorbent. Moreover, the maximum adsorption capacity
(qm) of the developed composite modified adsorbent was deter-
mined to be 211.93 and 151.73 mg/g as the model constant, KL was
established to be 7.05  103mg1 and 7.5  103 mg1 for the
Hg(II) and CH3Hg ions, respectively.
328 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333
Fig. 5. The factorial design plots of Hg(II)recovery(%) of; (a) main effects plot of response, (b) normal plot of the standardized effects, (c) Pareto Chart of the standardized effect, (d)
interaction plot for the response of data means.
Freundlich isotherm model is used to designate the multilayer
adsorption processes on the heterogeneous surface and it assumes
an exponential change in the energy distribution through the
adsorption sites. The nonlinear equation is (Freundlich, 1906):
1=n
qe ¼ Kf Ce
The Kf (mg/g) and n are the Freundlich constants designating the
adsorption capacity and the intensity of adsorption or the hetero-
geneity factor, respectively.
Fig. 8 also shows the non-linear affiliation between the qe and Ce
findings obtained for the adsorption of Hg(II) and CH3Hg onto the
MPGP sorbent. The R2 values of both non-linear plots were deter-
mined as 0.989 and 0.988 for the Hg(II) and CH3Hg species,
respectively, assuming that the adsorption of both mercury species
onto the composite sorbent could not be explained adequately by
the Freundlich isotherm model. Furthermore, the Kf constant was
determined as 4.25 and 3.03 as the 1/n parameter was found to be
0.66 and 0.680, respectively for the Hg(II) and CH3Hg ions. Thus, the
removal of mercury by the synthesized MPGP sorbent was pro-
gressed via chemical type-interaction (Lee and Chang, 2011).
3.4. Kinetic evaluation results
(3) The determination of the adsorption rate is essential in terms of
the adsorbent's effectiveness, understanding of the adsorption
mechanism and designing larger adsorption systems. The kinetics
of the adsorption processes of the Hg(II) and CH3Hg onto the MPGP
sorbent was studied under different temperature conditions of, 24,
30, 40 and 60  C. The pseudo-first order (PFO) and pseudo-second-
order (PSO) kinetic models were examined to analyze the adsorp-
tion rates for both mercury species. The linear equation of the PFO
model is (Lagergren, 1898):
lnðqe  qt Þ ¼ ln qe  k1 t (4)
where the adsorbed amounts of Hg(II) and CH3Hg onto the MPGP
sorbent at equilibrium any t time and was denoted by qe(mg/g) and
 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333 329

Fig. 6. The factorial design plots of CH3Hg recovery(%) of; (a) normal plot of the standardized effects, (b) Pareto Chart of the standardized effect, (c) main effects plot of response, (d)
interaction plot for the response of data means.

qt (mg/g), respectively, as the rate constant for the PFO model is
typified by k1(min1).
Fig. 9 demonstrates the PFO kinetic plots attained by graphing
the ln(qe-qt) data vs t. The model data derived from these plots were
tabulated in Table 4. The relatively low R2 values determined in the
range of 0.742e0.825 for Hg(II) and 0.749e0.795 for CH3Hg
exhibited that the kinetic mechanism of adsorption of both mer-
cury species could not be clarified satisfactorily by the PFO model.
Besides, as seen from Table 4, the great differences between the
experimental qe,exp and the calculated qe1,cal verified the inconve-
nience of the PFO equation for the kinetic assessment of the equi-
librium data.
On the other hand, the linear form of the PSO model equation
can be written as follows (Mckay and Ho, 1999)
PSO modeling data. The rate constant of the PSO model (k2; g
mg1min1) is found from the slope of these plots while the qe
value is established from the intercept points for them.
By linear regression analysis of the plots, the R2 values deter-
mined in the range of 0.990e0.992 for Hg(II) and 0.994e0.998 for
CH3Hg revealed that the kinetic mechanism of adsorption for both
mercury species could be recognized adequately by the PSO model.
In this regard, the kinetic rates for both mercury species may be
limited by the chemical adsorption between the mercury species
and the functional groups of the MPGP sorbent. Additionally, the
calculated qe values for the examined temperatures are close to the
experimental data, meaning that the PSO model equation closely
fits the adsorption data.

t 1 t 3.5. Thermodynamic evaluation results

¼ þ (5)
qt k2 q2e qe
Thermodynamic assessment of the experimental values pro-
Fig. 10 shows the plots of the t/qt vs t for the adsorption of Hg(II) vides a clearer understanding of the dependence of the adsorption
and CH3Hg onto the MPGP sorbent and also Table 4 indicates the process on temperature. With this aim, the adsorption of Hg(II) and
330 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333

Fig. 7. Non-linear Langmuir isotherms and regression analysis results.

Fig. 9. The kinetic plots obtained for the PFO model.

and 18.41, 17.36, 16.18 and 13.22 kJ/mol.K for CH3Hg at 297,
303, 313 and 323 K, respectively. These findings indicated that the
adsorption of both mercury species by the MPGP sorbent occurred
Fig. 8. Non-linear Freundlich isotherms and regression analysis results. more favorably and spontaneously at lower temperatures. The DH
parameter was calculated to be 50.18 and 54.96 kJ/mol for the
CH3Hg on to the MPGP composite sorbent was examined from the
adsorption of Hg(II) and CH3Hg. The negative value of DH showed
thermodynamic aspect at four different temperatures, at 297, 303,
that the adsorption of both mercury species had taken place
313 and 333 K. The change in Gibbs's free energy (DG) was calcu-
exothermically. These values fall in the area of chemisorption in-
lated based on the adsorption equilibrium constant, KD determined
teractions for both mercury adsorptions and, in addition to the
by using the following equation (Amin et al., 2016):
physical attraction forces, the metal-complexion could be domi-
nant for the Hg(II) and CH3Hg sorption (Fu et al., 2012).
DG ¼ RTlnKD (6)
Moreover, the DS parameter was determined to be 105.01 and
1123.63 J/mol.K, indicating that the randomness at the interface of
Cad solid and solution was decreased for the studied temperature range
KD ¼ (7)
Ce throughout the adsorption of Hg(II) and CH3Hg onto the MPGP
composite sorbent. The similar results regarding the negative
In eqs. (6)e(8), Ce(mg/L) and Cad(mg/L) signify the level of the
values of DS and DH were reported for the adsorption of Hg(II) and
Hg(II) and CH3Hg species which remained in the solution and were
CH3Hg from aqueous solution using the Lemna minor biosorbent
adsorbed by the MPGP composite, respectively, while R and T are
(Johari et al., 2013).
the universal constant (8.314 J/mol.K) and thermodynamic tem-
perature (K), respectively.
The changes in the adsorption enthalpy and entropy (DH and 3.6. Performance evaluation results for adsorption/desorption
cycling
DS) were calculated by substituting the intercept and slope values
of the plots (Fig. 11) in the following equation:
Cycling adsorption/desorption performance is one of the most
    important parameters to be considered in the preference of an
DS DH
lnKD ¼  (8) adsorbent for large-scale water clean-up systems. Therefore, it is
R RT
desired that the adsorbent should have a high reusability value
The DG was calculated to be 18.89, 18.53, 17.16 without a noteworthy loss in its cycling adsorption/recovery ca-
and 15.22 kJ/mol.K for Hg(II) adsorption pacity. In addition, the concentration of the eluent is another
 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333 331

Table 4
Kinetic parameters derived by evaluation of the PFO and PSO kinetic models.

Temperature ( C) Pseudo-first- order Pseudo-second-order

qe,exp (mg/g) k1 (1/min) qe1,cal (mg/g) R2 k2 (g/mg.min) qe2,cal (mg/g) R2

Hg(II) adsorption
24 3.52 10.6  102 1.11 0.825 3.1  102 3.44 0.991
30 3.36 10.1  102 1.08 0.795 2.6  102 3.27 0.990
40 3.28 5.6  102 1.05 0.762 2.5  102 3.13 0.992
50 3.17 1.7  102 1.04 0.742 2.3  102 3.06 0.992
CH3Hg adsorption
24 3.01 10.1  102 1.11 0.795 7.6  102 2.45 0.996
30 2.82 5.4  102 1.08 0.764 7.0  102 1.60 0.994
40 2.63 2.6  102 1.05 0.757 6.5  102 1.59 0.995
50 2.47 0.6  102 1.04 0.749 5.9  102 1.53 0.998

the used HCl and achieved the maximum in the case of using
1.0 mol/L concentrated-HCl (ii) the CH3Hg ions could be recuper-
ated in noticeable amounts, even by using HCl in low
concentrations.
On the other hand, to evaluate the influence of the adsorption/
desorption cycling on the reusability performance of the synthe-
sized MPGP sorbent, the cycling process was repeated ten times
using 5 mL of 1.0 mol/L HCl. As seen from the results shown in
Fig. 12, after the seventh cycle, the yield reduced gradually from
96% to 77% for the desorption of Hg(II) and from 95% to 72% for
CH3Hg. Moreover, after the tenth cycle, the adsorption and
desorption yields were reduced to 70% and 45%, and 58% and 40%
for Hg(II) and CH3Hg, respectively. These findings revealed that the
prepared MPGP sorbent can be reused for up to seven cycles for the
removal of both mercury species without a remarkable loss in its
adsorption/desorption performance.

3.7. Comparison of adsorption capacity of MPGP

As can be seen from Table 5, the number of investigations into

the simultaneous adsorption of Hg(II) and CH3Hg species is limited.
This table compares the sorption capacity of the MPGP composite
sorbent with different types of sorbents. The sorbent synthesized in
this work appears superior to most of the others. This case makes it
a promising material for the decontamination of the wastewater or
drinking water polluted by Hg(II) and CH3Hg ions.

Fig. 10. The kinetic plots obtained for the PSO model at four different temperatures.

concern to be taken into consideration during the recovery of the

species from the adsorbent. In this text, firstly, the effect of the HCl
(5 mL) concentration used as an eluent for the recovery perfor-
mance of the Hg(II) and CH3Hg ions was studied by using it in four
different concentrations, 0.1, 0.25, 0.5 and 1.0 mol/L. The yield was
found to be 10, 45, 75 and 97% in the recovery of Hg(II) while it was
determined as 95, 96, 97 and 98% for the recovery of CH3Hg,
respectively. These results indicated two facts:(i) The recovery
percentage for Hg(II) was higher by increasing the concentration of
Fig. 11. Plot of ln KD vs 1/T used in the calculation of thermodynamic parameters.
332 T.A. Saleh et al. / Journal of Environmental Management 211 (2018) 323e333

Fig. 12. The reusability performance through five-cycling adsorption/desorption processes.

Table 5
Comparison of sorption capacity (mg/g) of MPGP with different types of sorbents.

Sorbent Hg(II) CH3Hg Reference

Lemna minor 0.028 0.026 Johari et al., 2013

Raw smectite (S) 15.1 12.7 Say et al., 2008
Qurtamine smectite (QS) 13.4 21.6 Say et al., 2008
Dithiocarbamate modified PS/QS 63.4 69.8 Say et al., 2008
CP 521.5 100.3 Samana et al., 2016
CP-Char 46.1 176.5 Samana et al., 2016
CP-AC 142.4 84.2 Samana et al., 2016
RPSR 57.8 42.7 Saman et al., 2014
G-Chitosan 0.0077 0.0089 Kushwaha and Sudhakar 2011
BG-Chitosan 0.0065 0.0072 Kushwaha and Sudhakar 2011
MPGP 211.93 159.73 Present study

4. Conclusions solution decreased as the temperature increased. The cycling

The aim was to study Hg removal with the adsorbent of paly-
gorskite which was firstly treated by the magnetic agent and then
modified by polyamide via the interfacial polymerization. The SEM/
EDS, XRD, and BET analysis results showed that the magnetic
palygorskite modified with the polymer (MPGP) was synthesized
successfully characterized. In the second stage, the prepared MPGP
adsorbent was evaluated as a novel effective adsorbent for the
exclusion of Hg(II) and CH3Hg species from aqueous solutions. The
equilibrium data coincided with the Langmuir adsorption isotherm
and, based on this model, the removal capacity of MPGP was found
to be 211.93 and 159.73 mg/g for Hg(II) and CH3Hg, respectively.
The statistical analyses of the adsorption efficiency of MPGP were
examined based on the experimental design results. The full
factorial design was established to investigate the crucial factors
with their interactions in the sorption. The findings indicated that
the removal efficiencies of both mercury species were improved
with the contact time as the pH of the solution had more effect on
Hg(II) sorption than in case of CH3Hg. The interactions between the
pH and dosage were more significant than the other interactions.
The adsorption data obeyed the PSO kinetic model, signifying that
the adsorption process had taken place via a combination of
physical and chemical mechanisms. The thermodynamic evalua-
tion exhibited that the adsorption process of both mercury species
by MPGP exhibited both spontaneity and an exothermic character.
In addition, the randomness at the interface between solid and
regeneration treatments carried out by using 5 mL of 1.0 mol/L HCl
revealed that the MPGP has a good cycling adsorption/desorption
performance, especially up to seven cycles. Furthermore, the
developed MPGP sorbent shows good adsorptive potential for the
decontamination of wastewater or drinking water polluted by the
Hg(II) and CH3Hg ions.
Acknowledgments
The authors would like to acknowledge the support and fund
provided by King Fahd University of Petroleum & Minerals
(KFUPM) through Project No. IN161011 under the Deanship of
Research. The authors also thank Gaziosmanpaşa University and
Karadeniz Technical University due to allowing to this scientific
collaboration. Dr. Mustafa Tuzen also thanks Turkish Academy of
Sciences for financial support.
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