Spectrochimica Acta Part B 61 (2006) 1069 – 1073

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Analytical note
Determination of Hg(II) in waters by on-line preconcentration using Cyanex
923 as a sorbent — Cold vapor atomic absorption spectrometry
Taicheng Duan a , Xuejie Song a , Jingwei Xu a , Pengran Guo a , Hangting Chen a,⁎, Hongfei Li b
a
State Key Laboratory of Electroanalytical Chemistry, National Research Center of Electroanalytical and Spectroanalytical Chemistry, Changchun Institute of
Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b
Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
Received 28 March 2006; accepted 12 September 2006
Available online 7 November 2006

Abstract

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated
and simultaneously separated from methyl mercury. The preconcentrated Hg (II) was then eluted with 10% HNO3 and subsequently reduced by
NaBH4 to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences
on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min− 1 sample loading rate. The
detection limit was 0.2 ng L− 1 and much lower than that of conventional method (around 15.8 ng L− 1). The relative standard deviation (RSD) is
1.8% for measurements of 40 ng L− 1 of Hg and the linear working curve is from 20 to 2000 ng L− 1 (with a correlation coefficient of 0.9996). The
method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for
both samples were satisfactory.
© 2006 Published by Elsevier B.V.

Keywords: Solid phase extraction; Cyanex 923; On-line preconcentration; Cold vapor atomic absorption spectrometry

1. Introduction [14], diphenylthiocarbazone(DZ) [11,13], methylthymol blue

Due to their unique toxicity, mercury species have attracted
great attention in environmental contamination monitoring.
Many methods have been established for the determination of
mercury species in water, soil or other environmental matrices.
Most of these methods involved a preconcentration and/or
separation technique, because the content of mercury in
environmental samples was very low and not compatible with
the absolute detection limits of most analytical instruments [1–
4]. In recent years, various on-line techniques have been
proposed for Hg preconcentration or/and separation [5–8], of
which mini-column solid phase extraction (SPE) was most
commonly used. Chelating agents, such as dithizone [9–11],
dithiocarbamate derivatives [7,12,13], O,O-diethyl dithiopho-
sphoric acid [14], 8-hydroxyquinoline-2-mercaptobenzothia-
zole(MBT) [15], thionalide(2-mercapto-N-2naphthylacetamide)
⁎ Corresponding author.
E-mail address: htchen@ciac.jl.cn (H. Chen).
0584-8547/$ - see front matter © 2006 Published by Elsevier B.V.
doi:10.1016/j.sab.2006.09.005
(MTB) [16] and methylthiosalicylate [8] were added in solutions
to form mercury complexes, or physically or chemically
immobilized on solid supports, such as alumina, C18, silica
gel, polytetrafluoroethylene (PTFE) and exchange resins.
Some of the above mentioned SPE techniques could only
operate in a narrow pH range [9,16]. Buffering of the solution
was even required [8], which not only complicates the sample
handling procedure but also increases the risk of contamination,
while for mini-columns obtained through chemical immobili-
zation, special pretreatment of the surface of the solid support
was necessary. Obviously, the preparation of SPE mini-columns
through physical immobilization was much simpler. However,
lifetime of the column should be carefully examined before
putting it into practical use, since physical affinity was weaker
than chemical affinity.
Cyanex 923, a mixture of straight-chain alkylated phosphine
oxides, mainly (92.4%) with normal hexyl and octyl groups,
was a new neutral extractant which appeared in the last decade
mainly for hydrometallurgical purpose. Applications of Cyanex
1070 T. Duan et al. / Spectrochimica Acta Part B 61 (2006) 1069–1073
923 for extraction of inorganic Hg was previously hydro-
metallurgically studied [17,18]. It was found that Cyanex 923
could effectively extract HgCl2 or HgBr2 complexes from
aqueous Zn, Cd, Ca, Ba, Mg or Fe containing solutions.
Cyanex 923 has several excellent properties, including little
tendency to hydrolysis, low solubility and high stability in both
acid and basic solutions, which makes it very attractive for
preparation of SPE columns through physical immobilization.
In this work, we attempted to use the Cyanex 923 to prepare a
SPE column and develop an on-line preconcentration technique
to couple with CVAAS for the determination of inorganic Hg in
water samples. The analytical performance of the on-line
preconcentration technique was fully evaluated.
2. Experimental
2.1. Instrumentation
A PerkinElmer atomic absorption spectrometer (AAnalyst
800) equipped with a quartz cell (160 mm length, 7-mm
diameter and quartz windows) and a flow-injection (FI) system
(FIAS-100, PerkinElmer, Germany) was used. The FI system
consisted of a PerkinElmer membrane gas–liquid separator and
a flow-meter used to measure the argon flow-rate in the gas–
liquid separator. Tygon pump tubes of different internal
diameters were used for carrying the solutions. PTFE tube
with 0.5 mm diameter was used as transmission tubing. A
mercury electrodeless discharge lamp (EDL, PerkinElmer,
Germany) operated at 180 mA was used as the radiation source.
The mercury resonance line at 253.7 nm and a spectral bandpass
of 0.7 nm were adopted for measurements.
Fig. 1. Schematic diagram of the manifold for FI-online SPE-HG-AAS.
2.2. Reagent
All chemicals used were of at least analytical-reagent grade.
HCl and H2O2 (Tianjin Chemical Reagent Plant, China) were of
ultra-pure grade. Water was de-ionized, followed by sub-boiling
distillation. An inorganic mercury stock standard solution of
1000 mg L− 1 was prepared from mercury nitrate (Merk). A
methylmercury stock standard solution of 1000 mg L− 1 was
prepared by dissolution of methylmercury chloride (Merk) in
methanol. A Hg(II) stock solution of 1000 mg L− 1 was prepared
from spectral pure HgO (Merk), and to maintain the stability of
the solution, a proper amount of K2CrO4 solution was added.
Working mercury standard solutions were prepared daily. Purity
of the Ar carrier gas was 99.99%.
Silinized PTFE powder of 60-mesh size was purchased from
The First Chemical Plant (Shanghai, China). Cyanex923 used to
prepare the SPE column was supplied by Cytec Canada and was
purified [19] before immobilization.
Solid phase extraction column was prepared following
instruction in Ref. [20].
2.3. Sample collection and treatment
City lake and deep well water (Changchun, Jilin,China) was
respectively collected in a 1 L PTFE bottle and filtered through
a 0.45 μm filter (glass fiber) immediately after sampling and
then acidified to 1% (v/v) HCl. For samples with low levels of
Cr6+, the acidified solutions were ready for determination
without further treatment. Otherwise, the solutions were
adjusted to 1% H2O2 (v/v) and we waited for about 10 min to
reduce Cr 6+ to Cr3+.
 T. Duan et al. / Spectrochimica Acta Part B 61 (2006) 1069–1073
2.4. Preconcentration and separation procedure
The diagram of FI manifold is shown in Fig. 1. First a sample
solution of 25 mL volume was aspirated at 10 mL min− 1 to load
Hg2+ onto the mini-column, then a washing solution was
aspirated for 30 s at the same flow rate to rinse the residue of the
sample solution in the transmitting tube into mini-column.
Second the10% v/v HNO3 carrier solution desorbed Hg2+ from
the mini-column at 6.5 mL min− 1 and merged with the NaBH4
stream with a flow rate of 3.7 mL min− 1 to generate Hg vapor.
Then the generated Hg vapor was separated from the liquid
phase in the gas–liquid separator and was carried by the Ar gas
carrier at a flow rate of 50 mL min− 1 to the quartz tube for
measurement.
3. Results and discussion
3.1. Effect of HCl concentration on the preconcentration/
separation performance
The extraction of Hg2+ by Cyanex 923 in HCl medium can
be expressed by the following equation:
HgCl2aq þ nTRPO3 ↔HgCl2d nTRPO3org
where n = 0, 1, 2 and 3, and TRPO3 represents Cyanex 923.
While the formation of Hg2+ complex with chloride ions is:
Hg2þ þ nCl− ↔½HgCln 2−n
Since only the neutral HgCl2 can be extracted, the Cl− /Hg2+
ratio would obviously affect the extraction efficiency: insuffi-
cient Cl− leads to the formation of HgCl+ while much excess of
Cl− leads to the formation of HgCl3− or HgCl42−.
HgCH3+ is the major part of total organic Hg in environ-
mental samples. Although the concentration of HgCH3+ is
normally about 2 orders of magnitude lower to that of inorganic
mercury, the concentration of HgCH3+ may sometimes be close
to that of inorganic mercury. In such situations, NaBH4 and
Fig. 2. Effect of HCl concentration on the preconcentration/separation of Hg2+
and CH3Hg+. Sample volume, 5 mL; concentrations of Hg2+ and CH3Hg+ are
10 μg L− 1; sample loading rates, 10 mL min− 1; and eluent 10% HNO3.
1071
result in measurement error will reduce HgCH3+ if HgCH3+ is not
separated. In this study, complete separation of HgCH3+ was
realized by Cyanex 923 column.
Fig. 2 describes the effect of HCl concentrations on both Hg2+
and CH3Hg+ extraction and separation. When Hg2+ and HgCH3+
were added at the same amount, Hg2+ could be completely
extracted and the extraction of HgCH3+ is close to zero under
lower HCl concentrations. With the increase of HCl concentra-
tion, the extraction efficiency for Hg2+ decreases, while that for
CH3Hg+ increases. From Fig. 2, 1% HCl was considered as the
optimal concentration.
3.2. Selection of elution reagent and its concentration
It was proved that 0.01 M Na2S2O3 or 5% thiourea in 1%
HCl can effectively strip the extracted Hg2+ [17]. In this work,
we found that HNO3 was also an excellent stripping reagent; the
effectiveness of HNO3 as an eluent may come from its ability to
decompose HgCl2 into Hg2+. Obviously HNO3 of high purity is
easy to obtain.
HNO3 worked as both an H+ donor in the vapor generation
and an eluent in Hg2+ desorption. The relationship between Hg
absorbance intensities and HNO3 concentrations was that the
absorbance increased with concentration of HNO3 from 6% to
10% (v/v), and at higher HNO3 concentrations the absorbance
was stable.
H2SO4 was also tested for Hg2+ elution, since in many other
works H2SO4 was used as a very effective stripper for
recovering Cyanex 923 by stripping the metal ions [21].
However, it did not work for stripping Hg, the reason may be
the formation of HgSO4, which is very stable and can hardly be
decomposed by other reagents.
3.3. Effect of sample loading rate
Low sample flow rate means a long analysis run, while high
flow rate may lead to incomplete Hg adsorption. When flow
rates are from 2 mL min− 1 to 20 mL min− 1, the extraction
efficiency is around 100%. However, high back-pressure on the
column was observed at flow rates higher than 20 mL min− 1. In
addition, high flow rates lead to decrease in the long-term
stability of the column. Therefore, 10 mL min− 1 was used as the
optimal sample flow rate.
3.4. Effect of elution flow rate
Because HNO3 eluent solution was also the acidic carrier for
Hg vapor generation, the flow rate is thus one of the key factors
affecting Hg vapor generation. The influence from elution rate
is illustrated in Fig. 3, from which it can be concluded that an
elution flow rate of about 6.5 mL min− 1 is preferable.
3.5. Optimization of vapor generation conditions
Important parameters of the hydride generation system for
cold vapor generation that should be optimized included the flow
rate of the argon carrier and, the flow rate and concentration of
1072 T. Duan et al. / Spectrochimica Acta Part B 61 (2006) 1069–1073

way to eliminate Cr6+ interference would be to reduce Cr6+ to

Cr3+. In about 10 min, H2O2 of 1% v/v concentration could
slowly but effectively reduce Cr6+ to Cr3+ in 1% v/v HCl at room
temperature.
According to the above discussion, it should be stressed that
H2O2 must be also added in the standard solutions when
establishing the working curve, because relatively high
concentrations of K2CrO4 were employed for stabilization of
Hg2+ in stock solutions.

3.7. Stability of the resin and the column

When the prepared resin was exposed to ambient atmosphere

Fig. 3. Effect of elution flow rate on Hg signal. Sample volume, 5 mL;
concentrations of Hg2+, 1 μg L− 1; concentration of HCl, 1% v/v; sample loading
rate, 10 mL min− 1; concentration of NaBH4 solution, 0.3% v/v and flow rate of
NaBH4 solution, 3 mL min− 1.
for over half a year, no decrease in analytical performance of the
resin was observed. For Cyanex 923 used as the adsorbent
reagent, a properly prepared column can be repeatedly used at
least 300 times for standard solutions, and at least 50 times for
sample solutions and in the presence of interferences.

3.8. Analytical performance of the preconcentration/separation

the NaBH4 solution. High signal responses were observed at low system
carrier flow rates, in contrary to results in the literature [3]
showing that high flow rates were more preferable. This A linear calibration curve was obtained for Hg2+ concentra-
difference may be attributed to the different gas–liquid separator tions from 20 to 2000 ng L− 1, with a correlation coefficient of
designs. It was found that a flow rate of 30 mL min− 1 and a 0.9996. The detection limit was 0.2 ng L− 1, which is lower than
concentration of 0.3% NaBH4 in 0.05% NaOH were suitable for that of conventional methods (around 15.8 ng L− 1, obtained by
this system. a comparative experiment). The precision of the method for
aqueous standards was evaluated by analyzing 6 replicates with
3.6. Interference studies Hg2+ concentration of 40 ng L− 1, which gave a relative standard
deviation (RSD) of 1.8%. The sample throughput was 20
Under the above optimal conditions, besides H2O2, samples h− 1, at the 10 mL min− 1 sample loading rate for 25 mL
cations such as K+, Na+, Ca2+, Mg2+, Al3+, Fe3+, V4+, of sample uptake volume.
Mn2+, Cu2+, Ni2+, Cr3+, Cr6+, Sn4+ and Mo6+, anions such
as NO3−, SO42−, PO43−, CO32− and SiO42− and organic substances 3.9. Recovery test and analytical application
such as humic acid, acetic acid, ethanol, acetone and citric acid at
different concentrations were respectively added into 1 μg L− 1 The method was successfully applied to the determination of
Hg2+ solution to observe their influence on Hg2+ adsorption. It inorganic Hg in city lake water and deep well water from
was found that the proposed preconcentration system had a Changchun (Capital of Jilin Province, China). The deep well
strong anti-interference ability for most of the foreign species, as water was directly supplied for industrial use without any
revealed by the results in Table 1. treatment. Recovery test was also conducted to evaluate the
Considering that Cr6+ had a severe depression effect on Hg feasibility of the method; each of water sample was spiked with
adsorption, interferences caused by different levels of Cr6+ were 80 ng L− 1 of Hg2+. All the results were listed in Table 2.
studied. The results indicated that when the levels of Cr6+ varies Though the recoveries are a little low, they are still acceptable
from 0 to 2.5 mg L− 1, the Hg signal was reduced from 0 to 31%; for such low Hg2+ concentrations. And it reveals that both the
from 2.5 to 12 mg L− 1, the depression increases to 65%. As Cr3+ studied water sources in the area are free from Hg 2+
imposed almost no interference on Hg2 adsorption, an effective contamination, in comparison with the data given by the
environmental quality standards for surface and underground
Table 1
water (GB3838-2002 and GB/T14848-93, respectively).
Tolerance of foreign species in the determination of 1 μg L− 1 of Hg2+
Table 2
Species Tolerance ratio m/m
Results for the determination of inorganic Hg in real and spiked samples (mean
+ + 2+ 2+ 3+ 3+ 2+ 5
K , Na , Ca , Mg , Al , Fe , Ni , 10 ± s n = 3)
V4+, Cu2+, Sn4+, Ti4+, Mn2+, Cr3+
Samples Spiked ng L− 1 Found ng L− 1 Recovery %
Zn2+, Mo6+ 104
Cr6+ 102 City lake water 0 16.9 ± 1.6 91.4
−
PO3− 2− 2− 2−
4 , CO3 , SO4 , SiO4 , NO3 , H2O2 106 80 90.0 ± 0.8
Acetic acid, ethanol, acetone, 106 Deep well water 0 5.0 ± 0.3 95.1
citric acid, humic acid 80 81.4 ± 2.2
 T. Duan et al. / Spectrochimica Acta Part B 61 (2006) 1069–1073
4. Conclusion
The use of Cyanex 923 as the sorbent for Hg preconcentra-
tion possessed several advantages such as high stability, high
preconcentration efficiency, and strong anti-interference ability.
Conditions for Hg adsorption and desorption on the SPE
column made from Cyanex 923 were readily on-line coupled
with CV-AAS, which made the established method concise and
suitable for routine analysis.
Acknowledgement
This work was supported by the National Nature Science
Foundation of China (No.20274050).
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