Analytical Letters, 46: 706716, 2013

Copyright # Taylor & Francis Group, LLC

ISSN: 0003-2719 print=1532-236X online
DOI: 10.1080/00032719.2012.726679

Atomic Spectroscopy

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THIOL-MODIFIED MAGNETIC SILICA SORBENT FOR

THE DETERMINATION OF TRACE MERCURY IN
ENVIRONMENTAL WATER SAMPLES COUPLED WITH
COLD VAPOR ATOMIC ABSORPTION SPECTROMETRY
Guoqiang Xiang, Lulu Li, Xiuming Jiang, Lijun He, and
Lu Fan
School of Chemistry and Chemical Engineering, Henan University of
Technology, Zhengzhou, P. R. China
Core-shell magnetic silica has been prepared and then chemically modied with thiol groups. It
was used for magnetic solid phase extraction (MSPE) of trace Hg2 from environmental samples, followed by its determination by cold vapor atomic absorption spectrometry (CV-AAS).
The parameters for MSPE procedure, such as pH, elution conditions, ultrasonic time, and
effects of co-existing ions were investigated. The results showed that Hg2 ions are adsorbed
on the thiol-modied magnetic silica at pH 6.0 after a 10-min ultrasonic treatment and were
quantitatively eluted with 5.0 mL thiourea (2%, m/v) in nitric acid solution (0.1 M) after a
2-min ultrasonic treatment. Under the optimized experimental conditions, the adsorption
capacity of the new sorbent was 101.0 mg g
1 for Hg2. The detection limit of the proposed
method was 0.06 n g mL
1 for Hg2 and the enrichment factor was 16.6. The analytical data
obtained from a certied reference water sample (GBW00809) were in good agreement with
the certied value. The method has also been successfully applied to the determination of trace
Hg2 in rain water, well water and treated water from a sewage treatment plant. The recovery
of Hg2 from spiked samples was between 96.0% and 110.0%.
Keywords: CV-AAS; Environmental samples; Magnetic silica; Magnetic solid phase extraction; Mercury

INTRODUCTION
Mercury contamination in the environment and in living organisms continues
to be a critical issue of concern on a global scale (Taylora et al. 2005). The United
States Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA) lists mercury and its compounds in third place on the Priority Lists
Received 26 June 2012; accepted 27 August 2012.
Financial supports from National Nature Science Foundation of China (No. 21205028), Natural Science
Fundamental Research Fund of Science and Technology Department of Henan Province (112300410080), the
program for young teachers of universities in Henan province (2012GGJS-300) and Plan for Scientic
Innovation Talent of Henan University of Technology (No. 11CXRC11) are gratefully acknowledged.
Address correspondence to Guoqiang Xiang, School of Chemistry and Chemical Engineering,
Henan University of Technology, Zhengzhou, 450001, P. R. China. E-mail: xianggq@126.com
706

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MAGNETIC SILICA SORBENT FOR EXTRACTION OF Hg

707

of Hazardous Substances, and the European Water Framework Directive (2000=

60=EG) classies mercury as 1 of 30 precarious dangerous pollutants. With the
toxic effects of mercury on ecosystems and health well-established, the need to detect
mercury at extremely low concentrations persists.
Several analytical techniques such as spectrometry (Rajesh and Gurulakshmanan 2008), inductively coupled plasma atomic emission spectrometry=mass spectrometry (ICP-AES=MS) (Zhu and Alexandratos 2007; Yin et al. 2010), atomic
uorescence spectrometry (AFS) (Margetinova et al. 2008), and cold vapor atomic
absorption spectrometry (CV-AAS) (Shamsipur et al. 2005; Rofouei et al. 2011) have
been developed for the determination of mercury. Among these techniques, CV-AAS
is widely accepted technique for the determination of mercury due to its high sensitivity, simple operation, and relative freedom from matrix interferences as well as
low cost (Segade and Tyson 2007; Zhai et al. 2006). However, direct determination
of mercury in different samples is often difcult for both low concentration in samples
and complicated sample matrix. To solve this problem, a separationpreconcentration
procedure prior to analysis is a popular choice.
Recently, solid phase extraction (SPE) technique has become increasingly
popular as an effective separation-preconcentration procedure for metal ions prior
to their determination. Compared with traditional liquidliquid extraction, SPE
has the following advantages: (1) high enrichment factor; (2) convenient operation;
(3) rapid phase separation; (4) can be coupled with different detectors; and (5) is time
saving and cost saving (Camel 2003). It is well-known that the adsorption medium
plays an important role in improving the selectivity of SPE and much more attention
has been paid to the exploration of new adsorption materials for SPE in recent years
(Turker 2007). Many kinds of adsorption materials, such as chelating resins, silica
gel, carbon sorbents, inorganic based sorbents, biological adsorption material, and
nanomaterials have been used in SPE (Camel 2003; Turker 2007; Lemos et al. 2008).
Magnetic materials, interesting advanced composite materials, have received
increasing attention in the past few decades due to the following characteristics: unique
magnetic response, low cytotoxicity, easy chemical surface modication, and great
potential application in various elds (Gardimalla et al. 2005; Zhao et al. 2008; Deng,
Deng et al. 2005; Li et al. 2008). Magnetic separation technique (MST) is based on the
magnetic response of the magnetic material, which means that the suspended magnetic
material adheres to the target of interest (the container wall) and can be quickly separated
from a matrix by an external magnet. The application of magnetic materials in SPE could
greatly simplify the conventional column SPE procedure. The important adsorption process and desorption process could simply be completed in a container assisted by a magnet. The whole operation time is greatly reduced, and the SPE procedure, therefore,
provides low cost and easy operation without SPE cartridge and pump.
However, it should be pointed out that pure magnetic inorganic materials easily form a large aggregation and alter magnetic properties (Yang et al. 2004). And,
the pure magnetic inorganic materials were not selective and not suitable for complex samples (Pu et al. 2004). To solve the aforementioned problems, coating the
magnetic materials is a popular choice. Silica was considered to be one of the most
ideal coating medium for magnetic materials due to its reliable chemical stability and
easy surface functionalization (Kang et al. 2009; Liang and Wang 2010; Ashtari et al.
2005). For functionalization of the silica coating of magnetic materials, silylation

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reaction was the most popular method to combine the functional group on the silica
coating (Zheng and Hu 2010; Chen et al. 2009). This method has a shortcoming of
low concentration of the functional group on the surface of coated magnetic materials, which leads to a lower adsorption capacity of the modied magnetic materials.
To improve the analytical performance of magnetic materials for magnetic solid
phase extraction (MSPE), a new modication procedure should be developed.
The aim of this study was to produce thiol-modied magnetic silica as a new type
of sorbent for MSPE, and to develop a rapid, selective, and sensitive analytical method
for the determination of trace Hg2 in environmental water samples by CV-AAS.
EXPERIMENTAL

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Apparatus
Determination of mercury was carried out on an atomic absorption spectrometry (TAS 986; Beijing Purkinje General Instrument Co., Ltd., Beijing, China)
equipped with a hydride generation part (WHG-103A; Beijing Hanshi Instrument
Co., Ltd., Beijing, China). The optimum operation conditions were as follow: Wavelength 253.7 nm, Spectrum band width 0.4 nm, Lamp current 3 mA, Flow rate of Ar
gas 200 mL min
1, concentration of HCl 1%(v=v), concentration of KBH4 1.5%
(m=v) in NaOH solution (0.3%, m=v). FT-IR spectra in KBr was recorded by a
WQF-510 FT-IR spectrometer (Beijing Rayleigh Analytical Instrument Co., Ltd.,
Beijing, China). The pH values were measured with a PHS-3C pH-meter (Shanghai
Precision & Scientic Instrument Co., Ltd., Shanghai, China). A model ultrasonicator (KQ116, 40 kHz; Kun Shan Ultrasonic Instruments Co., Ltd., Beijing, China)
was used to disperse the magnetic materials in the solution. A magnet (Nd-Fe-B,
60 mm  35 mm  10 mm) was used for magnetic separation.
Standard Solution and Reagents
The stock solution of Hg2 (1.0 mg mL
1) was prepared by dissolving appropriate amounts of Hg(NO3)2 (Shanghai Reagent Factory, Shanghai, China) in diluted
nitric acid (5%, v=v) and made up to 100 mL with deionized water. Calibration solutions and test solutions were prepared by stepwise dilution of the stock solution. Tetraethoxysilane (TEOS) and Polyethylene-alt-maleic anhydride (Mw 100000500000)
were purchased from Sigma-Aldrich. L-cysteine (AR; Shanghai Huixing Biochemical
Reagent Company, Shanghai, China) and 3-aminopropyltrimethoxysilane (Aladdin
Reagent Company, Shanghai, China) were used for reaction directly. HNO3(pH
1.02.0), acetate-acetic acid buffer (pH 3.05.0) and NH3-NH4Cl buffer (pH
8.010.0) were used for pH adjustment. All other chemicals were of analytical reagent
grade. All stock standard solutions were stored in polyethylene bottles in a refrigerator at 6 C. All glassware were kept in 10% nitric acid for at least 24 h and washed
with deionized water before use.
Synthesis of Thiol-Modified Magnetic Silica Sorbent (MSS)
The preparation of the thiol-modied MSS was illustrated in Fig. 1. First, the
magnetic Fe3O4 was synthesized by co-precipitation of a mixture of FeCl3  6H2O

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MAGNETIC SILICA SORBENT FOR EXTRACTION OF Hg

709

Figure 1. The preparation of thiol-modied MNPs.

and FeCl2  4H2O with concentrated aqueous ammonia. The obtained magnetic
Fe3O4 was embedded in silica microsphere to obtain the monodispersed Fe3O4=
SiO2 microsphere through a modied Stober method (Deng, Wang et al. 2005). Then,
Fe3O4=SiO2 microsphere (1.0 g) and 3-aminopropyltrimethoxysilane (2.0 mL) were
placed into a round bottom ask containing anhydrous toluene (80 mL), then
reuxed at 110 C for 10 h with nitrogen protection. The product obtained by a magnet was washed by toluene and methanol, and then was dried at 80 C. In another
branch, polyethylene-alt-maleic anhydride (2.0 g) and L-cysteine (1.2 g) was dissolved
in N,N-dimethylformamide (200 mL), then reuxed at 130 C for 1 h. After reuxing,
the reactant was cooled to room temperature, and the aforementioned obtained
amino modied Fe3O4=SiO2 microphere (1.6 g) was added, and reuxed at 130 C
for 1.5 h. After cooling to room temperature, the resultant product was collected
by an external magnet. The obtained particles was washed with methanol (100 mL)
and deionized water (100 mL), and dried in vacuum.
Sample Preparation
Environmental water samples were collected from a sewage treatment plant
(treated water; Wulongkou, Zhengzhou city, China) and a well in Zhengzhou city.
The urban rainwater sample was collected in the wet season in Zhengzhou city.
The water samples were ltered through lter paper, and then ltered through a
membrane (0.45 mm). The pH of the samples was adjusted to 6.0 before analysis.
General Procedure for MSPE
The operation procedure of MSPE is described as follows: 100 mL standard
solution (or sample solution) containing Hg2(2.5 ng mL
1) was transferred to a
250 mL beaker, pH of the solution was adjusted to 6.0, and 0.2 g sorbent was added.
After ultrasonication for 10 min, the magnetic adsorbent was separated easily and
quickly by a at magnet and the supernatants were decanted directly. For elution
of the target ion, the sorbent was mixed with 5.0 mL thiourea (2%, m=v) in nitric acid

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solution (0.1 M). The eluent was collected after 2 min ultrasonication with a magnet.
Finally, trace mercury in the collected eluent was detected by CV-AAS.
RESULTS AND DISCUSSION

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Characterization of Thiol-Modified MSS

The thiol-modied MSS was characterized by FT-IR (Fig. 2). The typical
absorption peaks of the modied MSS conrmed its chemical structure. The peaks
appeared at 596 cm
1 and 1109 cm
1 and are attributed to the Fe-O stretching band
of Fe3O4 and the Si-O stretching band of silica on the surface of MSS, respectively.
Furthermore, the presence of the SH-CH2-CH- group was reected by the peaks at
2856 cm
1 and 2927 cm
1, which corresponds to C-H vibrations in different hybridizations. And, the characteristic N-H and C=O bands of the amide group corresponded to the peaks at 3456 cm
1(N-H) and 1643 cm
1(C=O) (Ma et al. 2003;
Jang and Lim 2010). The aforementioned details clearly demonstrated the successful
modication of MSS with the thiol group by reaction between L-cysteine and
polyethylene-alt-maleic anhydride.
Obviously, the most important function group of the prepared sorbent for
MSPE was the thiol group, and its amount on the surface of the sorbent was the
key factor for its analytical performance. The amount of thiol group on the obtained
MSS was determined according to the Ellman method (Ellman 1959). It was determined that the amount of thiol group on the thiol-modied MSS was 0.61 mmol g
1,
which brought great potential for the application of trace metal preconcentration
with large adsorption capacity to the sorbent.
Effect of pH
The pH is an important factor for the adsorption of Hg2 on the thiol-modied
MSS. The effect of pH on the adsorption efciency of Hg2 was investigated by

Figure 2. FT-IR spectra of thiol-modied MNPs. (Figure available in color online.)

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MAGNETIC SILICA SORBENT FOR EXTRACTION OF Hg

711

Figure 3. Effect of ultrasonic time on extraction efciency of Hg2 on thiol-modied MNPs.

testing Hg2 standard solution (25 ng mL
1) with pH varying from 1.07.0 according
to general procedure for MSPE. As showed in Fig. 3, the extraction efciency of
Hg2 on thiol-modied MSS was 100%, and kept constant within a pH range of
2.07.0. At lower pH, extraction efciency of Hg2 decreased. This may be explained
by the competitive adsorption and electrostatic repulsion between Hg2 and H at
lower pH. For further experiments, pH 6.0 was chosen for preconcentration of Hg2.
Optimization of Elution Condition
From the results in Fig. 3, it could be seen that extraction efciency of Hg2
was still larger than 90% at pH 1.0. Thus, typical acid eluent is possibly difcult
for quantitative elution of adsorbed Hg2. To obtain an effective elution of adsorbed
Hg2, the mixture of nitric acid and thiourea solution was chosen as eluent. The
effect of the mixture concentration was optimized, and the results indicated that
quantitative elution could be obtained using thiourea (2%, m=v) in nitric acid
solution (0.1 M) as the eluent.
By using thiourea (2%, m=v) in nitric acid (0.1 M) solution as the eluent, the
effect of the eluent volume on the elution of Hg2 was studied with eluent volume
varying from 420 mL. The results indicated that 5 mL was sufcient to elute Hg2
quantitatively. Therefore, 5 mL eluent was selected for the following experiment.
Effect of Ultrasonic Time
To minimize the pretreatment time, ultrasonic time for adsorption and elution
was also investigated. For adsorption process, the effect of ultrasonic time on the
extraction efciency of Hg2 was studied according to general procedure for MSPE
with the ultrasonic time varying from 530 min. The results indicated that quantitative extraction could be obtained with ultrasonic time larger than 10 min. The extraction efciency was obviously reduced when ultrasonic time was larger than 20 min.
These could possibly explain a certain time of ultrasonic agitation that made a

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homodispersed solution of adsorbent, which greatly improve the adsorption

efciency; and, longer ultrasonic time may lead to an increasing temperature of
solution by the ultrasonic heat effect, which may decrease the adsorption efciency.
For the elution process, the experimental results showed that 2 min was adequate for
quantitative recovery of Hg2 adsorbed on thiol-modied MSS with thiourea (2%,
m=v) in nitric acid solution (0.1 M) as the eluent. Finally, 10 min of ultrasonic time
for adsorption and 2 min of ultrasonic time for elution were chosen.

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Effect of Concomitant
The effect of potentially interfering ions on the preconcentration and determination of the target analyte was investigated. In this experiment, the Hg2 standard
solutions (2.5 ng mL
1) containing the added interfering ions were treated according
to general procedure for MSPE. The concentration of Hg2 in the eluent was determined in order to calculate the recovery. The tolerances of the potentially interfering
ions, dened as the maximum concentration that could achieve >90% recovery of
the target analyte, are given in Table 1. Table 1 shows that most of the present
cations had a large tolerable concentration (the ratio of concentrations between
interfering ions and analyte was more than 4000) under the selected conditions.
However, the tolerable concentrations of Ag and Cu2 were much smaller than that
of other ions. It is well-known that the binding ability between metal ions and SH
group could refer to the solubility product constants of the corresponding metal suldes. The solubility product constant of sulde is smaller; the binding ability
between the corresponding metal ion and SH group is greater. The solubility product constants of metal sulde for the presence of metal ions sorted in descending
order were as follow: Ksp(HgS) < Ksp(AgS) < Ksp(CuS) << Ksp(sulde of other
metal ions). Therefore, the binding ability among Hg2, Ag, Cu2, and SH groups
was much greater than that between other metal ions and SH. These facts may
explain the results shown in Table 1.
Sorbent Regenerability and Adsorption Capacity
The regenerability and stability of the sorbent was investigated by testing Hg2
standard solution (2.5 ng mL
1) according to general procedure for MSPE using the
same portion of adsorbent (0.2 g). It was observed that the sorbent could be reused
up to 30 runs with the recoveries of the target ion larger than 90%.
Table 1. Tolerance limits of potentially interfering ions
Ions

Tolerable concentration
(u gmL
1)

Recovery
(%)

K
Na
Mg2
Ca2
Zn2
Cd2
Pb2

2000
1000
800
20
10
10
50

92.8
107.2
98.5
101.7
91.2
109.1
90.8

Ions

Tolerable concentration
(ug mL
1)

Recovery
(%)

Ni2
Co2
Cu2
Ag
Al3
Fe3

50.0
50.0
0.5
0.2
30.0
20.0

105.7
109.1
103.8
94.9
92.8
91.0

MAGNETIC SILICA SORBENT FOR EXTRACTION OF Hg

713

The adsorption capacity of thiol-modied MSS was studied in order to

evaluate the amount of sorbent required to quantitatively concentrate the analytes
from a given solution. The method used was adapted from the procedure recommended by Maquieira, Elmahadi, and Puchades (1994). The adsorption capacities
of thiol-modied MSS for Hg2 was 101.0 mg g
1.

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Analytical Performance
Under the optimized experimental conditions, the analytical performance of
this method was evaluated. Based on the denition of IUPAC, the detection limit
(3r) of this method was 0.06 ng mL
1, and the relative standard deviation (RSD)
was 3.9% (c 1.0 n g mL
1, n 7). The calibration graph for the preconcentration
procedure was A 0.0435C 0.0328 (r2 0.99839) with concentration range of
0.25.0 ng mL
1. The enrichment factor (EF, calculated as the ratio of the slopes
for the calibration graphs with preconcentration and without preconcentration,
respectively) was 16.6.
For comparative purpose, the performance characteristics of this method and
other off-line SPE-CV-AAS systems reported in the literature are listed in Table 2.
The application of magnetic sorbent in SPE procedure greatly changed the SPE
procedure. The use of pump and SPE cartridge were avoided, and the magnetic separation greatly reduced the column experiments time and labor. Compared with traditional SPE procedure, the MSPE procedure was simple, effective, and quick. From
Table 2, it could be seen that the sorbent shows much larger adsorption capacity and
comparable detection limit with much smaller sample volume over other off-line
SPE-CV-AAS methods. Moreover, the sample volume and sample ow rate listed
in Table 2 conrmed that the MSPE procedure was quick and simple.

Table 2. Comparative data from some recent studies on off-line SPE=FAAS system
Analyte
Hg2

Hg2

Hg2
MeHg

Absorbent
Sulfur powder loaded with
N-(2-chloro benzoyl)-Nphenylthiourea
Agar powder modied with
2-mercaptobenzimidazole

Hg2
MeHg

Octadecyl-bonded silica membrane

disk modied by 2-[(2mercaptophyenylimino)methyl]
phenol (MPMP)
Staphylococcus aureus loaded
Dowex Optipore V-493

Hg2

Thiol-modied MSS

Adsorption
capacity

Detection
limit

Sample volume
and ow rate

35 mg g
1

3 pg mL
1

49 ug g
1

20 pg mL
1

3.8 pg mL
1

1000 mL 16 mL
min
1 (Pourreza
et al. 2009)
250 mL 6 mL min
1
(Pourreza and
Ghanemi 2009)
1500 mL 45 mL
min
1 (Ashkenani
et al. 2009)

6.5 mg g
1
(Hg2)
5.4 mg g
1
(MeHg)
101.0 mg g
1

2.5 pg mL
1
(Hg2) 1.7
pg mL
1
(MeHg)
60 pg mL
1

250 mL 4.0 mL
min
1 (Tuzen et al.
2009)
100 mL ultrasonication for 10 min
(this work)

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G. XIANG ET AL.
Table 3. Recovery for determination of Hg2 in environmental water samples. (n 3, ng mL
1)

Samples
Rain water

Well water

Treated water
(sewage treatment plant)

Added (ng mL
1)

Determined (n gmL
1)

Recovery (%)

0
1.0
2.0
0
1.0
2.0
0
1.0
2.0

1.41  0.17
2.51  0.16
3.46  0.10
0.34  0.02
1.40  0.12
2.37  0.05
1.30  0.17
2.26  0.14
3.45  0.03

110.0
102.5

106.0
109.5

96.0
107.5

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Sample Analysis
For real sample analysis, the standard calibration curve method was employed.
In order to evaluate the validity of the procedure, the method has been applied to the
determination of Hg2 in the certied reference sample (GBW0809 water sample).
The analytical results showed a good agreement between the determined values
(1.03  0.04 mg mL
1) and the certied values (1.00  0.05 m g mL
1).
The method was also applied to the determination of trace Hg2 in different
environmental water samples. The analytical results and the recoveries for the spiked
samples were given in Table 3. It could be seen that the recoveries for the spiked samples were between 96.0% and 110.0%.

CONCLUSIONS
A new thiol-modied MSS was synthesized and it was applied to MSPE
procedure as sorbent. The adsorption behavior of Hg2 on the thiol-modied
MSS was systematically investigated and it showed high selectivity and adsorption
capacity for Hg2. A simple, rapid, selective, and reliable method was developed
for the determination of trace Hg2 in environmental water samples by coupling
MSPE and CV-AAS.

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