Journal of Environmental Chemical Engineering 4 (2016) 1839–1849

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Journal of Environmental Chemical Engineering

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Adsorption of mercury(II) on dithizone-immobilized natural zeolite

Mudasir Mudasir* , Karelius Karelius, Nurul Hidayat Aprilita, Endang Tri Wahyuni
Chemistry Department, Faculty of Mathematics and Natural Sciences, Gadjah Mada University, Sekip Utara, P.O. Box Bls. 21, Yogyakarta 55281, Indonesia

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

Article history: Adsorption of Hg(II) ions onto selective adsorbent of dithizone-immobilized natural zeolite (DIZ) from
Received 6 January 2016 Wonosari, Yogyakarta, Indonesia has been investigated in batch mode. Some parameters influencing
Received in revised form 29 February 2016 immobilization of dithizone and adsorption of Hg(II) were optimized including effect of temperature and
Accepted 8 March 2016
reaction time on the effectiveness of dithizone immobilization as well as effect of pH, contact time and
Available online 9 March 2016
initial concentration of Hg(II) ion on the efficiency of the Hg(II) adsorption. Preliminary application of the
adsorbent in the removal of Hg(II) ion in river water spiked with Hg(II) was also studied. The FT-IR and
Keywords:
XRD analytical results show that the surface of natural zeolite can be modified by immobilization of
Mercury
Selective adsorbent
selective organic ligand towards Hg(II) ions. The optimum conditions for the adsorption of Hg(II) is
Natural zeolite achieved at pH 5 and 90 min of contact time. Kinetics and adsorption isotherm studies suggest that the
Dithizone capacity, affinity and selectivity of the DIZ in adsorbing hazardous metal ions such as Hg(II) is
Immobilization significantly improved compared to those of non-immobilized activated natural zeolite (AZ). The Hg(II)
adsorption capacity for AZ and DIZ at optimum condition is 8.0 and 13.1 mmol/g, respectively and the
both adsorption follows first-order reaction. It has also been demonstrated that the DIZ adsorbent may be
applied in the removal of Hg(II) ion in the river water spiked with Hg(II) ion up to 99.36% from the initial
concentration of 8 mg L
1 in two serial batch adsorptions.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Many toxic heavy metal ions have been discharged into the
environment as industrial wastes, causing serious soil and water
pollution [1]. Mercury (Hg), lead (Pb), copper (Cu), iron (Fe), and
chromium (Cr) are common metals that tend to accumulate in
organisms, causing numerous diseases and disorders [2]. Hg(II) has
especially received increasing attention as a serious pollutant due
to its toxicity and bio-accumulative properties. In aquatic system,
mercury can be converted by bacteria to methyl mercury, which
can be magnified hundreds of thousands of times through aquatic
food chain, posing a potential risk to humans and wildlife in the
aquatic that consume fish. The major resources of mercury
pollution in the aquatic are industries including electrical and
medical equipment (batteries and thermometers), paint and color
industries, catalyst, fungicides or pesticides. In addition, coal
combustion, geothermal gas and waste incineration emit large
quantities of mercury into the atmosphere [3]. Numerous
processes exist for removing dissolved heavy metals, including
ion exchange, precipitation, phytoextraction, ultrafiltration, re-
verse osmosis, and electrodialysis [4]. However, these methods
* Corresponding author.
E-mail addresses: mudasir@ugm.ac.id, dasir01@yahoo.com (M. Mudasir).
generally require high cost and technology, thus making it not
suitable for developing countries like Indonesia. Therefore, the use
of alternative low-cost materials as potential sorbents for the
removal of heavy metals has been increasing recently [5,6].
Zeolites are naturally occurring hydrated aluminosilicate
minerals. They belong to the class of minerals known as
“tectosilicates”. Most common natural zeolites are formed by
alteration of glass-rich volcanic rocks (tuff) with fresh water in
playa lakes or by seawater [7]. The structures of zeolites consist of
three-dimensional frameworks of SiO4 and AlO4 tetrahedra. The
aluminum ion is small enough to occupy the position in the center
of the tetrahedron of four oxygen atoms, and the isomorphous
replacement of Si4+ by Al3+ produces a negative charge in the
lattice. The net negative charge is balanced by the exchangeable
cation (sodium, potassium, or calcium). These cations are
exchangeable with certain cations in solutions such as lead,
cadmium, zinc, and manganese [8,9]. The fact that zeolite
exchangeable ions are relatively innocuous (sodium, calcium,
and potassium ions) makes them particularly suitable for
removing undesirable heavy metal ions from industrial effluent
waters. However, like many other natural adsorbants, the
adsorption of zeolite towards metal ions is not selective, especially
when alkaline and alkaline-earth metal ions are also available in
the solution in high level of concentrations. Therefore, modifica-
tion of the surface of natural adsorbants including zeolite is

http://dx.doi.org/10.1016/j.jece.2016.03.016
2213-3437/ ã 2016 Elsevier Ltd. All rights reserved.
1840 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849
frequently done using a specific and sensitive ligand for heavy
metal ions to enhance the capacity and selectivity of the
adsorbants [10,11]. For example, some host materials has been
used for immobilization of sugarcane bagasse waste biomass for
biosorption of chromium [12] and Mangifera indica waste biomass
for biosorption of Pb(II) [13]. Moreover, pre-treated biomaterials
such as rosa bourbonia phyto-biomass for removal of Pb (II) and Cu
(II) [14], groundnut (Arachis hypogaea) shell for divalent ions [15] as
well as lemon grass (Cymbopogon citratus) for Pb(II), Cd(II) and Zn
(II) ions [16] also has been reported as promising adsorbants of
heavy metal ions. Meanwhile, Asasian et al. has reported
elimanation of mercury by adsorption onto activated carbon
prepared from the biomass material [17].
Dithizone (diphenylthiocarbazone) is a suitable ligand for such
purposes because it contains several N-donor atoms,

NH as well
as

SH groups which is excellent for analytical and spectroscopic
applications. This compound is also very specific for chelating
heavy metal ions such as Pb(II), Cd(II), Cu(II) and Hg(II) [18,19].
Therefore, it is quite reasonable to use this chelating compound as
modifiying agent in the surface of various adsorbent materials such
as alumina [20], polymer poly (EGDMA-HEMA) microbeads [10]
and silica gel [11,21,22]. The immobilization of dithizone onto the
surface of the above polymer as well as silica gel has been reported
to be successfully used for the removal and selective pre-
concentration of heavy metals.
The aim of this study is to prepare a mercury-selective
adsorbent by immobilization of dithizone onto the surface of
zeolite and to study its adsorption characteristics towards mercury
(II) ion. The modified adsorbent is intended to be used for the
adsorption of mercury pollutant in industrial liquid waste as well
as the supporting material in the solid-phase extraction process for
pre-concentration of mercury ion. Dithizone has been selected as
the organic ligand in this study because this ligand is very selective
for Hg, Cd and Pb. In this study, we use natural zeolite from
Wonosari, Yogyakarta, Indonesia as a supporting material for the
immobilization of dithizone because it is easily obtained in
Indonesia and its price is cheaper than the synthetic polymer or
silica gel.
2. Materials and methods
2.1. Materials
Mercury(II) chloride salts (HgCl2) and dithizone (1,5-diphe-
nylthiocarbazone) were purchased from Merck, Germany. Natural
zeolite was obtained from Wonosari, Yogyakarta, Indonesia. Zeolite
activation and dithizone immobilization were prepared and
characterized according to previously reported procedure
[23,24]. Organic solvents were of reagent grade and used as
received. For all solutions, double distilled water was used and the
buffer solutions were prepared by mixing citric acid and sodium
citrate for pH < 7 and sodium dihydrogen phosphate (NaH2-
PO4H2O) and sodium hydrogen phosphate (Na2HPO412H2O) for
pH: 7–9 and the pH-value of the resulting solution was checked by
pH-meter.
2.2. Instrumentations
The pH measurements were conducted by a TOA pH meter
model HM5B calibrated against two standard buffer solutions of
pH 4.0 and 9.2. Infrared spectra of natural zeolite and dithizone-
immobilized zeolite were measured from KBr pellets by a
Shimadzu FT-IR/8201 PC spectrophotometer. Mercury(II) determi-
nation was performed by a GBC 932 AA atomic absorption
spectrophotometer equipped with GBC HG-3000 vapour genera-
tion accessory at Laboratory of Analytical Chemistry, Chemistry
Department, Gadjah Mada University, Yogyakarta, Indonesia. X-ray
diffraction (XRD) spectra of natural zeolite and dithizone-loaded
natural zeolite were recorded on Phillips model PW 3710 BASED
XRD spectrophotometer (Shimadzu 6000X, radiation source: Cu,
K-lambda 1.5402 nm).
2.3. Dithizone immobilization on zeolite
The following procedure which is analog to the previously
reported procedure [22–24] was applied for immobilization of
dithizone on the surface of zeolite. Zeolite (4.0 g) was added to
80 mL toluene and mixed with 1.0311 g dithizone in a 500 mL flask.
The mixture was heated and stirred for 4 h and the temperature of
the mixture was varied at 50, 70, 90 and 110  C. The product was
filtered and washed consecutively with toluene, ethanol and water
several times until the filtrate showed no characteristic color of
dithizone. The dithizone-immobilized zeolite (DIZ) was then dried
in an oven at 70  C for 6 h and filtered through 200-mesh filter. The
obtained DIZ was then characterized and used for adsorption
study.
2.4. Adsoption study
2.4.1. Effect of pH on the Hg(II) adsorption
The experiment was done by batch system. The adsorbent
(20 mg, 200 mesh) was interacted with 10 mL of Hg(II) ion (5 mg/L)
solution and the pH of the solution was varied from 3.0 to 9.0 using
buffer solution. The mixture was stirred using horizontal shaker for
60 min. The mixtures was then filtered and the concentration of Hg
(II) ion in the filtrate was determined by cold-vapor (CV) AAS. For a
control solution, the same concentration of Hg(II) solution at
corresponding evaluated pH was treated in the similar procedure
but without the addition of adsorbent.
2.4.2. Effect of contact time on the Hg(II) adsorption
This experiment was carried out to evaluate kinetic aspects of
Hg(II) ion adsorption on the DIZ adsorbent. A similar procedure to
that described in the previous section (effect of pH) was applied
but the stirring/contact time was varied from 5 to 180 min. The
obtained data were then evaluated by modified Langmuir-
Hinshelwood equation [16]:

lnðC0 C Þ 
A
¼ k1 ðt CA Þ þ K ð1Þ
CA
where Co is initial concentration of metal ion and CA is
concentration of metal ion at equilibrium. Plot of ln(C0/CA)/CA
versus t/CA gives the slope and Y-intercept equal to first-order
adsorption rate (k1) and adsorption equilibrium constants (K),
respectively.
2.4.3. Effect of initial concentration of metal ions on the adsorption
capacity
The effect of initial concentration of Hg(II) ions on the
adsorption capacity of DIZ adsorbent was examined by conducting
adsorption experiment in various concentration of Hg(II) ion. The
similar procedure to pH effect study was applied but the
concentration of Hg(II) was varied in the range of 0–10 mg/L.
The obtained data were evaluated by Langmuir isotherm adsorp-
tion model (Eq. (2)) to determine adsorption capacity (b) and
equilibrium constant (K).
C 1 1
¼ þ C ð2Þ
m bK b
where C is concentration of Hg(II) ion at equilibrium and m is mole
of Hg(II) ion adsorbed by 1.0 g of adsorbent. The value of K was then
 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849
used to calculate the adsorption energy (E) based on the equation
of standard Gibbs-Hemholtz relation (Eq. (3)).
E =
DG = RT ln K
where R is gas constant (8314 J/mol K) and T is absolute
temperature (K).
2.4.4. Removal of Hg(II) from aqueous solutions
Fifteen milliliter of synthetic sample solution (river water)
containing 8 mg/L Hg(II) was interacted with 0.02 g AZ or DIZ
adsorbents. The mixture was stirred for 90 minutes and the
adsorbent was filtered using Whatman 42 filter. The filtrates were
collected and subjected to cold vapor atomic absorption spectro-
photometric analysis (CV-AAS) for the determination of Hg(II) ion
concentration. For the second adsorption, the same procedure as
first adsorption was applied to 10 mL of filtrate obtained from the
first adsorption and the filtrates were again subjected for CV AAS
for the determination of Hg(II) concentration remaining in the
filtrate after second adsorption.
Fig. 1. Infrared spectra of dithizone-immobilized natural zeolite (DIZ) at various temperature of reflux, 50  C (A), 70  C (B), 90  C (C) and 110  C (D).
1841
3. Results and discussion
3.1. Dithizone immobilization and its characterization
(3)
3.1.1. Dithizone immobilization on zeolite
Dithizone immobilization on zeolite has been done by mixing
dithizone dissolved in toluene and natural zeolite that has been
activated with hydrofluoric acid (HF) for 4 h [22–24]. The mixture
was stirred and heated at various temperatures of 50, 70, 90 and
110  C. The results obtained were then filtered and washed
subsquently with toluene, ethanol and double-distilled water
until no dithizone trace was detected in the filtrate. The obtained
dithizone-zeolite was dried in an oven at a temperature of 70  C for
6 h. After drying, the dithizone-zeolite was sieved to ensure the
homogeneity of particle size. The adsorbants obtained from the
above process was a reddish brown solid hereinafter called
dithizone-immobilized zeolite (DIZ).
In this experiment, the adsorbent was first washed with toluene
to remove the remaining free (non-immobilized) dithizone on the
1842 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849
surface of zeolite. The further washing of the adsorbent using
ethanol and water is aimed to remove semi-polar and polar
impurities, respectively. The obtained adsorbant was again dried in
the oven to remove the remnants of solvents that still exist on the
surface of DIZ adsorbent. The immobilization of dithizone in this
study is basically coating the solid surface of natural zeolite with
selective organic compound with the hope that the active groups
available on the organic ligand can give additional serve as an
active site of adsorbent. Organic ligand, such as dithizone, has been
known to have several active groups such as

SH and

NH in its
structure, therefore it is expected to enhance the interaction
facilities between Hg(II) and the surface of the adsorbent via
covalent interactions.
There are several factors that affect the immobilization of
dithizone on the surface of zeolite including temperature, contact
time and the amount of dithizone used in immobilization. In this
study we have specifically investigated the effect of various heating
temperature (50, 70, 90 and 110  C) on the effectiveness of
dithizone immobilization on the surface of natural zeolite. The
adsorbents obtained from different heating temperature of mixing
were characterized by FT-IR spectroscopy and the results are
shown in Fig. 1.
Comparison of the infrared spectra of AZ (Fig. 1A) and those of
DIZ (Fig. 1B) reveals that immobilization process conducted at
Fig. 2. XRD patterns of dithizone-immobilized zeolite at various temperature of reflux, 50  C (A), 70  C (B) and free dithizone (C).
temperature of 50 and 70  C gives the adsorbent with higher
content of dithizone than that carried out at temperature of 90 and
110  C. This conclusion can be derived by directly observing the
higher vibration intensity of dithizone immobilized at temperature
of 50 and 70  C as compared to that obtained at temperatures of
90 and 110  C. The effectiveness of immobilization at lower
temperature may be attributed to the stability of dithizone towards
oxidation at lower temperatures. As a result, the immobilization
carried out at 50 and 70  C undergoes more effectively. At higher
temperature e.g. 90 or 110  C, and with the existence of
atmospheric air, dithizone can be easily damaged by oxidation,
therefore it becomes more difficult to immobilize dithizone on the
surface of the natural zeolite.
The DIZ adsorbents obtained at various temperatures were also
subjected to X-ray diffraction (XRD) analysis. For the purpose of
comparison, the XRD patterns of free dithizone and DIZ prepared at
temperature of 50, 70  C are presented in Fig. 2, while the
important data of the XRD spectra are collected in Table 1. It is
clearly observed from Table that the peaks characteristic for
dithizone appear more intense on DIZ prepared at temperature of
50  C than those done at 70  C. Therefore, for the next experiment,
we have selected temperature of 50  C as immobilization
temperature of dithizone. Another reasons for the selection of
this temperature is that heating at lower temperatures is more
 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849 1843

Table 1 Table 2
Interpretation of 2u and d-space values as well as the relative intensity (I/Io) of XRD Interpretation of 2u, d-space values as well as the relative intensity of the XRD peaks
peaks for dithizone-immobilized zeolite (DIZ) obtained at heating temperature of for dithizone-immobilized zeolite (DIZ).
50 and 70  C.
2u(degree) d (spacing) I/Io Interpretation
Materials 2u (degree) d (spacing) I/Io I
9.5400 9.2633 26 dithizone
9.5400 9.2633 26 116 9.8481 8.9742 41 zeolite
13.5250 6.5416 26 114 13.5250 6.5416 26 dithizone
DIZ 15.3756 5.7579 52 230 15.3756 5.7579 52 dithizone
prepared at 50  C 19.7064 4.5014 48 215 19.7064 4.5014 48 dithizone
32.7899 2.7899 11 49 22.3818 3.9690 65 zeolite
25.7457 3.4575 100 zeolite
9.3200 9.4815 3 12 26.4010 3.3732 41 zeolite
13.5416 6.5334 29 115 27.8320 3.2030 49 zeolite
DIZ 15.3765 5.7579 13 50 28.2876 3.1524 31 zeolite
prepared at 70  C 19.7370 4.4945 40 160 32.0546 2.7899 11 dithizone
32.0696 2.7887 9 36

10.8532 8.1452 16 340

13.4141 6.5954 20
Free dithizone 14.8671 5.9539 100
19.0712 4.6499 40
32.3946 2.7615 10
easily achieved and maintained than the higher one. Moreover,
heating at lower temperature also reduces the risk of the oxidation
process of dithizone.
3.1.2. Characterization of dithizone-immobilized zeolite
The effect of dithizone immobilization on the surface of zeolite
may be observed from the changes in the wavenumber of infrared
spectra of functional groups by comparing the infrared spectra of
AZ, DIZ and free dithizone (see Fig. 1B–D). It is clearly shown in
Fig. 1D that the infrared spectra of free dithizone has very sharp
absorption bands at wavenumber of 1496.7 cm
1 and 1438.8 cm
1,
indicating the presence of the double bond C¼C stretching of the
aromatic phenyl group, whereas absorption band at wavenumber
of 748.3 cm
1 and 678.9 cm
1 represents the vibration of aromatic
C

H bending, which is normally observed in 900–690 cm
1.
Absorption band at wavenumber of 2912.3 cm
1 is attributed to
the presence of benzene substitution. Absorption band at
3552.6 cm
1 indicates the existence of N

H stretching vibration,
while the sharp absorption band at 1589.2 cm
1 belongs to the
N

H bending vibration. Weak absorption band in the region
around 2500 cm
1 indicates the presence of

S

H group, while
the weak peak at 2200 cm
1 region is due to the presence of the
C¼N. Absorption band at wave number 1350–1000 cm
1 is the
C

N stretching vibration.
Upon immobilization of dithizone onto zeolite surface as
presented in Fig. 1C, the FT-IR spectra significantly change (Fig. 1B),
which is characterized by the shift of absorption and the existence
of new absorption bands. These phenomena suggest the successful
immobilization of dithizone onto the zeolite surface. Absorption
band at wavenumber of 1488.9 cm
1 and 1461.9 cm
1 indicates the
presence of C¼C double bonds of the aromatic phenyl group which
is supported by the appearance of absorption band at wavenumber
of 3012 cm
1, showing the stretching vibration of aromatic C¼C.
The absorption at 2854.5 cm
1 shows the stretching of aliphatic
C

H vibration, and absorption at wavenumber of 763.8 cm
1 and
686.6 cm
1 indicate the presence of aromatic C

H bending
vibration. Absorption band at wavenumber of 1311.5 cm
1 shows
the stretching of the C

N vibration, while that at wavenumber of
3448.5 cm
1 indicates the presence of N

H stretching vibration.
Weak absorption band at wave number 2345.3 cm
1 is likely due to
the presence of the S

H stretching vibration. All of the IR bands
mentioned above indicate the presence of dithizone in the zeolite
material. Meanwhile, absorption which is characteristics for
zeolites still appears as a strong absorption at 1049.2 cm
1,
420 indicating the presence of internal asymmetric stretch of the
2078
834
primary building blocks of zeolite, e.g. Si

O and Si

O

Si.
215 Absorption band at wavenumber of 1639.4 cm
1 shows the O

H
bending vibration of silanol group. Also, absorption band appears
at 470.6 cm
1 and 428.2 cm
1 suggesting the availability of
bending vibration of Si-O-Si [25].
Additional characterization of the obtained adsorbents has
been performed using XRD analysis. In this case, the d space and 2u
angle values which are characteristic for both zeolites and
dithizone are examined and compared to determine whether
the dithizone has been successfully immobilized on surface of the
zeolite. Based on the results of XRD analysis of AZ (Figure not
shown), DIZ (Fig. 2A) and free dithizone (Fig. 2C), it is easily noticed
that several peaks which are characteristic for both zeolites and
dithizone can be found in DIZ, indicating that dithizone has
successfully been immobilized on the surface of the zeolite. The
detailed XRD peaks of DIZ are listed in Table 2. This finding is
consistent with the results of IR spectroscopic analysis and
supported the conclusion that immobilization of dithizone has
been successfully done as discussed in the previous section.
3.2. Adsorption study of Hg(II) ions
In this study, the ability of DIZ to adsorb Hg(II) has been
systematically evaluated by examining several factors that affect
the ability of DIZ in adsorbing Hg(II). The parameters studied
include the effect of pH, adsorption kinetics and adsorption
isotherms. Evaluation of the effect of pH on the Hg(II) adsorption of
the adsorbent has been conducted with the purpose to determine
the optimum pH of adsorption. The adsorption kinetics was
studied on the basis of adsorption rate constant data evaluated by
using the Langmuir-Heinshelwood equation and Santosa models
[26]. Furthermore, evaluation of adsorption isotherms has also
been carried out to obtain the adsorption capacity, the equilibrium
constant as well as the adsorption energy at constant temperature.
This evaluation has been determined by the Langmuir-Heinsel-
wood equation. The adsorption energy data obtained from this
evaluation is then used to classify the interaction mechanism
operated in the adsorption processes between adsorbate of Hg(II)
and the adsorbent of DIZ, e.g. physical or chemical interaction and
the results are compared with those done using AZ. Fig. 3 gives the
scheme of possible interaction mechanism between Hg(II) and the
active sites of DIZ adsorbant.
3.2.1. Effect of pH on the Hg(II) adsorption
Study of the effect of pH on the adsorption of Hg(II) has been
conducted by interacting 5 mg/L of Hg(II) solution with DIZ
adsorbent at different pH of 3–9. For the purpose of comparison,
adsorption of Hg(II) on AZ is also conducted. After interaction, the
remaining metal ions in the solution was determined by cold vapor
1844 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849
NH
Zeolite N + Hg2+
C N
S N
Fig. 3. Possible interaction mechanism between Hg(II) and the active sites of dithizone-immobilized zeolite (DIZ) adsorbant.
AAS method to calculate the adsorbed Hg(II). In this study, the
control solution, i.e. the same concentration of Hg(II) solution at
various pH but without the addition of the adsorbent was also used
for the purpose of error correction that may arise from the
precipitation of Hg(II) ions at certain pH or from metal loss caused
by the adsorption of metal ions on the surface walls of the
container during the process of interaction.
The pH of the solution plays an important role in the adsorption
process, because the effectiveness of the adsorption is determined
by the chemical form (speciation) of Hg(II) ions in solution and
active groups on the surface of the adsorbent. These speciations is
basically pH dependent. Fig. 4 gives the results of the effect of pH
on the amount of adsorbed Hg(II) on the adsorbents.
Fig. 4(A) and (B) clearly show that there is a significance
difference in the amount of the adsorbed Hg(II) on each adsorbent
at the same pH. In general, it can be concluded that the ability of
dithizone-immobilized zeolite in adsorbing Hg(II) is higher than
that of zeolite itself. The activated zeolite without immobilization
of dithizone is able to adsorp Hg(II) but the adsorbed Hg(II) is
relatively small. This may be due to the role of pores and active sites
available in zeolite, such as aluminol, silanols and siloxanes. In
contrast, we clearly observe that the ability of zeolite-immobilized
dithizone to adsorb Hg(II) are relatively high, doubled than that of
activated zeolite. This high ability of adsorption is probably due to
the involvement of not only the pores and active site of zeolite, but
also the additional active groups from immobilized dithizone on
the surface of the zeolite such as

SH and

NH. This provides
much more active groups that are ready to interact with metal ions,
e.g. Hg(II).
The twice increase in the Hg(II) adsorption ability of dithizone-
immobilized zeolite may also be explained with respect to Hard
and Soft Acid-Base (HSAB) principle. In dithizone-immobilized
Fig. 4. Effect of pH on the adsorption of Hg(II) on dithizone-Immobilized zeolite (A) and activated zeolite (B).
NH
Zeolite N
C N
S N
Hg
zeolite adsorbent, there are

SH and

NH active groups which
are classified as soft bases according to the HSAB theory. This
functional groups prefer to interact with soft acid such as Hg(II)
ions. Therefore, it is quite easy to understand that Hg(II) ion will
favorably bind to the active groups of dithizone, leading to much
more Hg(II) ion is adsorbed by dithizone-immobilized zeolite as
compared to that adsorbed by activated zeolite.
In Fig. 4, it appears in general that Hg(II) ion adsorbed by the
two adsorbents increase with increase of the pH of metal ion
solution and after reaching the maximum value, the amount of
adsorbed Hg(II) starts to decrease. This trend may be explained as
follow, at low pH, the concentration of H+ ion in the solution is
high, resulting in the active groups on the surface of the adsorbent
be protonated and produce a partially positive charge on the
functional groups/active site of adsorbent. This condition is not
favorable for the occurence of the interaction between the
positively charged Hg(II) and the protonated active groups on
the surface of adsorbent, due to electrostatic repulsion. Further-
more, the high concentration of H+ in solution at low pH also
induces strong competition between H3O+ ions and the Hg(II) ion
in solution to bind to the active group on the surface of the
adsorbent. Therefore it is understandable that the higher acidity of
the solution (lower pH) leading to the lower adsorption of Hg(II)
ions on the adsorbent surfaces.
The amount of Hg(II) adsorbed by the two types of adsorbent
tends to increase with the increase of pH of the solution. In this
study, we found that the optimum pH for the adsorption of Hg(II)
on zeolite is at pH 7, which is close to the reported pH of 8 for the
adsorption of Hg(II) onto activated carbon prepared from the
biomass material [17]. At pH 7, it is expected that the protonated H+
on the surface of the adsorbent is released, so that the active
groups on the surface of the adsorbent is becoming negatively
 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849 1845

Fig. 5. Effect of initial concentration of Hg (II) on the amount of Hg(II) adsorbed by dithizone-immobilized zeolite (A) and activated zeolite (B).

charged. On the other hand, Hg(II) ion in the solution is still in the
form of positive ion, leading to very supportive condition for the
interaction between Hg(II) and the active groups on the surface of
the adsorbent. In case of DIZ, the optimum pH of adsorption is
reached at pH 5. The lower optimum pH for DIZ compared to AZ is
probably due to the effect of dithizone immobilization. The same
optimum pH of 4–6 has been reported by Yu, et al. [21] for the
adsorption of Hg(II) on dithizone-immobilized silica gel, while
optimum pH of 7 has also been reported for the adsorption of Hg(II)
onto surface of dithizone-alumina [20]. At pH 5, the amount of H+
ions available in solution is not much enough to be able to
protonate the active group of the adsorbent, so that the
equilibrium reaction between metal ions (M2+) and dithizone
ligand (H2DZ) to form metal-dithizone complex, M(HDZ)n favor-
ably goes the right side, i.e. the formation of metal dithizonate
complexes:
M2+ + H2O + nH2DZ ? M(HDZ)n + H3O+
However, further increasing of pH results in the decrease of the
amount of adsorbed Hg(II). This may be attributed to the
deposition of Hg(II) as Hg(OH)2 (Ksp Hg(OH)2 = 3.13  10
26). Also,
the functional groups on the adsorbent will undergo de-proton-
ation at higher pH, resulting in a partially negative charged active
site. Similarly, the Hg(II) ion at higher pH also tend to form
negatively charged complex in the excess of OH
ions. Therefore,
electrostatic repulsion of negatively charged species occurs in the
solution, as the result, the metal ions are becoming very difficult to
interact with the active groups of the adsorbent, leading to the
decline in the number of adsorbed metal ions.
3.2.2. Isotherm adsorption
Isothermal adsorption models are often used to determine the
adsorption capacity and it shows a correlation between the activity
of the adsorbent and the adsorbed amount of a substance at
constant temperature is the Langmuir adsorption isotherm. This
model assumes that the adsorbent surface is homogeneous and the
magnitude of the adsorption energy is equivalent to each active
adsorption sites [27]. Each of the active sites of the adsorbent will
adsorb one molecule of adsorbate. When the adsorption sites has
not been saturated yet with adsorbate molecules, the increase in
the concentration of the adsorbate will always be accompanied by
an increase in the amount of metal ions adsorbed. Conversely, if the
adsorption sites have been saturated with the adsorbate molecule,
the increase in adsorbate concentration will not increase the
amount of metal ions adsorbed [28].
In this study, the adsorption isotherms of Hg (II) on the two
types of adsorbent has been studied using the following procedure,
a solution of Hg(II) with various concentrations of 0.5, 1, 2, 4, 6,
8 and 10 mg/L was interacted with the adsorbent at optimum pH
and interaction time of corresponding adsorbent and the results

Fig. 6. Effect of interaction time on the amount of adsorbed Hg(II) ion on dithizone-immobilized zeolite (A) and activated zeolite (B).
1846 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849
Table 3
Langmuir isothermal adsorption parameters on Hg(II) on activated zeolite adsorbent (AZ) and dithizone-immobilized zeolite (ZID).
Langmuir isothermal adsorption parameters
Adsorbent Adsorption capacity (b) (mol g
1) Equilibrium constant (K) (L mol
1)

6 6
AZ 8.00  10 1.92  10
ZID 13.1 10
6 7.71 106
are presented in Fig. 5. The figure shows that the two adsorbents
give the same pattern of Hg(II) adsorption, i.e. the greater the initial
concentration of metal ions, the more metal ions are adsorbed by
the adsorbent. The amount of adsorbed Hg(II) ion is then constant
at a certain concentration of Hg(II). This situation is happened
because the metal ions in solution occupy active sites of the
adsorbent, the greater the concentration of metal ions in the
solution, the more active sites of the adsorbent are occupied by
metal ions, if all the active sites on the surface of the adsorbent has
been occupied by Hg(II) ions, no more Hg(II) ion can be adsorbed by
the adsorbent, and therefore the amount of adsorbed Hg(II)
remains constant. This condition indicates that the equilibrium
between the active sites on the adsorbent and Hg(II) ion has been
reached, hence the addition of Hg(II) ion will not result in any
significant change in the amount of Hg(II) ion adsorbed by the
adsorbent.
For adsorption using AZ (Fig. 5B), it is observed that the Hg(II)
adsorption with initial concentration in the range of 0.5–2 mg/ml
has been undergone slowly, whereas at concentrations above
2 mg/L, adsorption occur rapidly and achieve optimum conditions
at concentration of 4 mg/L. The slow adsorption may occur because
of the active groups available in AZ are silanols, aluminol and
siloxane which is classified as hard base according HSAB theory. At
low concentration, Hg(II) ion is difficult to interact with active
groups on the surface of the adsorbent due to the low selectivity
and affinity of the adsorbent towards soft-acid of Hg(II) ion. At high
concentration, the amount of Hg(II) ion in the solution is quite
large, therefore, it increases the possibility of interaction between
the Hg(II) ion and the active groups on the surface of the adsorbent,
resulting in faster adsorption process of the adsorbent and Hg(II)
ion. The same condition is also applied to DIZ adsorbent (Fig. 5A),
however in this case the adsorption of Hg(II) on the adsorbent
involves not only the active group of the zeolite, but also the active
groups of ditizone, which have great affinity and selectivity to ions
Hg(II). Therefore, the adsorption using DIZ adsorbent achieves the
optimum condition at higher initial concentration than that of
activated zeolite, e.g. at 6 mg/L, indicating that DIZ has more active
sites with greater affinity and selectivity that can be occupied by
Hg(II) ion.
Adsorption thermodynamic parameters including adsorption
capacity, adsorption equilibrium constant and adsorption energy
can be determined by applying the Langmuir adsorption isotherm
models to the obtained data, according to the following equation:
C 1 C
¼ þ
m bK b
Table 4
The kinetic parameters of Langmuir-Heishelwood adsorption for of Hg(II) on activated zeolite (AZ) and dithizone-immobilized zeolite (DIZ).
Langmuir-Heishelwood kinetic parameters
Adsorbent 1st order adsorption rate constants (min
1)

7
AZ 1.00  10
DIZ 4.50  10
3
adsorption energy (kJ mol
1) Plot Linearity (r)
36.09 0.9993
39.55 0.9998
By plotting C/m against C, the value of K (equilibrium constant)
and b (adsorption capacity) can be calculated from the slope and
the intercept the graph. From the K value, the adsorption energy
can then be calculated using the following standard relation:
Eads = DG = RT ln K
where R is the general gas constant (8.314 J/mol K) and T is the
temperature (Kelvin). The results of the calculation of Langmuir
isothermal adsorption parameters are presented in Table 3.
Based on the data summarized in Table 3, it is shown that the
adsorption capacity of Hg(II) for DIZ adsorbent (13.1 10
6 mol
g
1) is comparable the to reported value of 20  10
6 mol g
1 for
dithizoze-silica gel at pH = 6 [20]. The little bit lower result in this
study is probably due to the lower amount of dithizone that can be
immobilized onto the surface of zeolite compared to that of silica
gel. However, it is clearly observed that the adsorption capacity and
adsorption equilibrium constant of Hg(II) for DIZ adsorbent is still
higher than those of AZ. This suggests that the immobilization of
dithizone on zeolite has increased the adsorption capacity of
zeolite due to the increase in the number of new active sites from
immobilized dithizone. The functional groups of dithizone has
been known to have high affinity and selectivity to Hg(II) ion. The
above explanation is also supported by finding that the value of the
equilibrium constant of the reaction is quite large, meaning that
the complex formation reaction favorably goes to the right side, e.g.
the formation of the products. Hence, much more Hg(II) ion is
binding to the active groups of dithizone immobilized on the
zeolite. Adsorption process can occur by means of physical
interaction (physisorption), chemical interaction (chemisorption)
or mixture of them. Adamson [29] categorized adsorption as
physisorption if its adsorption energy is less than 20.92 kJ/mol and
considered as chemisorption if its adsorption energy is more than
20.92 kJ/mol. Based on this classification, we may conclude that the
adsorption of Hg(II) on both AZ and DIZ adsorbents is classified as
chemisorption because the their adsorption energy is higher than
20.92 kJ/mol, i.e. 36.09 kJ/mol and 39.55 kJ/mol, respectively. The
possible chemical interactions operated in the adsorption process
are electrostatic interaction between Hg(II) ion and silanol, or
aluminol groups of zeolite (in AZ and DIZ adsorbents), as well as
coordination covalent bonds between Hg(II) ion and functional
groups of immobilized dithizone on the surface of the zeolite (in
DIZ only).
3.2.3. Kinetics of adsorption
Adsorption kinetics was studied by determining the adsorption
rate constant and adsorption equilibrium constants. The data were
Equilibrium constants (mol
1 L) Plot linearity (r)
2
2.76  10 0.8109
4.77  104 0.9692
 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849 1847

Fig. 7. The effectiveness of activated zeolite (AZ) and zeolite-immobilized ditizon (ZID) in the removal of Hg(II) in the river water samples taken from the west bridge (1) and
the eastern bridge (2) of river Progo, Bantul DIY spiked with Hg(II). Before adsorption (blue), after first adsorption (red) and after second adsoption (green). (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version of this article.)

obtained by interacting 5 mg/L of Hg(II) solution with the two types
of adsorbent at different contact time of 5, 15, 30, 60, 90, 120 and
180 min and at corresponding optimum pH of adsorption. Effect of
interaction time on the amount of adsorbed Hg(II) ion is presented
in Fig. 6.
Adsorption kinetics study is aimed to determine the value of
adsorption rate constant which is able to give information on the
rate of adsorption process. The information about the time
required to achieve adsorption equilibrium is very useful to
determine the contact time required to achieve optimum result of
adsorption. Generally, when the adsorption equilibrium has been
reached, the increase in interaction time will not significantly
change the amount of metal ions adsorbed by the adsorbent.
Fig. 6 shows clearly that the amount of Hg(II) adsorbed by DIZ is
always larger than that adsorbed by AZ. This finding again supports
the active groups on the surface of the adsorbent. The difference in
value of optimum contact time between the two types of adsorbent
is presumably due to the longer time needed for the complexation
between dithizone on the surface of zeolite and Hg(II) ion. Since
there is various active groups available on DIZ, the interaction
involves not only the active groups of the zeolite, but also the active
groups of dithizone, e.g. via chelate formation. Therefore it can
easily be understood that the time required for DIZ to reach
equilibrium is much longer compared to that needed by AZ.
The data obtained from this experiment was then evaluated to
determine the adsorption kinetic parameters, e.g. the rate of
adsorption (k) and adsorption equilibrium constants (K), using the
following Langmuir-Heishelwood adsorption kinetics model:
  
ln C0 C k1 t
þK ¼
A

the explanation that the dithizone immobilized on the surface of C0
CA C0
CA

the zeolite has improved both selectivity and affinity/capacity of  
the adsorbent towards Hg(II) ion due to the existence of additional ln C0 =C
A t
In plot of versus C0
C , the values of K and k1 are
active groups from dithizone, i.e.

SH and

NH. These two active C 0
C A A

groups have preferency to interact with Hg(II) ion, leading to more respectively given by the Y-intercept and the slope of the plot.
Hg(II) ion is adsorbed by DIZ as compared to that adsorbed by AZ. Results of k and K calculation are presented in Table 4.
Based on Fig. 6, it can also be observed that in general the In order to obtain the best model of the adsorption kinetics, the
amount of metal ions adsorbed by the adsorbent increases with the kinetic parameters which have been evaluated by Langmuir-
increase in interaction time between adsorbents and Hg(II) ion. Heinshelwood equation are compared with those obtained by the
Aftrer reaching optimum value of time, the adsorbed Hg(II) kinetic model proposed by Santosa [26], as follows:
remains relatively constant. The general trend of Hg(II) adsorption   
ln C0 C k1 t
on AZ and DIZ is relatively the same. However, in case of DIZ, it is A
¼ þK
observed that at the first 5 min of contact time the amount of Hg(II) CA CA
adsorbed on the adsorbent increases significantly and reaches a  
ln C0 =C
constant value after 90th minute of contact time. On the other side, Plot of A
versus CtA gives K and k1 values respectively as the Y-
CA
the adsorption of Hg(II) by AZ occurs slowly at the beginning of
intercept and slope of the plot. Detailed calculation results are
adsorption, and reaches a constant value after 60th minute of
presented in Table 5.
interaction. The constant value of adsorption indicates that the
equilibrium has been achieved between Hg(II) ions in solution and

Table 5
Parameters of adsorption kinetics calculated by model of Santosa [26] for Hg(II) ion on activated zeolite (AZ) and dithizone-immobilized zeolite (DIZ).

Parameters of adsorption kinetics according to Santosa model [26]

Adsorbent 1st order adsorption rate constants (min
1) Equilibrium constants (mol
1 L) Plot linearity (r)

3
AZ 8.10  10 2.76  103 0.9479
DIZ 13.0  10
3 4.77  105 0.9720
1848 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849
Comparing Tables 4 and 5, it is clearly observed that the kinetic
parameters evaluated by Santosa model [26] gives better results
from the point of view of linearity (r-value). The data presented in
Tables 4 and 5 also suggest that the value of the adsorption rate
constant (k) for DIZ is larger than that of AZ. This indicates that the
immobilization of dithizone on the surface of zeolite increases the
rate of adsorption. In the adsorption of Hg(II) by AZ, the metal ion
interact with active groups of siloxane, silanol and aluminol groups
which according to HSAB (Hard Soft Acid-Base) principle are
classified as the hard base, hence it would be more difficult for soft
acid species like Hg(II) to interact with. This reason explains the
lower rate constants observed for the Hg(II) adsorption on AZ. On
the other hand, the higher value of adsorption rate constant for DIZ
is probably due to the diversity of active groups available on the
surface of adsorbent as a result of dithizone immobilization on the
surface of the zeolite. The active groups of

SH and

NH are
classified as soft bases according to HSAB theory which have great
affinity and selectivity towards soft acid such as Hg(II). As a result, a
lot of Hg(II) has been able to be adsorbed by DIZ in a relatively short
time. The fact that the value of the equilibrium constant (K) for DIZ
is larger compared to that of AZ also supports this explanation. This
finding indicates that the adsorption capacity of DIZ towards Hg(II)
is larger than that of AZ, resulting in more Hg (II) ion is able to be
adsorbed by the DIZ adsorbant.
3.3. Removal of mercury(II) from river water spiked with Hg(II)
Application of adsorbent for the removal of Hg(II) ion in the
river water spiked with Hg(II) has been studied by diluting a
solution containing certain concentration of Hg(II) ion with filtered
river water in a 100 mL of volumetric flask so that the final
concentration of Hg(II) in the solution is 8 mg/L. The river water
used for the study was taken from Progo river, Bantul, Yogyakarta
Province, Indonesia at two points of sampling, before and after the
bridge. The detailed composition of the river water is not
specifically determined in this study, but it is expected to contain
some heavy metal ions other than Hg(II) as well as domestic waste
because the river is flowing across the city of Yogyakarta and home
industrial and domestic wastewaters are normallly thrown directly
to the rives. The AZ and DIZ adsorbents were then interacted with
the two types of Hg(II)-spiked river water samples at optimum
conditions of Hg(II) adsorption. The mixture solution was then
filtered and analyzed using CV-AAS to determine the content of Hg
(II) remaining in the filtrate. To determine the effectiveness of the
adsorbent in the adsorption of Hg(II) in the samples, the filtrate
from the first interaction was interacted again with the two
adsorbents in the same way as for the first interaction. Detailed
results of experiment is presented in Fig. 7. It can be seen from this
figure that approximately 51.73% of Hg(II) ion can be removed from
the solution at first adsorption by AZ and up to 80.89% by using DIZ.
For the second adsorption, up to 97.98% and 99.36% of Hg(II) has
been able to be removed from the solution using AZ and DIZ
adsorbents, respectively. Based on these results, again we see that
the DIZ adsorbent has greater effectiveness in the removal of Hg(II)
ion from the river water samples compared to AZ adsorbent. This
better performance of the modified adsorbant can be achieved
because of the influence of the higher affinity and selectivity of
functional groups of dithizone that has been immobilized on the
surface of the zeolite towards Hg(II) ion.
4. Conclusion
Dithizone-immobilized zeolite (DIZ) adsorbent has been
prepared by mixing natural zeolite and dithizone in the toluene
medium at 50  C for 4 h to yield brown-reddish adorbent with high
affinity and selectivity to Hg(II) ion. The optimum conditions for
the adsorption of Hg(II) ion using this adsorbent is achieved at pH 5
and 90 min of contact time. The kinetic study suggests that the rate
of adsorption of Hg(II) on DIZ is higher than that of activated zeolite
(AZ). Adsorption isotherm experiment reveals that the adsorption
Hg(II) on DIZ is best described by Langmuir model with adsorption
capacity, equilibrium constant and energy higher than that of AZ.
This higher performence of DIZ has been found to be the effect of
the functional groups of dithizone immobilized on the surface of
the zeolite. This modified adsorbent has been successfully applied
in the removal of Hg(II) ion in the river water spiked with Hg(II) ion
with satisfied results, suggesting that the modified adsorbant may
be used in the future for removal of Hg(II) in industrial waste or
used as promising material for solid phase extraction and
preconcentration of Hg(II).
Acknowledgement
This work is partially supported by Directorate General of
Higher Education (DGHE), Ministry of Education and Culture, The
Republic of Indonesia through National Strategic Research Grant
(Penelitian Stranas) fiscal year 2014 contract no. LPPM-UGM/1041/
LIT/2014 dated May 5, 2014.
References
[1] S.H. Lin, R.S. Juang, Heavy metal removal from water by sorption using sur-
factant-modified montmorillonite, J. Hazard. Mater. B 92 (2002) 315–326.
[2] V.J. Inglezakis, M.D. Loizidou, H.P. Grigoropoulou, Ion exchange of Pb2+, Cu2+,
Fe3+ and Cr3+ on natural clinoptilolite: selectivity determination and influence
of acidity on metal uptake, J. Colloid Interface Sci. 261 (2003) 49–54.
[3] P. O’Neil, Mercury in Environmental Chemistry, second ed., Chapman and Hall,
London, 1995.
[4] L.B. Khalil, M.W. Rophael, W.E. Mourad, The removal of the toxic Hg(II) salts
from water by photocatalysis, Appl. Catal. B Environ. 36 (2002) 125–130.
[5] N. Barka, M. Abdennouri, M. El-Makhfouk, S. Qourzal, Biosorption charac-
teristics of cadmium and lead onto eco-friendly dried cactus (opuntia ficus
indica) cladodes, J. Environ. Chem. Eng. 1 (2013) 144–149.
[6] S.M. El-Bahy, Z.M. El-Bahy, Synthesis and characterization of polyamidoxime
chelating resin for adsorption of Cu(II), Mn(II) and Ni(II) by batch and column
study, J. Environ. Chem. Eng. 4 (2016) 276–286.
[7] V. Badillo-Almaraz, P. Trocellier, I. Davila-Rangel, Adsorption of aqueous Zn(II)
species on synthetic zeolites, Nucl. Instrum. Methods Phys. Res. B 210 (2003)
424–428.
[8] R.M. Barer, Zeolites and Clay Minerals as Sorbent and Molecular Sieves, Ac-
ademic Press, New York, 1987.
[9] D.W. Breck, Crystalline molecular sieves, J. Chem. Educ. 41 (1964) 678–689.
[10] B. Salih, A. Denizli, C. Kavakli, R. Say, E. Piskin, Adsorption of heavy metal ions
onto dithizone-anchored poly (EGDMA-HEMA) microbeads, Talanta 46 (1998)
1205–1213.
[11] M.E. Mahmoud, M.M. Osman, M.E. Amer, Selective pre-concentration and solid
phase extraction of mercury(II) from natural water by silica gel-loaded
dithizone phases, Anal. Chim. Acta 415 (2000) 33–40.
[12] I. Ullah, R. Nadeem, M. Iqbal, Q. Manzoor, Biosorption of chromium onto native
and immobilized sugarcane bagasse waste biomass, Ecol. Eng. 60 (2013) 99–
107.
[13] R. Nadeem, Q. Manzoor, M. Iqbal, J. Nisar, Biosorption of Pb(II) onto immo-
bilized and native Mangifera indica waste biomass, J. Ind. Eng. Chem. 35 (2016)
185–194.
[14] Q. Manzoor, R. Nadeem, M. Iqbal, R. Saeed, T.M. Ansari, Organic acid pre-
treatment effect on Rosa bourbonia phyto-biomass for removal of Pb(II) and Cu
(II) from aqueous media, Bioresour. Technol. 132 (2013) 446–452.
[15] A. Babarinde, G.O. Onyiaocha, Equilibrium sorption of divalent metal ions onto
groundnut (Arachis hypogaea) shell: kinetics, isotherm and thermodynamics,
Chem. Int. 2 (2016) 37–46.
[16] A. Babarinde, K. Ogundipe, K.T. Sangosanya, B.D. Akintola, A.E. Hassan,
Comparative study on the biosorption of Pb(II), Cd(II) and Zn(II) using Lemon
grass (Cymbopogon citratus): kinetics, isotherms and thermodynamics, Chem.
Inter. 2 (2016) 89–102.
[17] N. Asasian, T. Kaghazchi, M. Soleimani, Elimination of mercury by adsorption
onto activated carbon prepared from the biomass material, J. Ind. Eng. Chem.
18 (2012) 283–289.
[18] Z. Marczenko, Separation and Spectrophotometric Determination of Elements,
Ellis Horwood Ltd., Chichester, West Sussex, UK, 1986, pp. 88–94 (Chap. 3).
[19] L.C. Thomas, G.J. Chamberlin, Colorimetric Chemical Analytical Methods, The
Tintometer Ltd., Salisbury, England, 1980.
 M. Mudasir et al. / Journal of Environmental Chemical Engineering 4 (2016) 1839–1849
[20] M.E. Mahmoud, M.M. Osman, O.F. Hafez, A.H. Hegazi, E. Elmelegy, Removal and
preconcentration of lead(II) and other heavy metals from water by alumina
adsorbents developed by surface-adsorbed dithizone, Desalination 251 (2010)
123–130.
[21] H.-M. Yu, H. Song, M.-L. Chen, Dithizone immobilized silica gel on-line pre-
concentration of trace copper with detection by flame atomic absorption
spectrometry, Talanta 85 (2011) 625–630.
[22] M. Mudasir, D. Maryanti, G. Pramiyanti, R. Roto, Preconcentration study of Pb
(II) and Cd(II) from aqueous solution using silica gel loaded with dithizone, J.
Ion Exch. 18 (2007) 516–517.
[23] M. Mudasir, K. Wijaya, S. Suseno, P.D. Ola, A. Suseno, Proceeding of 2nd In-
ternational Conference for Young Chemist (ICYC-2006): Environmental
Chemistry, 24-27 May 2006, USM, Penang, Malysia, 2016, pp. 1–9.
1849
[24] M. Mudasir, D. Siswanta, P.D. Ola, Adsorption characteristics of Pb(II) and Cd(II)
ions on dithizone-loaded natural zeolite, J. Ion Exch. 18 (2007) (418–323).
[25] R.M. Silverstein, B.C. Bassler, T.C. Morrill, Spectrometric Identification of Or-
ganic Compounds, 4th edition, John Wiley & Sons, New York, 1981.
[26] S.J. Santosa, D. Siswanta, A. Kurniawan, W.H. Rahmanto, Hybrid of chitin and
humic acid as high performance sorbent for Ni(II), Surf. Sci. 601 (2007) 5155–
5161.
[27] E. Guibal, J.M. Tobin, Chitosan sorbent for platinum sorption from diliute
solution, Ind. Eng. Chem. Res. 38 (1998) 4011–4023.
[28] J. Oscik, Adsorption, Ellis Harwood Limited, England, 1982.
[29] A.W. Adamson, Physical Chemistry of Surfaces, 5th edition, John Wiley and
Sons Inc., New York, 1990.