Journal of Environmental Chemical Engineering 4 (2016) 2487–2499

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Journal of Environmental Chemical Engineering

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

High removal efficiency of Hg(II) and MeHg(II) from aqueous solution

by coconut pith—Equilibrium, kinetic and mechanism analyses
Norasikin Samana , Khairiraihanna Joharib , Shiow-Tien Songa , Helen Konga ,
Siew-Chin Cheua , Hanapi Mata,c,*
a
Advanced Materials and Process Engineering Laboratory, Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai,
Johor, Malaysia
b
Department of Chemical Engineering, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar, Perak, Malaysia
c
Advanced Materials and Separation Technologies (AMSET) Research Group, Health and Wellness Research Alliance, Universiti Teknologi Malaysia, 81310 UTM
Skudai, Johor, Malaysia

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

Article history:
Received 15 February 2016 This study was conducted to investigate the high efficiency of coconut pith (CP) adsorbent in removing
Received in revised form 11 April 2016 Hg(II) and MeHg(II) ions from aqueous solution. The CP adsorbent was characterized using a scanning
Accepted 30 April 2016 electron microscope (SEM), nitrogen adsorption-desorption (NAD) analysis, determination of pH at zero
Available online 2 May 2016 point charge (pHpzc), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron
spectroscopy (XPS). Adsorption performance of the CP adsorbent at various parameters was conducted
Keywords: by varying the initial pH of solution, adsorbent dosage, initial pH, temperature, and contact time. It was
Coconut pith found that adsorption capacity, adsorption rate and enthalpy of the Hg(II) adsorption were higher
Adsorption
compared to the MeHg(II). The adsorption capacity of Hg(II) was 2.60 mmol/g, which was five times
Mercury
higher than MeHg(II). The adsorption isotherm analysis showed that the Hg(II) and MeHg(II) adsorption
Equilibrium
Kinetics data fitted to the Langmuir and Freundlich models, respectively. The overall mechanism of both mercury
Mechanism adsorptions is a combination of physical and chemical processes in which the film diffusion was the rate
controlling-step. The adsorbent regenerability study results showed that the Hg(II) adsorption remained
stable up to five adsorption cycles, which was better than MeHg(II). The selectivity studies reveal the
potential application of the CP adsorbent for the treatment of oilfield produced water (OPW) and natural
gas condensate (NGC) that are rich in mercury ions as well as other cations.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction wastewater and soil promotes the easy transformation of the

The presence of mercury in the environment has become of a
great public concern due to its toxicity in which poses a significant
threat to the public health and ecological systems [1]. In the
environment, mercury may exist in three different forms namely
elemental mercury (Hg
), organic mercury (e.g. methylmercury,
MeHg) and inorganic mercury (e.g. HgCl2). Organic mercury
especially methylmercury is recognized as the most toxic mercury
form to humans [2]. The inorganic mercury is less adsorbed by
living organisms as compared to the elemental mercury and
organic mercury. However, in the presence of organic matters in
* Corresponding author at: Advanced Materials and Process Engineering
Laboratory, Faculty of Chemical and Energy Engineering, Universiti Teknologi
Malaysia, 81310 UTM Skudai, Johor, Malaysia.
E-mail address: hbmat@cheme.utm.my (H. Mat).
inorganic mercury to a more toxic organic mercury such as
methylmercury [2,3]. Since various transformations of mercury in
the environment are generated from ionic mercury, it is necessary
to control the low level of mercury discharge into the environment.
Numerous treatment methods such as chemical precipitation,
conventional coagulation, adsorption, ion exchange, and reverse
osmosis have been applied to control the discharge of mercury
from various effluents [4]. Among these methods, adsorption is
more preferred due to its simplicity, economical and high quality of
treated effluents [5]. In an adsorption process, the removal
efficiency depends on the properties of the adsorbate and surface
chemistry of the adsorbent [6]. Materials such as silicas, carbons,
zeolites, synthetic polymers, agricultural residues, biomass, peats,
and industrial residues, are the most common adsorbents that
have been used to adsorb mercury in aqueous solutions. However,
some adsorbents are expensive; thus, persistent efforts have been
made for developing highly effective, low-cost and locally available

http://dx.doi.org/10.1016/j.jece.2016.04.033
2213-3437/ ã 2016 Elsevier Ltd. All rights reserved.
2488 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499
adsorbents [7]. The waste materials from agricultural industry are
a common source of low-cost adsorbents due to their abundance
and less expensive as compared to other materials [8].
The agricultural materials like other lignocellulosic materials
consist of lignin, hemicellulose, cellulose, lipids, proteins, simple
sugar and other organic matter [7]. These components have variety
of oxygen functional groups (e.g. hydroxyl, carboxyl, phenol and
ketone) that facilitate the adsorption of various pollutants. Many
researchers have published and highlighted the use of agricultural
residues as low-cost materials to adsorb mercury ions such as
coconut fruit/tree residues [9–11], grains residues [12,13], sago
residues [14] fruits and vegetables residues [15–17]. These
agricultural residues have been utilized as adsorbents either in
pristine or modified forms.
The utilization of unmodified agricultural residues (usually
used after washing, drying and grinding) can reduce the
production and energy costs associated with chemical and thermal
treatments of the agricultural residues in adsorbent synthesis [8].
Although variety of residues have been studied as potential
adsorbent for targeting mercury ions, however, most of them have
only focused on inorganic mercury, Hg(II) removal. Adsorbents
such as desiccated coconut waste [10], coconut fiber [11], rice
straw [12,13], and Carica papaya wood [16] show a high adsorption
capacity towards Hg(II). However, they cannot guarantee to have a
high adsorption capacity towards organic mercury ions such as
methyl mercury and phenyl mercury. The development of
adsorbents that is capable of removing both organic ions is
required since in many cases both mercury ions may exist together
in the waste solutions. The various mercury ions in waste solution
may also result from transformations that occur within the waste
solutions [18].
In this study, the performance of coconut pith adsorbent in the
removal of inorganic and organic mercury ions (Hg(II) and MeHg
(II)) was investigated. The coconut pith was used widely as
adsorbents for removing various heavy metals such as Cr(IV), Cd
(II) and Ni(II). So far, there has been no study conducted to
investigate the comparative adsorption behavior of both mercury
ions. Thus, the batch adsorption of both mercury ions at various
adsorption conditions such as pH, concentration, loading, contact
time, and temperature was investigated. The adsorption data
were analyzed using the existing models to evaluate the
mechanisms of the adsorption process. The mercury-loaded
adsorbent was characterized using various analytical techniques
in order to obtain a better understanding on the nature of the
mercury ion interactions and their adsorption mechanisms with
the surface of the CP adsorbent, which could lead to an
enhancement in mercury adsorption. The adsorption selectivity
of both mercury ions over other metal ions as well as adsorbent
regenerability was also investigated due to the industrial
importance, found in many industries such as the removal of
mercury and other metals from natural gas condensate and
produced water from oil and gas exploration activities.
2. Materials and methods
2.1. Materials
Cocos nucifera pith (or coconut pith) was purchased from the
T&H Coconut Fiber Sdn. Bhd. (Johor, Malaysia). Methylmercury (II)
chloride (CH3HgCl, 13% Cl), sodium hydroxide (NaOH, 99%), nitric
acid (HNO3, 65%), hydrochloric acid (HCl, 37%), potassium nitrate
(KNO3, 99.0%), potassium iodide (KI, 99.5%), were purchased from
Merck (Germany), while mercury (II) nitrate monohydrate (Hg
(NO3)2H2O, 99%) was purchased from Sigma-Aldrich (USA). All
chemicals were used as received. The double-distilled water was
used for all experimental studies except for the preparing of stock
mercury ions solutions, which were prepared using deionized
water produced by using the Purite Water System (U.K).
2.2. Methods
2.2.1. Adsorbent preparations
The CP was ground, sieved into particle size range of between
75 mm and 100 mm, and washed repeatedly using double-distilled
water to eliminate water-soluble impurities. After washing, the
sample was dried in an oven at 50.0  1.0
C overnight and further
dried in a vacuum oven at 30.0  1.0
C for 5 h. The sample was then
stored in a desiccator for characterizations and adsorption
experiments.
2.2.2. Adsorbent characterizations
Moisture and ash contents were determined using a proximate
chemical analysis of biomass, according to ASTM E1756-08 [19]
and ASTM E1755-01 [20], respectively. It involved a measurement
of weight loss, following the combustion of about 1 g of sample in a
ceramic crucible at 105.0  1.0
C and 575  1.0
C, respectively. The
pH at point zero charge (pHpzc) was determined using a
potentiometric titration method. A series of 25 mL of 0.1 M
KNO3 having an initial pH values between 2.0 and 12.0 were
prepared. The CP adsorbent (50 mg) was placed in each flask, then
was agitated at 200 rpm in the controlled temperature shaker for
48 h; which was sufficient to achieve equilibrium. The initial pH
values (pHi) of the solutions were adjusted using either HCl or
NaOH solution. The equilibrium pH (pHe) and final pH (pHf) were
measured using a Mettler Toledo Delta 320 pH meter. The pHpzc
was obtained from the plot of DpH (pHi–pHf) against pHi; the
intersection point at which the DpH is equal to zero (DpH = 0).The
cation-exchange capacity (CEC) of the CP adsorbent was deter-
mined via the barium chloride method [21].
The surface morphology of the CP adsorbent was analyzed
using a JEOL model JSM-6390LV scanning electron microscope
(SEM). The adsorbent was coated with a thin gold layer and
scanned at an accelerating voltage of 10 kV. The surface area and
porosity of the adsorbent were determined by using a nitrogen
adsorption-desorption (NAD) isotherm analysis measured using a
surface area analyzer model Micromeritics ASAP 2020 (USA). The
sample was first degassed at 120
C overnight and the NAD analysis
was measured at 196.15
C. A Fourier transform infrared (FTIR)
spectrophotometer (PerkinElmer Model 2000) was used to
identify the functional groups on the adsorbent surfaces before
and after mercury adsorption. The FTIR spectra was analyzed using
a KBr disc method and was scanned at wavenumber range from
4000 cm1 to 400 cm1. The X-ray photoelectron spectroscopy
(XPS) analysis was conducted using an AMICUS XPS instrument
(Kratos Analytical Inc., UK) equipped with a monochromatic Al Ka
radiation at 1486.8 eV, operated at 15 kV and 10 mA. The FTIR and
XPS analyses were carried out for the adsorbents before and after
Hg(II) and MeHg(II) adsorptions.
2.2.3. Adsorption studies
The adsorption performance of Hg(II) and MeHg(II) was studied
using a batch procedure. The stock solutions of 5 mmol/L of each
Hg(II) and MeHg(II) were prepared from Hg(NO3)2H2O and
CH3HgCl salts, respectively. The stock solutions were diluted as
required using double-distilled water.
The batch adsorption experiment was carried out at equilibri-
um and at different contact times. In equilibrium adsorption
experiments, effects of solution pH, adsorbent dosages, initial
mercury concentrations, and temperatures were investigated. For
each experiment, 50 mg of adsorbent was placed in a 125 mL
polycarbonate Erlenmeyer flask having 50 mL of aqueous mercury
solutions of known concentration and shaken two days at 200 rpm
 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499
using a controlled temperature shaker at 30.0  1.0
C. After two
days of shaking, which was long enough to achieve equilibrium
conditions, the mixture was filtered using nylon membrane filters
(0.80 mm) and the residual mercury concentration in the
supernatant was determined using an atomic absorption spectro-
photometer (AAS, Perkin-Elmer precisely HGA 900). For low
mercury concentrations (< 0.2 ppm), the cold vapour-atomic
absorption spectrophotometer (CV-AAS) was used. All analyses
were carried out in triplicate, and the mean values were reported.
No results were accepted if the standard relative error was greater
than 3%. The adsorption capacity at equilibrium, Qe (mmol/g) and
removal efficiency, hr (%) of mercury were calculated using Eqs. (1)
and (2), respectively:
Q e ¼ ½ðCo  Ce ÞV=m
hr ð%Þ ¼ ½ðCo  Ce Þ=Co   100
where Co and Ce are the solution mercury concentrations
respectively at initial and equilibrium (mmol/L), m is the adsorbent
mass (g) and V is the mercury solution volume (L).
The effects of contact time or time dependent adsorption were
studied by varying the initial mercury concentrations (0.25 mM,
0.5 mM and 1.0 mM) and temperatures (30
C, 45
C and 60
C). For
a selected time interval, a small amount of sample was collected for
mercury concentration determination. The adsorption capacity at
time t, Qt (mmol/g) was calculated using Eq. (3),
Q t ¼ ½ðCo  Ct ÞV=m
where Co and Ct are the mercury concentrations respectively at t = 0
(initial) and time t, respectively (mmol/L).
2.2.4. Adsorbent reusability studies
The reusability of the CP adsorbent was investigated by carrying
out the mercury adsorption-desorption experiment. The mercury
loaded-CP adsorbent obtained from the first adsorption experi-
ment was initially washed repeatedly using double-distilled water
and dried. Thereafter, the mercury-loaded CP was mixed with
Fig. 1. SEM image of CP adsorbent.
2489
desorption solution and the mixture was shaken overnight at
30.0  1.0
C using a controlled temperature shaker. The mixture
was then filtered and the CP adsorbent was washed repeatedly
using double-distilled water. The CP adsorbent was dried in an
oven at 50.0  1.0
C, followed by drying in a vacuum oven at
30.0  1.0
C for five hours to further eliminate water vapor. The
regenerated CP adsorbent was reused in the next cycle of
adsorption experiment. The adsorption and desorption cycles
were repeated for five times. It must be noted that the adsorbent
dosage used was constant at 1 g/L. The adsorption performance of
each adsorption cycle was evaluated by its regenerated adsorption
capacity, Qe,r (mmol/g) and regeneration efficiency, hreg (%). The
regeneration efficiency was calculated using Eq. (4),
ð1Þ hreg ð%Þ ¼ 100Q e;r =Q e;o ð4Þ
where Qe,o is the adsorption capacity of the virgin adsorbent
ð2Þ (mmol/g).
2.2.5. Adsorbent selectivity
The adsorption selectivity of mercury ion onto the CP adsorbent
was studied by using oilfield produced water (OPW) and natural
gas condensate (NGC) which were supplied by a local petroleum
company. The concentrations of mercury ion in both produced
water and natural gas condensate were low, therefore, 0.25 mM of
Hg(II) and MeHg(II) were spiked into the OPW and NGC
respectively, in order to increase the mercury concentration to
detectable levels. The adsorption study was carried out using the
same procedure as described in Section 2.2.3. After the adsorption
ð3Þ
process, the mixture was filtered and the filtrate was collected
for metal concentration determination. The concentration of heavy
metals in produced water was directly measured by using an
inductively coupled plasma-mass spectrometry (ICP-MS, Perki-
nElmer model ELAN 6100). The ICP-MS is capable of measuring
multi-elements at once, having detection limit between 0.1 ppt
and 100 ppb.
In the case of NGC, after two days of adsorption process, the
mixture was filtered and the filtrate was collected for metal
digestion process according to the method reported by Zettlitzer
2490 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499

et al. [22]. The metal digestion procedure was required to recover

heavy metals in the NGC so that the concentration of heavy metals
could be determined using the ICP-MS. For this purpose, 25 mL of
the NGC was mixed with 250 mL of aqua-regia solution and stirred
for 3 h at 160
C. The aqua-regia solution was prepared by mixing
100 mL of hydrochloric acid (HCl, 37%) with 35 mL of nitric acid
(HNO3, 65%) and diluted with double-distilled water to the final
volume of 500 mL in a volumetric flask. After three hours of
digestion, the mixture was cooled to room temperature, and
thereafter, the organic NGC and aqueous solution were separated
using a separating funnel. The aqueous solution containing eluted
metal ions was analyzed using the ICP-MS. The amount of metals
adsorbed onto the CP adsorbent was calculated based on a mass
balance. The experiments were conducted in duplicate and the ICP-
MS measurements were done in triplicate. For both cases, the
mean data were reported.
The adsorption selectivity of metal ions in OPW and NGC was
evaluated by calculating the adsorption capacity, Qe (mmol/g) and
distribution coefficient, Kd (L/g) of the respective metal ions. The Kd
can be determined by using Eq. (4).
Kd ¼ ðCo  Ce ÞV=mCe ð5Þ

3. Results and discussions

3.1. Adsorbent characterizations

The moisture and ash contents of CP-Pure were 12.04 (wt.%) and
3.16 (wt.%), respectively. The ash content suggests that the coir pith
contains low extracts with little or no waxes and resin, when
compared with other non-woody lignocellulosic materials [23].
The value of pH at point zero was 6.2  1.48, which was slightly
lower than other reported data [24]; and the cationic exchange
capacity (CEC) was 0.44  0.03 meq/g, which was higher than
previously measured [24]. Fig. 2. FTIR spectra of CP and mercury loaded CP adsorbents.
The surface morphology of the CP adsorbent as given by the
SEM image was not smooth and some nodes were observed (Fig. 1).
The particles had irregular shapes and surfaces. The surface area,
total pore volume, and average pore diameter were 3.275 m2/g,
1.315  102 cm3/g, and 3.60  103 cm3/g, respectively. These
values were much lower compared to other CP adsorbent data
as reported by previous researchers [24].
The FTIR analysis was conducted to identify the functional
groups responsible for mercury adsorption. The vibrations were
contributed by the structures of cellulose, hemicellulose and
lignin. The FTIR spectrum of CP adsorbent is given in Fig. 2. A broad
and strong peak at 3399 cm1 is attributed to the O H stretching.
The CH stretching and bending vibrations from CH3 were
observed at wavelength of 2918 cm1 and 1447 cm1, respectively.
The C¼O stretching peak of ketone, aldehyde and carboxylic from
lignin and hemicellulose were observed at 1727 cm1. The peak at
1440 cm1 is attributed to the C O stretching and C OCH3
deformation, while the peak at 1375 cm1 is attributed to the C O
and C C stretching vibrations.
Fig. 3. Effect of pH on adsorption capacity of Hg(II) and MeHg(II) adsorption onto CP
adsorbent.
3.2. Equilibrium mercury adsorption
presented in Fig. 3. Generally, a high adsorption capacity was
3.2.1. Effect of pH observed for Hg(II) as compared to the MeHg(II). The Hg(II)
The pH of metal aqueous solution has been identified as the adsorption capacity was found to be constant, around 0.25 mmol/
most important variable governing the metal ions adsorption on g over the pH range studied. The adsorption by chelation and
the adsorbents. The pH of the solutions will change the metal complexes seemed to be dominant for the Hg(II) adsorption
physicochemical state of the mercury species in the solution, because no significant difference towards pH was observed. This
ionization state of the functional groups, as well as the total result was in contrast to that of the MeHg(II), in which the initial
charge present on the adsorbent surfaces. The effect of pH on pH greatly affected the MeHg(II) adsorption capacity. The Qe of
mercury ions adsorption by the CP adsorbent is graphically MeHg(II) was found to be the lowest at pHi = 2, but increased as
 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499
the pH increased to a maximum (0.16 mmol/g) in between pH
6 and 7, and thereafter the adsorption decreased.
At pH < pHpzc, the surface of the adsorbent is positively charged
due to protonation of the acidic functional groups. At lower pH,
mercury species with positive charge (i.e., Hg2+ and CH3Hg+) are
dominant, attributed to electrostatic repulsion with the positively
charged surface adsorbent, thus lower adsorption capacity was
observed. In addition, the presence of high concentration of H+ at
lower pH also provides a strong competition with mercury ions for
the available adsorption sites. With increasing pH, deprotonated
sites on the adsorbent surfaces increased, resulting in stronger
attraction for positively charged metal ions. However, for Hg(II)
adsorption, the physicochemical state of mercury species in the
solution and ionization state of the functional groups at various pH
values did not affect the adsorption performance. This result might
be due to a strong affinity of the Hg(II) ion towards active sites
compared to MeHg(II) ion.
As can be seen in the small figure inside Fig. 3, the equilibrium
pH tended to change from the original pH. The pHe of Hg(II)
adsorption became less acidic or more basic, which might be due to
the adsorption of H+ alongside with the Hg2+. On the other hand,
for MeHg(II) adsorption, the pHe of the MeHg(II) did not show any
significant changes as compared to that of the initial pH (pHi). The
optimum adsorption pH was obtained at the pHi of 6, thus it was
chosen for the subsequent experiments of both mercury species.
3.2.2. Effect of adsorbent dosage
The adsorption of Hg(II) and MeHg(II) at different dosages using
their concentration of 0.25 mM was studied. The hr of mercury ions
increased with the adsorbent dosage from (0.4 to 3.0) g/L (Fig. 4).
Fig. 4. Effect of adsorbent dosage of (a) Hg(II) and (b) MeHg(II) adsorption onto CP
adsorbent (solid and dashed lines represent Qe and h, respectively).
2491
However, the hr of the Hg(II) removal reached almost 100%
regardless of adsorbent dosages, which was clearly higher as
compared to the MeHg(II). The hr of MeHg(II) increased
significantly from (26 to 75) % when using (0.4 to 3.0) g/L of
adsorbent dosage, respectively.
The increase of adsorbent dosage reduced the amount of
mercury adsorbed onto a unit mass of adsorbent and the effect was
more pronounced at higher adsorbent dosage. This was because a
fixed mass of adsorbent can only adsorb a certain amount of
adsorbate, which means that with more adsorbent dosage, the
larger the quantity of adsorbate can be adsorbed by the adsorbent.
In addition, because of the high dosage, the particle interaction
may desorb some of the metal ions, which are only loosely and
reversely bound to the adsorbent surfaces [9].
3.2.3. Effect of mercury concentration
The effect of mercury ion concentrations was studied by using
the adsorbent dosage of 1.0 g/L. It was observed that more than 90%
of Hg(II) was adsorbed for the entire concentration ranges (Fig. 5).
However, the hr of the MeHg(II) reduced significantly, as its initial
concentration increased. At lower concentration, the ratio of
mercury molecules available to adsorbent active sites is low,
therefore there is a higher probability for the mercury ions to be
adsorbed. At higher concentration, the available active sites for
adsorption become fewer hence reducing the removal perfor-
mance, since substantial mercury molecules remain in the
solution. It was found that the Qe of MeHg(II) was lower than
Hg(II) which contradicted the report that the adsorption capacity

of metal ion was higher in the presence of Cl thanNO 3 [25]. Thus,
the lower Qe of MeHg(II) might be due to the inability of the bulkier
group of the MeHg(II) to diffuse inside the adsorbent, thereby
reducing the adsorption capacity [15].
3.2.4. Adsorption isotherm
An adsorption isotherm is critical in optimizing the usage of
adsorbent. The adsorption isotherms of Hg(II) and MeHg(II) were
obtained by using 0.2 g/L and 1.0 g/L of adsorbent dosage,
respectively. The adsorption isotherms of Hg(II) and MeHg(II)
are shown in Fig. 6. The adsorption isotherm of the Hg(II) using
1.0 g/L of adsorbent dosage did not reach the plateau Qe, which
means that, the CP adsorbent was still capable to adsorb Hg(II), but
at a higher Hg(II) concentration, it could not be carried out because
it resulted in the precipitation of mercury ion. The Qe at this
condition was only 1.6 mmol/g. Therefore, in order to achieve the
saturation or the maximum adsorption capacity (Qe max), the
Fig. 5. Effect of initial concentration on adsorption capacity of Hg(II) and MeHg(II)
adsorption onto CP adsorbent.
2492 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499

the adsorption process was favorable as the dimensionless

Fig. 6. Adsorption isotherm of Hg(II) and MeHg(II) onto CP adsorbent.
adsorbent dosage for Hg(II) adsorption was reduced to 0.2 g/L and
the Qe max was found to be 2.60 mmol/g. The Qe max of the MeHg(II)
was 0.50 mmol/g. Table 1 shows the comparison of Qe max of CP
adsorbent with other materials towards Hg(II) and MeHg(II)
adsorption. It was found that the CP adsorbent still give a higher
adsorption capacity towards both mercury ions despite its low
surface area and simple preparation procedure.
The adsorption isotherms of both mercury ions were further
analyzed using the Langmuir, Freundlich, Dubinin–Radushkevich
(D–R) and Temkin isotherm models. The isotherm equations and
its linearization forms are shown in Table 2. The constant
parameters of the isotherm models were calculated using a linear
plot of the isotherm equations. Table 3 shows the adsorption
isotherm parameters of the Langmuir, Freundlich, D–R and Temkin
models for the adsorption of Hg(II) and MeHg(II) onto the CP
adsorbent.
The Langmuir isotherm model assumes that the adsorption
occurs on a homogeneous surface by monolayer adsorption
without interaction between adsorbed ions, uniform energies of
adsorption onto the surface, and no transmigration of adsorbate in
the surface plane. As can be seen in Table 3, the monolayer
adsorption capacity, Qm L was found to be close to the experimental
Qe max. The parameter b is related to the affinity of active sites with
the adsorbate and it can be seen that the Hg(II) adsorption
presented a stronger affinity than MeHg(II). It was also found that
constant separation factor, RL (RL = 1/[1 + bCo]) over the initial
concentration range used was between 0 and 1. This result
indicates that the adsorption is favorable. The values of n from the
Freundlich isotherm model also supported the favorability of the
Hg(II) and MeHg(II) adsorption onto the CP adsorbent. The kF
values for Hg(II) indicated that the CP adsorbent had a higher
adsorption capacity compared to MeHg(II). The mean free energy
calculated from the D–R model (EDR) of Hg(II) and MeHg(II) was
17.033 kJ/mol and 11.396 kJ/mol, respectively. These results indi-
cated that the Hg(II) and MeHg(II) adsorption fell within the
chemisorption/ion exchange mechanisms [26]. The binding energy
calculated from the Temkin isotherm model also showed that the
absorption of Hg(II) and MeHg(II) was of chemisorption or ion
exchange mechanism. This result was only acceptable at the
temperature of 30
C. If the adsorption occurs at other temper-
atures, the mechanism might be different due to the different
nature of the thermodynamic properties of the adsorbent-
adsorbate interactions.
In order to identify the most fitted isotherm models to the
experimental data, the model having a high coefficient of
determination (r2) value was normally chosen as the best fit to
describe the adsorption isotherm data. However, Ho [27] reported
that the use of non-linear method would be better for comparison
to obtain the best isotherm model. The isotherm fitting was plotted
based on the non-linear equations, using the model constant
parameters obtained from the linear equation plot analysis [14]. In
addition, another three error functions have been used together to
determine the most fitted model namely, average relative error
(ARE), Marquardt’s percent standard deviation (MPSD) and
normalized standard deviation (DQ) [28]. The r2 of the Hg(II)
adsorption was the highest (r2 > 0.99) for the Langmuir isotherm
model and a good fitting was observed for the whole concentration
studied (Fig. 6). Other isotherm models show lower values
(r2 < 0.80) and other error functions (ARE, MPRD, and DQ) were
bigger than the Langmuir error functions. In the case of MeHg(II)
adsorption, the r2 of the Freundlich and D-R models exceeding
0.99 and other error functions (e.g. ARE, MPSD, and DQ) were the
lowest compared to that of the Langmuir and Temkin models.
However, from the fittings (Fig. 6), the Freundlich matched the
experimental data better than those of the Langmuir, D-R, and
Temkin. Therefore, the isotherm of Hg(II) and MeHg(II) were
concluded to follow the Langmuir and Freundlich isotherm
models, respectively.

Table 1
A comparison of mercury ion adsorption onto low-cost adsorbents as reported in the literature.

Adsorbents Surface area (m2/g) Hg species Qe.max References

(mmol/g)
CP 3.275 Hg(II) 2.60 This study
3.275 MeHg(II) 0.50
CP-Char 464.28 Hg(II) 0.23
MeHg(II) 0.88
CP-AC 505.00 Hg(II) 0.71
MeHg(II) 0.42
Garlic (Allium sativum L.) powder 0.126 Hg(II) 0.003 Eom et al. [17]
RPSR  Hg(II) 0.288 Saman et al. [14]
 MeHg(II) 0.21 3
Coconut milk waste 9.67 Hg(II) 2.23 Johari et al. [10]
Rice straw 8.46 Hg(II) 0.44
Rice straw-MPTES 11.46 Hg(II) 0.78
Lemna minor  Hg(II) 0.14  103
 MeHg(II) 0.13  103
Carica papaya wood 0.955 Hg(II) 0.35 Basha et al. [16]
Palm shell powder 2.23 Hg(II) 0.006
CP-poy(hydroxyethylmethacrylate) 93.5 Hg(II) 0.80 Anirudhan et al. [9]
CP-polyacrylamide 42.3 Hg(II) 1.27 Anirudhan et al. [24]
 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499 2493

Table 2
Non-linear and linear adsorption isotherm and chemical reaction kinetic model equations.

Models Non-linear equation Linear equation

Isotherm models
Langmuir Qe = Qm LbCe/(1 + bCe) Ce/Qe = 1/Qm L b +Ce/Qm L
Freundlich Qe = kfCe1/n ln Qe = ln kf + 1/n ln Ce
Dubinin-Radushkevich (D-R) Qe = Qm exp(bDRe2) ln Qe = ln Qm  2bDRe2
where e = RT ln (1 1/Ce)
Temkin Qe = RT/bT [ln (ATCe)] Qe = (RT/bT) ln AT + (RT/bT) ln Ce

Chemical reaction kinetic models

Pseudo-first order (PFO) Qt = Qe [1  exp(k1t)] ln (Qe  Qt) = ln Qe  k1t
Pseudo-second order (PSO) Qt = t/(1/k2Qe2 + t/Qe) t/Qt = 1/(k2Qe2) + (1/Qe)t
Elovich – Qt = (1/b) ln(ab) + (1/b) ln t

3.2.5. Effect of temperature
The effect of temperature on the adsorption of Hg(II) and MeHg
(II) was studied by varying the adsorption temperatures at
(30, 45 and 60)
C. It was observed that the adsorption of Hg(II)
and MeHg(II) increased with temperature, thereby suggesting the
endothermic nature of the adsorption process, where the net heat
is adsorbed during the adsorption process.
The thermodynamic parameters namely the standard Gibbs
free energy (DG
), standard enthalpy change (DH
) and standard
entropy change (DS
) are calculated using Eqs. (6)–(8), respective-
ly.
DGo ¼ RTlnKb
sign of DG
for both Hg(II) and MeHg(II) adsorption indicates that
the adsorption was spontaneous. The magnitude of DG
increased
with temperature, implying an increased degree of spontaneity at
high temperature. The positive value of DH
indicates that the
adsorption process was endothermic in nature [29]. The DH
value
could be used to measure the interaction force between adsorbent
and adsorbate, giving an indication of the bonding strength of the
interactions. The DH
value of the Hg(II) and MeHg(II) adsorption
was found to be in the range of chemisorption mechanism. The
positive values of DS
suggest that the randomness of the solid-
solution interface has increased [29], which indicate a good affinity
of CP adsorbent towards mercury ions.
ð6Þ
3.3. Mercury adsorption kinetics

RTlnKb ¼ TDSo  DHo ð7Þ The adsorption behavior of Hg(II) and MeHg(II) onto the CP
adsorbent against time was studied by varying the initial mercury
concentrations (0.25 mM, 0.5 mM and 1.0 mM) and temperatures
D So DHo (30
C, 45
C and 60
C). The adsorption kinetics of Hg(II) and MeHg
lnKb ¼  ð8Þ
R RT (II) at various temperatures and initial mercury concentrations are
where R is the universal gas constant (8.314 J/mol K) and T is the presented in Fig. 7. The adsorption rate of the mercury ions
adsorption temperature (K). Parameter Kb is the equilibrium adsorption was initially rapid, then gradually approaching
constant, which relates the ratio of adsorbate concentration on the equilibrium and finally achieved equilibrium at contact time of
solid adsorbent (mmol/g) to the adsorbate concentration in the 360 min. The rapid adsorption rate at the beginning of adsorption
solution (mmol/L) at equilibrium, Kb = Qe/Ce. process could be explained by the high number of active-binding
The thermodynamic parameters of the Hg(II) and MeHg(II) ions sites available on the CP adsorbent surfaces and faster interactions,
adsorption onto the CP adsorbent are given in Table 4. The negative thus creating a bigger mercury concentration gradient between the
solution and adsorbent surfaces. The adsorption rate of Hg(II) was
more rapid than that of MeHg(II) for all conditions studied.
Table 3 Adsorption of metal ions onto the adsorbent surfaces is
Adsorption isotherm parameters of mercury adsorption onto CP adsorbent. basically governed by four consecutive steps: (a) transport of
Parameters Hg(II) MeHg(II)
metal ions from the bulk solution to adsorbent surfaces (external
mass transfer); (b) transfer metal ions from the film to the external
Qe max (mmol/g) 2.60 0.50
surface of the adsorbent (film diffusion); (c) transfer of metal ions
Langmuir from external surface to the internal structure of the adsorbent
Qm L (mmol/g) 2.60 0.53 (internal pore diffusion or intra-particle diffusion); and (d)
b (l/mmol) 40.513 5.362 adsorption of metal ions on active sites via physical or chemical
r2 0.994 0.956
interactions. The internal pore diffusion involves pore diffusion
Freundlich (diffusion within the pore volume) and surface diffusion (diffusion
kf (lnm1n/g) 0.011 0.009 along the surface of pores) [30]. The first three steps are
n 5.184 2.329 categorized as physical steps (or diffusion process), while the
r2 0.707 0.991

Dubinin-Radushkevich (D-R) Table 4

Qm DR (mmol/g) 4.66 1.46 Thermodynamic properties of mercury adsorption onto CP adsorbent.
bDR  109 (J/mol) 1.723 3.850
EDR (kJ/mol) 17.033 11.396 Parameters Temperature (
C) Hg(II) MeHg(II)
r2 0.729 0.993 DH
(kJ/mol)  110.713
DS
(J/mol K) 374.604
Temkin DG
(kJ/mol) 30  4.832  63.196
bT  103 (kJ/mol) 7.428 26.023 45  8.467  66.326
AT (l/mmol) 2821.957 87.836 60  14.086  69.456
r2 0.767 0.948
2494 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499

where V is the volume of the solution (mL), m is the mass of

adsorbent (g), S is the external surface area per mass of adsorbent
(m2/g), bL is the external mass transfer coefficient in liquid phase
(cm/s), CAO and CA are the initial concentration and concentration
of adsorbate (mmol/mL), respectively. Several models have been
developed to estimate the value of bL [31,32]. In this study, the
value of bL was estimated according to the method suggested by
Ocampo-Pérez et al. [31]. The term on the right of Eq. (10) is the
slope of the concentration-decaying curve. The first two data
points at t = 0 and t = 5 min, were used to estimate the slope of the
concentration decaying curve, in which the adsorption can be
assumed to be exclusively controlled by the external mass transfer.
It was found that the external mass transfer coefficients of Hg
(II) were higher than MeHg(II) (Table 5). The MeHg(II) has a larger
molecular size than Hg(II), it thus diffused slower than Hg(II). At
the same concentration, the bL values increase with temperature
for both mercury ions. At higher temperatures, mercury ions
diffused faster because more energy is available for the diffusion
process thus increasing the bL value. The relationships of bL, the
diffusivity of the adsorbate molecule (DM) and temperature are
given in Eqs. (11) and (12):
   
DM ¼ 7:4  108 ðwMB Þ0:5 T = mf V0:6 A ð11Þ

bL ¼ DM =d ð12Þ

where d is the thickness of the film layer (cm), f is the associate

parameter of water = 2.60, MB is the molecular weight of water
(18 g/mol), mf is the viscosity of fluid (water) = 0.89 cp, and VA is the
liquid molar volume of adsorbate at normal boiling temperature.

 Film diffusion

The film diffusion is a transport of adsorbate across the liquid

Fig. 7. Adsorption kinetics of Hg(II) and MeHg(II) onto CP adsorbent at different (a)
temperatures and (b) initial concentrations. Value in the bracket (p;q) in the legend
represents (p) temperature (
C) and (q) initial mercury concentration (mM).
fourth step is a chemical bonding interaction. Several authors have
proposed different models to describe these adsorption kinetic
steps using either physical or chemical based models in order
obtain an insight of the mechanism of metal ion adsorption on the
adsorbent surfaces. In the present study, the adsorption data were
analyzed consecutively following the physical and chemical steps
involved in the adsorption process.
film surrounding the adsorbent particles. According to Eq. (12), the
mass transfer rate is inversely proportional to the film thickness.
The thicker the liquid film, the slower the transfer rate because the
film becomes a diffusion barrier.
Many models have been developed to determine the film
diffusion coefficient (Df) [33]. One of such models is given by
Eq. (13) which was developed based on Fick’s law [34]. The film
diffusion coefficient (Df) is calculated from the slope of the Qt/Qe
against t0.5 at the early stage of kinetic data by assuming the
adsorbent was spherical in shape with radius Rp (cm) [34].
 0:5
ðQ t =Q e Þ ¼ 6 Df =pR2P t0:5 ð13Þ
Table 5
Diffusion model parameters of Hg(II) and MeHg(I) adsorption onto CP adsorbent.

(a) External mass transfer [C]o T bL  105 Df  1012 Deff  1010

(mM) (
C) (cm/s) (cm2/min) (cm2/min)
When adsorbent particles are in contact with a solution Hg(II) adsorption
containing mercury ions, the mercury molecules first migrate 0.25 30 4.349 2.914 7.518
from the bulk solution to the surface of liquid film. The 45 4.792 4.265 14.118
60 5.620 4.765 20.155
concentration of adsorbate decreases from the value of CA at bulk
0.50 30 5.415 5.082 15.558
to Ce,A at the particle surface due to the external film resistance. 1.00 30 5.595 5.969 19.305
The rate of external mass transport (Nt) is presented by Eq. (9).

MeHg(II) adsorption
Nt ¼ VdCt =dt ¼ mbL S CA  Ce;A ð9Þ 0.25 30 1.804 1.061 2.941
45 2.716 1.516 3.251
When t ! 0 then Ce,A ! 0 and CA ! CA0, thus Eq. (9) can be 60 3.143 2.105 4.919
simplified to: 0.50 30 1.004 2.497 4.093
1.00 30 0.742 2.719 5.004
½dðCA =CAO =dt ¼ mSbL =V ð10Þ
 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499 2495

The value of Df estimated using Eq. (13) is given in Table 5. The
Df increased with temperature and initial concentration. The Df of
Hg(II) adsorption values range from 2.914  1012 cm2/min to
5.969  1012 cm2/min, while lower Df was observed for MeHg(II)
with the value range from 1.061 1012 cm2/min to 2.719  1012
cm2/min.
 Internal diffusion
The internal diffusion is a transport of adsorbate from the
external surface of adsorbent (at film boundary) to the internal
surfaces of the adsorbent particles. The transport process has been
assumed to occur by pore diffusion and surface/solid phase
diffusion [33]. The pore diffusion is the transport of adsorbent
within the pores of the adsorbents. Surface diffusion is the
transport of molecules adsorbed on the interior surface of solid
materials from one site to another direction of decreasing
concentration [30]. By this definition, the ‘lumped’ effective
diffusion coefficient, Deff is adopted incorporating the effect of
pore diffusion and surface diffusion. The mass transport at the
internal surface is given by Eq. (14).
Nt ¼ Dp @C=@r þ rs Ds @Q=@r ð14Þ
second order (PSO), and Elovich kinetic models were used to
analyze the Hg(II) and MeHg(II) adsorption onto CP adsorbent. The
mathematical expressions of those reaction kinetic models are
shown in Table 2.
The calculated parameters of the reaction kinetic modeling
analysis of Hg(II) and MeHg(II) adsorption onto the CP adsorbent
are tabulated in Table 6. The adsorption capacity calculated from
the PSO kinetic model (Qe2) is very close to the experimental Qe (Qe.
exp). The increase of mercury initial concentrations resulted in
higher Qe2 and initial adsorption rate (ho2). A similar trend was
obtained for the initial adsorption rate calculated from the PFO
(ho1) and Elovich (a) kinetic models. However, the rate of
adsorption analyzed from the PSO (k2) was found to decrease
with increasing temperature from 30
C to 60
C.
By comparing the r2, ARE and MPSD values of all adsorption
kinetic models, it was found that the PSO kinetic model best fitted
to the experimental data. These results indicated that the
Table 6
Reaction based kinetic model parameters of Hg(II) and MeHg(II) adsorption onto CP
adsorbent.
Co (mM) 0.25 0.50 1.00

Thus, the Deff is defined as (Ho et al. [30]): T (
C) 30 45 60 30 30

Hg(II) adsorption
Deff ¼ Dp þ rs Ds @Q=@C ð15Þ
Qe exp (mmol/g) 0.217 0.232 0.245 0.495 1.012
where Deff is the effective pore diffusion coefficient, Dp is the pore
PFO
diffusivity, and Ds is the surface diffusivity. Qe1 (mmol/g) 0.118 0.099 0.094 0.193 0.316
Several models have been developed to determine the Deff. One k1 (1/min) 0.028 0.032 0.038 0.034 0.039
of such models is the Boyd plot, which can be obtained by plotting ho1 103 (mmol/g min) 3.172 3.185 3.578 6.632 1.213
Bt against time, where the Bt can be expressed by the following r2 0.8636 0.8677 0.8729 0.9055 0.8228
ARE 61.6154 68.8921 70.8609 71.5395 75.9665
equation [35].
MPSD 71.3835 80.7258 81.2244 83.5692 86.6670
Bt ¼ 0:4977  lnð1  FÞ; Fvalue > 0:85 ð16Þ
PSO
Qe2 (mmol/g) 0.220 0.232 0.250 0.497 1.026
k2 (mmol/min) 0.790 0.936 1.006 0.518 0.320
p p ho2  102 (mmol/g min)
Bt ¼ ð p  ½p  ðp2 F=3ÞÞ2 ; Fvalue < 0:85 ð17Þ 3.811 5.038 6.289 12.795 33.667
r2 0.9979 0.9987 0.9983 0.9997 0.9989
F is defined as the ratio of amount adsorbed at time t to amount at ARE 2.6008 2.2246 2.2494 1.2532 2.7455
equilibrium (F = Qt/Qe). The slope (s) of the Boyd plot is used to MPSD 4.0356 3.9387 4.3360 2.3882 5.6795

calculate the Deff value according to the following relationship Elovich

(Eq. (18)). b (g/mmol) 25.128 25.518 25.517 12.859 6.487
2
a (mmol/g min) 0.122 0.201 0.331 0.674 2.054
2
s ¼ p Deff =Rp ð18Þ r2 0.9545 0.9181 0.8859 0.9146 0.8175
ARE 11.3625 12.0871 12.1332 10.8130 14.2657
It should be noted that the value of Bt becomes less reliable as MPSD 16.2829 17.3956 16.8036 15.8741 19.0528
the equilibrium is approached [35], therefore, the plot is only
examined at the initial period. The Deff value of Hg(II) was much MeHg(II) adsorption
Qe exp (mmol/g) 0.126 0.169 0.202 0.168 0.202
higher than MeHg(II). This is due to fact that Hg(II) ion has a
PFO
smaller radius than MeHg(II), and the smaller ion will diffuse faster Qe1 (mmol/g) 0.089 0.115 0.124 0.119 0.134
than the larger one. The Deff values of Hg(II) and MeHg(II) were k1 (1/min) 0.018 0.024 0.027 0.021 0.025
found in the range of 13.258  1010 cm2/min to 19.305  1010 ho1 103 (mmol/g min) 1.587 2.763 3.339 2.500 3.352
cm2/min and 2.941 1010 cm2/min to 5.004  1010 cm2/min, r2 0.9563 0.9940 0.9578 0.9271 0.9465
ARE 51.1318 50.1476 55.3214 49.7557 51.1839
respectively.
MPSD 64.3212 62.8488 7.9632 62.3630 63.3802

 Surface interaction step PSO

Qe2 (mmol/g) 0.109 0.161 0.198 0.158 0.200
k2 (mmol/min) 0.899 0.645 0.639 0.584 0.474
The surface interaction step involves the adsorption of
ho2 (mmol/g min) 1.073 1.674 2.506 1.454 1.893
adsorbate by active sites of adsorbents, in which the adsorption r2 0.9967 0.9948 0.9988 0.9996 0.9998
rate can be represented in the same manner as the rate of chemical ARE 13.3716 9.4859 7.9632 9.8493 8.0146
reaction. Several chemical reaction models have been reported in MPSD 18.2221 12.5184 10.0961 12.7513 9.8286
the literature to describe the chemical reaction step. The modeling
Elovich
normally assumed the overall rate of adsorption is exclusively
b (g/mmol) 44.356 33.369 25.269 28.828 23.320
controlled by the adsorption rate of the adsorbate on the surface of a (mmol/g min) 0.025 0.042 0.061 0.040 0.046
adsorbent assuming that both external and internal mass transport r2
0.9854 0.9971 0.9754 0.9900 0.9903
are neglected. In this study, three most common chemical reaction ARE 5.4299 4.2087 8.2554 9.1467 7.5580
MPSD 7.7115 5.9463 10.7545 14.5184 11.520
kinetic models namely the pseudo-first order (PFO), pseudo-
2496 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499
adsorption of Hg(II) and MeHg(II) followed the PSO kinetic model,
suggesting that the adsorption is controlled by the chemisorption
process. It might involve valency forces through sharing or
exchange of electrons between the active sites of the CP adsorbent
and mercury ions.
 Rate-limiting process
During the adsorption process, the kinetics of adsorption
process may be controlled by either diffusion or the surface
reaction process. The features of these two processes are often
difficult. According to the chemical reaction kinetic based model,
the kinetic data analysis of the Hg(II) and MeHg(II) adsorption onto
the CP adsorbents followed the PSO kinetic model, suggesting that
the chemical process is a rate-limiting step, without considering
the physical (or diffusion) process.
For a diffusion step, there are three main steps of diffusion
process, which are external mass transfer, film diffusion and
intraparticle diffusion (including pore and surface diffusion). Since
the rapid stirring was conducted during the adsorption process,
bulk diffusion effect was assumed negligible and film diffusion
becomes a dominant role during the external mass transfer
process. Therefore, in order to determine the rate-limiting step of
these two diffusion processes (i.e. film diffusion and intraparticle
diffusion), the kinetic data were quantitatively analyzed by using
the Weber-Morris plot (Qt versus t0.5). If the plot gives a straight
line passing through the origin, the intraparticle particle diffusion
is the sole-limiting step; otherwise, other diffusion processes can
be the limiting step [36]. The Weber-Morris plot did not pass
through origin; thereby the intraparticle diffusion was not the rate-
limiting step. There were three-line regions observed for both Hg
(II) and MeHg(II) adsorption, which indicated the presence of more
than one step diffusion process. An additional confirmation to
identify the rate-limiting step between film and internal particle
diffusion could be obtained from the Boyd plot [37]. The Boyd plot
of Bt versus time in the initial period of Hg(II) and MeHg(II)
adsorption onto the CP adsorbent showed a straight line that
crosses at the Y-axis. These results indicated that the film diffusion
was the rate-limiting step. If a straight line of Boyd plot passes
through the origin, it indicated that the adsorption process was
governed by intraparticle diffusion [37]. In order to confirm that
the diffusion coefficient of the two steps was calculated and
compared. The value of Df was smaller than Deff, thus diffusion
through the film is slower than the intraparticle diffusion,
confirming the film diffusion as the rate-limiting step. This
conclusion was made when considering only the diffusion step
processes.
It is noted that in the above discussion that the rate limiting-
step was chosen according to the classification of the process
mechanism. Ho et al. [30] stated that one of the general guidelines
to estimate the controlled process is according to the time
equilibrium is achieved. If the equilibrium is achieved within three
hours, the process is reaction kinetic controlled and above twenty-
four hours, it is a diffusion-controlled process. If the equilibrium
achieved is in between three to twenty four hour period, either or
both reaction and diffusion process may be the rate-limiting step
[30]. In this study, it was found that the adsorption of Hg(II) and
MeHg(II) achieved equilibrium at the maximum contact time of
6 h. Therefore, either or both reaction and diffusion processes can
be the rate-limiting process. A more appropriate quantitative
approach to determine the rate-limiting step is by their activation
energy (Ea) value. The Ea value was determined from the plot of kid
against the reciprocal temperature (Arrhenius plot). The kid is the
intraparticle diffusion rate by the Weber-Morris plot. If the Ea value
is less than 25–30 kJ/mol, the adsorption is controlled by a
diffusion process; otherwise, for energy greater than 25–30 kJ/mol,
it is controlled by the chemical process [30]. The calculated values
of Ea of Hg(II) and MeHg(II) adsorption were 16.370 kJ/mol and
23.640 kJ/mol, respectively, which indicate the diffusion process
was the rate-limiting step.
3.4. Mechanism of mercury adsorption
Throughout the kinetic adsorption studies, two mechanism
processes have been proposed to interpret the adsorption
behaviors of Hg(II) and MeHg(II) namely physical and chemical
processes. The physical process mechanism involves diffusion
steps namely external mass transfer, film diffusion, pore diffusion,
and surface diffusion [38]. The chemical process mechanism refers
to the chemical interaction between the adsorbate and active sites
of the adsorbents. The interaction can be classified as either
physisorption or chemisorption interaction depending on the
nature of the bonding formation. The physisorption has a weak
chemical interaction that could be due to the intermolecular forces
of attractions between adsorbent active site and the adsorbate
such as the van der Waals forces, London dispersion forces, H-
bonding, and classical electrostatic forces. The chemisorption
interactions such as ion exchange, chelation and metal complex are
however identified as strong interactions.
The CP adsorbent had a low surface area and low porosity,
therefore, the mechanism of adsorption tend to be that of surface
covering rather than pore filling. The FTIR result showed that the
CP adsorbent surfaces most possibly contained oxygen active
groups from phenol, ether, aldehyde, carboxylic, ketone, and
hydroxyl compounds. These active groups play an important role
that promotes chemical interactions with mercury ions during the
adsorption process. The monolayer adsorption capacities of the
Langmuir isotherm model of Hg(II) and MeHg(II) were 2.60  103
mol/g and 5.30  104 mol/g, respectively, which were higher than
the CEC value (0.44 meq/g or 4.4  104 mol/g). This result showed
that the ionic exchange process was not a dominant mechanism of
the adsorption. As previously discussed in Section 3.2.1, it can be
concluded that the adsorption of Hg(II) was mainly through metal-
complexion, because there was no significant changes in Qe at
various initial pH values was observed. On the contrary, 41% of the
total MeHg (II) adsorbed was found to be pH dependent, which was
assumed to be due to the ion-exchange process. The remaining 59%
was pH independent, which might be due to the chelation or
metal-complexes process. The mean free energy from the D-R
isotherm model (ED-R) and binding energy from the Temkin (bT)
isotherm model indicate that strong chemical interactions were
present during the adsorption of Hg(II) and MeHg(II). Adsorption at
various temperatures found that high temperature favors an
endothermic reaction. It can be deduced that the chemical reaction
occurs due to the formation of stronger bonds at high temper-


atures. The DH values of both mercury adsorptions fall in the
region of strong chemisorption interactions. Therefore, it can be
concluded that the chelation and metal-complexion might be a
dominant process for the Hg(II) and MeHg(II) adsorption. In order
to obtain more insight into the chemistry and reaction state of
adsorbate and its interaction with binding sites, the FTIR and XPS
analyses of the fresh and mercury-loaded CP were carried out.
The intensity of some FTIR peaks was reduced and other peaks
appeared apparently because of the mercury ions adsorption
(Fig. 2). The OH bending vibrations at 1609 cm1 shifted to a
higher wavenumber for the CP-Hg(II) and CP-MeHg(II). The peak
intensity at 1382 cm1 from the C H bending vibration strongly
sharpened and shifted to 1395 and 1372 cm1 after Hg(II) and
MeHg(II) adsorption, respectively. The peaks at 1507 and
1447 cm1 of the C H bending vibration appeared strongly after
the MeHg(II) adsorption. However, these peaks almost diminished
after the Hg(II) adsorption. Fig. 8 shows a wide scan of the CP
 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499 2497

adsorbent before and after the Hg(II) and MeHg(II) adsorptions.

The mercury element peaks detected in XPS spectra were Hg4f and
Hg4d. The Hg4fwas observed at the region between 100 eV to
106 eV, while Hg4d was observed at binding energy between
355 eV to 380 eV. The high resolution of the Hg4f peak is shown in
Fig. 9(a). The slight but significant changes of O1s and C1s peaks
were observed for the CP adsorbent before and after adsorption.
The optimum binding energy of O1s (Fig. 9(b)) decreased from
532.6 eV to 351.8 eV and 532.1 eV after Hg(II) and MeHg(II)
adsorption, respectively. The C1s spectrum of CP adsorbent
consisted of three peaks (Fig. 9(c)). A strong peak at 285 eV might
be attributed to sp3 of CC bond and other two peaks at 286.5 eV
and 288.8, indicating the presence of CO and O C¼O,
respectively [39]. The peak at 286.5 eV might come from phenol,
hydroxyl or ether groups, and the peak at 288.8 eV might be due to
the presence of carboxylic, ketone and ester groups in the lignin,
hemicellulose and cellulose compounds. After adsorption, the
binding energy of the C O and OC¼O shifted to 285.7 eV and
288.3 eV, respectively. The mercury ions might form complexes
with the oxygen groups such as phenol-Hg, hydroxyl-Hg,

Fig. 9. XPS spectrum of CP and mercury loaded-CP adsorbents: (a) Hg4f; (b) O1s; and
(c) C1s.

carboxylate-Hg or ether-Hg, thus changing the optimum binding

energy of O1s and C1s.

3.5. Adsorbent regeneration and selectivity studies

The adsorbent regeneration is important since it will determine

the adsorption process viability. Thus, it was investigated. Since the
adsorption mechanism of Hg(II) and MeHg(II) involved chemical
reaction process, therefore, the regeneration of mercury-loaded CP
was performed using chemical solutions. In this study, two types of
desorption agents were used namely 0.1 M hydrochloric acid (HCl)
and potassium iodide (KI) solutions. The adsorption desorption
processes were carried out for five adsorption cycles. Fig. 10 shows
the adsorption performance of Hg(II) and MeHg(II) up to
Fig. 8. XPS wide scan of CP and mercury loaded-CP adsorbents.
2498 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499

Table 7
Initial concentration (Co), adsorption capacities (Qe) and distribution coefficient
(Kd) of mercury ions and other metals adsorption in OPW and NGC by using CP
adsorbent.

Cations Co  103 (mM) Qe  103 (mmol/ hr (%) Kd (L/g)

g)
Oilfield produced water (OPW)
Hg(II) 276.41  5.03 234.02  0.47 85.26  0.05 5.74  0.03
Zn 0.44  0.09 0.42  0.0005 95.04  0.01 19.03  0.02
V 3.34  0.16 1.63  0.04 49.09  1.01 0.96  0.04
Cu 2.49  0.29 0.91  0.06 40.00  2.54 0.66  0.07
As 1.94  0.18 1.10  0.04 57.07  2.13 1.32  0.12
Ba 1.99  0.33 0.66  0.05 33.16  2.47 0.49  0.06
Ni 0.04  0.01 0.02  0.002 41.75  3.81 0.72  0.11
Mg 4556.06  125.93 1154.44  99.56 25.45  2.16 0.34  0.04

Natural gas condensate (NGC)

MeHg(II) 259.81  0.08 98.02  7.14 38.00  2.82 0.61  0.07
Zn 14.71  0.56 10.53  1.07 71.43  7.16 2.60  0.90
V 567.72  39.36 479.97  1.34 88.52  0.28 7.66  0.20
Cu 183.71  5.92 168.34  0.21 92.33  0.02 11.96  0.01
As 107.46  15.59 88.69  0.13 82.51  0.24 4.69  0.07
Ba 1.76  0.56 1.06  0.07 63.32  3.43 1.73  0.26
Ni 48.73  1.69 47.69  0.19 97.92  0.25 43.61  5.04
Mg 53.21  5.50 40.30  0.47 75.68  0.81 3.09  0.14

Fig. 10. Regeneration efficiency of (a) Hg(II) and (b) MeHg(II) adsorption in multi-
adsorption cycles.
5 adsorption cycles. The Cycle 1 represents the adsorption onto the
fresh CP adsorbent, while the Cycles 2–5 are adsorption after
regeneration. After a sequence of 4 desorption cycles using KI
solution (KI-regenerated CP), the hreg of Hg(II) adsorption
remained higher than 95%. In contrast, for the CP regenerated
using HCl solution (HCl-regenerated CP), high hreg (i.e. hreg > 95%)
of Hg(II) adsorption can only be achieved up to 2 desorption cycles.
For the MeHg(II) adsorption, the hreg of HCl-regenerated CP
reduced gradually from 94.6% to 55.2% for the first to fourth cycles
of desorption. The hreg of MeHg(II) onto KI-regenerated CP
however, remained constant around 77% after the first to third
cycles of desorption process. Thereafter, the hreg was reduced to
66.5%. In general, the performance of KI-regenerated CP was better
than HCl-regenerated CP. This is because, anion I has the greatest

affinity towards Hg ions as compared to anion Cl , and anion I
tends to form a complex with Hg in solution compared to O Hg
complexes on adsorbent surfaces. Therefore, more Hg ions can be
desorbed using KI solution, and consequently increased the
adsorption performance of the regenerated adsorbent. It can be
concluded that the CP adsorbent can be reused for removing Hg(II)
ions without significantly decreasing its adsorption performance.
Adsorbent selectivity towards Hg(II) and MeHg(II) was carried
out using OPW and NGC, respectively. In order to increase the
mercury ion concentration detectable levels, 0.25 mM of Hg(II) and
MeHg(II) was spiked into the OPW and NGC, respectively. The
concentration of cations present in both OPW and NGC was
measured. It was found that the Mg existed in high concentration
in OPW, while the V, Cu and As in NGC. The concentrations of
cations in the OPW and NGC after the addition of mercury species
are shown in Table 7. The adsorption selectivity of mercury ions
was decreased in the presence of foreign cations in OPW and NGC.
In OPW, the Zn adsorption had the highest Kd and hr, which
indicate the highest selectivity, followed by Hg(II). However, in the
case of NGC, the selectivity of Ni was the highest, followed with Cu,
V, Ad, Mg, Zn, Ba and MeHg(II). The difference of metal selectivity
trends of both OPW and NGC indicates that the chemical properties
of the adsorbate medium play an important factor in determining
the effectiveness of the cations adsorption process. In addition, the
existing other metal ions in the OPW and NGC increased the
mercury ions competition towards the adsorption sites and
reduced their adsorption efficiency.
4. Conclusions
The adsorption of the Hg(II) and MeHg(II) onto the coconut pith
adsorbent from aqueous solution conducted in a batch adsorption
system at various experimental conditions showed that both
mercury ions have different adsorption characteristics. The Hg(II)
adsorption capacity did not give a significant change over the pH
range studied, but it was highly affected towards the MeHg(II)
adsorption. The adsorption capacity of Hg(II) was 2.5 mmol/g,
which was 5 times higher than that of MeHg(II) (0.5 mmol/g). The
Hg(II) and MeHg(II) adsorption isotherm data were best described
by the Langmuir and Freundlich isotherm models, respectively. The
adsorption process of both Hg(II) and MeHg(II) was an endother-
mic and spontaneous process. The rate of Hg(II) adsorption was
faster than MeHg(II) and increased with temperature and initial
concentration. The pseudo-second order kinetic model fitted well
to the kinetic data but the overall rate was controlled by the film
diffusion. The enthalpy, mean energy and binding energy values
indicated the formation of mercury-complexes was a dominant
mechanism for both mercury ions adsorption onto the CP
adsorbent. It was further evidenced from the changes of the FTIR
and XPS spectra of the CP adsorbent before and after mercury
adsorption. The regenerability study of Hg(II) adsorption onto the
CP adsorbent showed a better result as compared to the MeHg(II).
A high selectivity of Zn and Hg(II) in OPW was observed, while the
selectivity of MeHg(II) in NG condensate was low, but a higher
selectivity was observed for Ni and Cu.
 N. Saman et al. / Journal of Environmental Chemical Engineering 4 (2016) 2487–2499
Acknowledgements
The financial supports from the Ministry of Agriculture (MOA),
Malaysia (Project No. 05-01-06-SF1006/79410) and MyBrain15
scholarship from the Ministry of Higher Education (MOHE),
Malaysia are gratefully acknowledged.
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