Journal of Hazardous Materials 233234 (2012) 207212

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Journal of Hazardous Materials
j our nal homepage: www. el sevi er . com/ l ocat e/ j hazmat
Sensitive determination of trace mercury by UVvisible diffuse reectance
spectroscopy after complexation and membrane ltration-enrichment
Changhai Yin, Jibran Iqbal, Huilian Hu, Bingxiang Liu, Lei Zhang, Bilin Zhu, Yiping Du

Shanghai Key Laboratory of Functional Materials Chemistry, and Research Center of Analysis and Test, East China University of Science and Technology, Meilong Rd. 130,
Shanghai 200237, China
h i g h l i g h t s
A simple, sensitive and selective solid phase reectometry method is proposed for the determination of trace mercury in real water samples.
The merits of the method include high enrichment efciency, low cost, easy operation and no solvent elution or desorption.
Hgdithizone nanoparticles formed in solution can be enriched on the surface of the membrane.
The method will be useful in monitoring the environment in view of mercury pollution.
a r t i c l e i n f o
Article history:
Received 14 March 2012
Received in revised form4 July 2012
Accepted 5 July 2012
Available online 13 July 2012
Keywords:
UVvisible diffuse reectance spectroscopy
(DRUVS)
Mercury(II)
Dithizone
Membrane ltration
a b s t r a c t
A simple, sensitive and selective solid phase reectometry method is proposed for the determination of
trace mercury in aqueous samples. The complexation reagent dithizone was rstly injected into the prop-
erly buffered solution with vigorous stirring, which started a simultaneous formation of nanoparticles
suspension of dithizone and its complexation reaction with the mercury(II) ions to make Hgdithizone
nanoparticles. After a denite time, the mixture was ltered with membrane, and then quantied directly
on the surface of the membrane by using integrating sphere accessory of the UVvisible spectropho-
tometer. The quantitative analysis was carried out at a wavelength of 485 nm since it yielded the largest
difference in diffuse reectance spectra before and after reaction with mercury(II).A good linear corre-
lation in the range of 0.24.0 g/L with a squared correlation coefcient (R
2
) of 0.9944 and a detection
limit of 0.12 g/L were obtained. The accuracy of the method was evaluated by the analysis of spiked
mercury(II) concentrations determined using this method along with those determined by the atomic u-
orescence mercury vapourmeter and the results obtained were in good agreement. The proposed method
was applied to the determination of mercury in tap water and river water samples with the recovery in
an acceptable range (95.7105.3%).
2012 Elsevier B.V. All rights reserved.
1. Introduction
Mercury is a toxic and hazardous element and its contamination
in water is a global problem because it can cause sensorineu-
ral hearing loss and impaired speech perception [1]. The allowed
level of mercury in drinking water is 1.0g/L recommended by
the World Health Organization (WHO). It is considered as a highly
dangerous element because of its accumulative and persistent
character in the environment and biota [2]. Therefore, it is quite
important to develop reliable methods for its determination in
environment.
Several analytical techniques have been applied for the deter-
mination of mercury, including atomic absorption spectrometry

Corresponding author. Tel.: +86 21 64250551; fax: +86 21 64252947.

E-mail address: yipingdu@ecust.edu.cn (Y. Du).
(AAS) [35], atomic uorescence spectrometry (AFS) [68], induc-
tively coupled plasma optical emission spectrometry (ICP-OES) [9],
inductively coupled plasma-mass spectrometry (ICP-MS) [10,11],
electrochemical method [12] and spectrophotometry [13]. Some
sophisticated instrumental techniques are extensively used as
standard methods in the determination of mercury but they still
possess some disadvantages, such as high cost of instruments,
matrix interference and time consuming. Spectrophotometry has
been most commonly used for quantitative analysis of mercury
in solution, due to the relatively inexpensive instrumentation and
simple operation procedure, although its biggest drawback is the
lowsensitivity which only can detect mercury at ppm(mg/L) level
normally [14].
However, mercury usually exists in the environment at ppb
(g/L) level with complicate matrix, so extraction and preconcen-
tration procedures are often indispensable. Solid phase extraction
(SPE) is a popular and growing preconcentration technique, which
0304-3894/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2012.07.016
208 C. Yin et al. / Journal of Hazardous Materials 233234 (2012) 207212
has successfully been used for preconcentrating and separating
trace mercury from different matrixes [1520]. Compare to con-
ventional liquidliquid extraction, solid phase extractionpossesses
some merits, such as easier manipulation, fewer solvent con-
sumption, higher preconcentration factor and easier couple with
analytical instruments suchas UVvisible, ICP-MS, ICP-AES andCV-
AFS. As to the SPE procedure, the nal step is the elution of the
extracted metal ions from the membrane disk or columns using a
solution containing acid or other solvents prior to the determina-
tion. However, it is tedious and time-consuming. Thus, it would be
very meaningful to develop a practical simple and fast spectropho-
tometric method for the determination of trace mercury with high
sensitivity and accuracy.
In recent years, colorimetric solid phase extraction (C-SPE) has
been utilized, which is based on the extraction of analytes onto
a proper support loaded with a colorimetric reagent and then
quantied directly on the solid support surface using reectance
spectroscopy [2136]. The main advantage of C-SPE is that the elu-
tionstep of SPE canbe completely eliminated. The direct analysis of
analytes on the surface of solid support is convenient because of its
simplicity and rapidity for routine analyses. However, the reagent
is weakly immobilized on a solid support and easily released as
it ows through the support. Also the analytes complex with the
reagent just onthe surface of solidsupport andthe results are sensi-
tive to the ltration rate, ltering of too much water might partially
ush the reagent and cause errors [37,38].
To these problems, the aim of this work was to develop a
method to detect ppb (g/L) level mercury with UVvisible diffuse
reectancespectroscopy. Thereagent dithizoneemployedtodetect
the mercury was not impregnated on the membrane, but formed
colored nanoparticles by complexation with mercury(II) ions in
solution. The complexes were then collected on the surface of a
membrane by ltering and quantied directly on the surface of the
membrane by using integrating sphere accessory of the UVvisible
spectrophotometer. Some parameters such as pH, the amount of
dithizone, the reaction time, effect of potentially interfering ions
and the enrichment efciency were investigated in detail. The pro-
posed method has been satisfactorily applied to the determination
of trace mercury in real water samples.
2. Experimental
2.1. Apparatus
A UVvisible spectrophotometer Evolution 220 (Thermo Fisher
Scientic Inc., USA) equipped with an integrating sphere accessory
was used for UVvisible diffuse reectance spectra measurements.
A model PHS-25 pH meter (Mettler Toledo instrument (Shanghai)
Co., Ltd.) was used for pH measurements. Ultra-pure water was
obtained from an ultra-pure water purication system (SARTO-
RIUS arium611DI, 18.2M, Germany). Atomic uorescence mercury
vapourmeter (German Jena Analytical Instruments AG, Germany)
was used to evaluate the enrichment efciency and validate the
accuracy. SHB-III Vadose water vacuum pump (Shanghai Weikai
instrument equipment Co., Ltd., China) andFiltrationdevices (Tian-
jin Jinteng experiment equipment Co., Ltd., China) were used for
membrane ltration-enrichment. 85-2 magnetic stirrer (Shanghai
Zhiwei electric appliance Co., Ltd., China) was used for stirring the
solution to complex.
2.2. Materials and reagents
A stock standard solution of mercury(II) at a concentration
of 1.0g/L was prepared by dissolving 0.1354g analytical reagent
gradeHgCl
2
(Reagent grade, Sinopharm, Shanghai, China) in100mL
water with 5.0mL 1% (v/v) hydrochloric acid and kept in refrigera-
tor at 4

C. Working standard solutions were obtained by stepwise

dilution of the stock standard solution with ultra-pure water. A
complexationreagent solutionof dithizone(1.0g/L) was prepared
bydissolvingtheappropriateamount of this reagent inacetone. The
glycine buffer (pH=2.8) solutionwas preparedby using glycine and
hydrochloric acid. All other reagents were analytical reagent grade,
and were dissolved by ultra-pure water to obtain their solutions.
WX mixed cellulose membranes (Shanghai Diqing ltration tech-
nology Co., Ltd., China) used as solid phase support in the present
study were with the pore size of 0.22m, 50mmdiameter.
2.3. Sample preparation
Water samples were collected in prewashed (with detergent,
ultra-pure water, dilute HNO
3
and ultra-pure water, respectively)
polyethylene bottles. Tap water was collected from our labora-
tory. River water was taken at the depth of 50cm of Qingchun
river of Shanghai, China. All water samples were ltered with
0.22m micropore membrane acidied with hydrochloric acid
before analysis. Organic mercury species were treated into mer-
cury(II) according to Ref. [39]. Briey, 1000mL water samples were
decomposed with 4.0mL 50g/L potassiumpermanganate solution
and 4.0mL 50g/L potassium persulfate solution in boiling water
bath for 2h, in order to convert all the mercury species to mer-
cury(II). After that, 100g/L hydroxylamine hydrochloride solution
was added to reduce the residual oxidant.
2.4. Experiment procedure
In this method, the dithizone was dissolved in acetone (1.0g/L)
anddilutedtoworkingsolution(6.0mg/L). Then, 2.0mL of this solu-
tion was injected into 500mL of the properly buffered (pH=2.8)
examined solution, under vigorous stirring with magnetic stirrer,
which started a simultaneous formation of nanoparticles suspen-
sionof dithizoneandits complexationreactionwiththemercury(II)
ions [40]. After 2.0min, the Hgdithizone nanoparticles were l-
tered with WX mixed cellulose membranes with the aid of vacuum
pump. The UVvisible diffuse reectance spectra of the mem-
branes were measured by using integrating sphere accessory of the
UVvisible spectrophotometer.
3. Results and discussion
3.1. UVvisible diffuse reectance spectra of Hgdithizone
complex
Dithizone is one of the most popular reagent employed in
the spectrophotometric determination of mercury(II) in solution
[4143], andis selectedfor mercury(II) sensingbecauseof its higher
selectivity and sensitivity. Furthermore, dithizone and its complex
Hgdithizone showlowsolubility in water. This property is partic-
ularly advantageous to prepare the dithizone nano-dispersion that
may easily be captured by the membrane when ltration [44].
The color of membranes changed from steel blue to reddish
brown in the presence of different concentrations of mercury(II)
solution at pH=2.8 when dithizone was added in. As is shown in
Fig. 1, the UVvisible diffuse reectance spectra of Hgdithizone
complexonmembranes were recordedinthe range of 400800nm.
Clearly there are two peaks at 485nm and 602nm in the diffuse
reectance spectra, which are due to Hgdithizone complex and
dithizone, respectively. The former peak at 485nmwas chosen for
analysis. From Fig. 1 we can also nd that absorbance at 485nm
that is related to the Hgdithizone complex clearly increases with
mercury(II) concentration, while that at 602nm related to the
dithizone decreases with mercury(II) concentration. This is easy
C. Yin et al. / Journal of Hazardous Materials 233234 (2012) 207212 209
Fig. 1. UVvisible diffuse reectance spectra of membranes with different mercury(II) concentrations (0.24.0g/L).
to understand because with the increase of mercury(II) concentra-
tion, the amount of Hgdithizone complex increases and dithizone
decreases.
3.2. Inuence of experiment conditions
To obtain satisfactory results, some experiment conditions such
as pH of the solution, concentration of the reagent, and reaction
time were thoroughly investigated and optimized.
3.2.1. Effect of pH
The pH is proven to be a critical parameter for the determina-
tion of mercury(II). Fig. 2 shows the effect of pH from1.0 to 5.0, as
this pHrange is suitable for the formationof Hgdithizone complex
in solution. The inuence of pH on the formation of Hgdithizone
complex can be expressed from an complexation reaction equa-
tion: Hg
2+
+2H
2
L =Hg(HL)
2
+2H
+
(where H
2
L is dithizone). Clearly
Fig. 2. The effect of pHfrom1.0 to 5.0 on the diffuse reectance absorbance, [Hg
2+
]:
2.0 g/L. [dithizone]: 6.0g/L; reaction time: 2.0min.
lowpHshould easily cause decomposition of the complex Hg(HL)
2
,
while high pH may cause hydrolysis of Hg
2+
. Therefore, the pH
should keep in a suitable range for optimized diffuse reectance
absorbance signal because higher and lower acidic conditions are
harmful to make stable Hgdithizone complex. As is shown in Fig. 2
a relatively favorable pH value range was 2.03.0, and the maxi-
mum absorbance was obtained at pH=2.8, therefore pH=2.8 was
selected for further experiments.
3.2.2. Effect of dithizone concentration
The concentration of dithizone solution used for the deter-
mination of mercury(II) is probably the main parameter that
must be investigated since it primarily determines the diffuse
reectance absorbance. The inuence of dithizone concentration
on the determination of 2.0g/L of mercury(II) was investigated in
the concentration range of 1.59.0g/L. As is shown in Fig. 3, the
diffuse reectance absorbance signal at 485nmis increasedquickly
Fig. 3. Effect of dithizone concentration on the diffuse reectance absorbance
[Hg
2+
]: 2.0g/L. pH: 2.8; reaction time: 2.0min.
210 C. Yin et al. / Journal of Hazardous Materials 233234 (2012) 207212
withthe increase of dithizone concentrationto 6.0g/L, and higher
dithizone concentration would not increase the absorbance sig-
nicantly. The increase of absorbance results from the reaction
between dithizone and mercury(II) ions and the Hgdithizone
complex coated membrane has maximum absorbance at 485nm.
The amounts of Hgdithizone increase with dithizone rst and
then tend to a constant for no enough mercury for formation
Hgdithizone complex. The concentration of dithizone of 6.0g/L
was selected for the further studies because it ensures a suf-
cient reagent for allowing the total reaction of the mercury(II). The
further excess of dithizone will inevitably affect the direct mea-
surement of diffuse reectance absorbance of the Hgdithizone
complex.
3.2.3. Effect of reaction time
The reaction time is the next parameter need to be consid-
ered. Generally, the reaction between mercury(II) and dithizone
is a time-dependent process and the maximum absorbance sig-
nal is attained when the system is at equilibrium. And complete
equilibrium needs to attain for accurate and reproducible analy-
sis. The effect of reaction time was studied in our work with the
time range of 2.020.0min under roomtemperature and vigorous
stirring. The results showed that the diffuse reectance absorbance
at 485nm almost kept constant when the reaction time was from
2.0 to 20.0min. The reaction between mercury(II) and dithizone
is so quick under our experiment condition that it has completed
within 2.0min, therefore the reaction time was xed to 2.0min for
convenience and rapidity.
3.3. Enrichment efciency
The extraction percentage of mercury(II) to the membrane
was estimated using atomic uorescence mercury vapourmeter to
detect the amount of mercury(II) in the ltrate after membrane l-
tration. The owrate, which affects the enrichment, was controlled
by vacuum degree of the vacuum pump. Five different vacuum
degrees were set: 0.005MPa, 0.020MPa, 0.045MPa, 0.065MPa
and.095MPa, the diffuse reectance spectra of the membranes
have no signicantly change by varying the vacuum degree from
0.005to0.065MPa, but the absorbance decreasedquickly whenthe
vacuum degree reached to 0.095MPa. Therefore the vacuum was
xed to 0.05MPa for rapidity and higher absorbance signal. Four
mercury(II) solutions with concentrations of 0.5, 2.0, 5.0, 10.0g/L
were used to react with dithizone, the vacuum degree was xed
to 0.05MPa when the complex was ltrated with membranes. The
results of mercury(II) detection using atomic uorescence mercury
vapourmeter showed that no mercury in the ltrate solutions was
detected for the four solution samples, that meant the mercury(II)
in the ltrate solutions were less than 0.5ng/L (the limit of detec-
tion of the atomic uorescence mercury vapourmeter), accordingly
enrichment efciency was estimated to be more than 99.9%. The
high enrichment efciency ensures the method developed in the
study has high sensitivity and high reliability for ppb (g/L) level
mercury detection.
3.4. Linear response range of the proposed method
Calibration curve was obtained according to the procedure
described above. Mercury(II) standard solutions with concentra-
tions of 0.2, 0.5, 0.75, 1.0, 1.5, 2.0, 3.0, and 4.0g/L were prepared
to build calibration curve. Absorbance response signals chosen for
calibration were obtained from the diffuse reectance spectra at
485nm. As shown in Fig. 4, absorbance and mercury(II) concentra-
tionhas a good linear correlationinthe range of 0.24.0g/L witha
squaredcorrelationcoefcient (R
2
) of 0.9944. The limit of detection
(LOD) was estimated using three times standard deviation dened
Fig. 4. Calibration curve for different Hg (II) concentrations in range of 0.24.0g/L.
as C
L
=3S
B
/m (where C
L
, S
B
and m are the limit of detection, stan-
dard deviation of six measurements of the blank sample and slope
of the calibration curve, respectively), that was 0.12g/L.
3.5. Effect of potentially interfering ions
There are always many ions existedinreal water samples, so the
effect of potentially interfering ions should be investigated before
the application of the proposed method. The interference from
some potential coexisting ions was studied for 2.0ppb of mer-
cury(II) solution in the presence of different amounts of coexisting
ions using the proposed method. The tolerance ratio was dened
as the maximum concentration of a coexisting ion to the concen-
tration of a determined target ion causing an error not greater than
5% in the measurements. The tolerance ratios of coexisting ions to
2.0g/L Hg
2+
were more than 5000 for Na
+
, K
+
, NH
4
+
, Ca
2+
, Mg
2+
,
Al
3+
, 1000 for Fe
3+
, Zn
2+
, Mn
2+
, Pb
2+
, Cd
2+
, Co
2+
, 5 for Cu
2+
under
our experiment condition. The copper(II) was found to interfere
to the determination of mercury severely at pH=2.8 because it
may form Cudithizone complex and yield a strong absorption at
485nm. Fortunately, to add masking reagents, such as EDTA, would
eliminate its interference. The EDTA can mask Cu
2+
by formation
water-soluble complexes, which cannot be captured by the mem-
brane when ltration. It is noteworthy that EDTA did not interfere
withthedeterminationof ppb(g/L) level mercury(II). For Cu
2+
, the
tolerance ratio was enhanced to 1000 after adding 6mL 1g/L EDTA.
Allowance of the concentration ratios of anions were also exam-
ined including Cl

, Br

, NO
3

, PO
4
3
, CO
3
2
, SO
4
2
and CH
3
COO

.
We set the ratio from10,000 to 1,000,000, and no interference was
observed for Hg
2+
determination. The results were listed in Table 1.
Table 1
The tolerance ratios of ions on the determination of 2.0g/L of Hg (II).
Potential interfering ions Tolerance ratio
Na
+
, K
+
, NH
4
+
, Ca
2+
, Mg
2+
, Al
3+
5000
Fe
3+
, Zn
2+
, Mn
2+
, Pb
2+
, Cd
2+
, Co
2+
1000
Cl

, Br

, NO
3

, PO
4
3
, CO
3
2
, SO
4
2
, CH
3
COO

No effect
Cu
2+
5
a
Cu
2+
1000
a
Tolerance ratio after 6mL 1g/L EDTA solution was added before the experiment
procedure.
C. Yin et al. / Journal of Hazardous Materials 233234 (2012) 207212 211
Table 2
Analytical results of mercury determination in spiked water samples by the proposed method and the atomic uorescence mercury vapourmeter.
Samples Added (g/L) Measured (g/L)
a
Error (g/L)
b
This method Recovery (%) Mercury vapourmeter Recovery (%)
Tap water
0.5 0.52 0.04 104.0 0.51 0.03 102.0 0.01
1.5 1.45 0.12 96.7 1.57 0.13 104.7 0.12
3.0 3.14 0.07 104.6 3.15 0.10 105.2 0.01
River water
0.5 0.52 0.03 104.0 0.49 0.01 98.5 0.03
1.5 1.50 0.13 105.3 1.46 0.11 99.5 0.04
3.0 2.87 0.11 95.7 3.22 0.13 104.0 0.05
a
Value =meanSD (n=3).
b
Value =mean (this method) mean (mercury vapourmeter).
3.6. Application to real samples
Tap water and river water samples were analyzed by atomic
uorescence mercury vapourmeter rst and there was no mercury
found. To assess the proposed method, some synthetic water sam-
ples were prepared by adding appropriate amounts of standard
mercury(II) solution to the tap water and river water to make
the concentrations at 0.5, 1.5, and 3.0g/L. We detected mercury
concentrations of the samples with the proposed method and
atomic uorescence mercury vapourmeter to assess accuracy, and
each sample was analyzed three times for calculation of standard
deviation (SD). As shown in Table 2, the recovery of the added
amounts was in the range of 95.7105.3% and the standard devi-
ation (SD) was from 0.03g/L to 0.13g/L, which demonstrated
that the proposed method exhibited a good reliability. By com-
paring the results of various samples obtained from the proposed
method with the atomic uorescence mercury vapourmeter,
there were no signicant differences in view of SD values and
measured concentrations. As can be seen, the errors between the
two methods ranged from 0.12g/L to 0.04g/L, therefore they
are in good agreement with each other. These results demon-
strated the applicability of the proposed method to determine ppb
(g/L) level concentration of mercury in the environmental water
samples.
4. Conclusions
Asensitive solidphase reectometry methodfor mercury deter-
mination was developed by UVvisible diffuse reectance spec-
troscopy after complexation and membrane ltration-enrichment.
Besides high enrichment efciency, the merits of this method
include lowcost, loworganic reagent consumption and easy oper-
ation. No solvent elution or desorption is required because the
amount of the colored Hgdithizone complex is directly mea-
sured on the surface of membrane by integrating sphere accessory
of spectrophotometer. Mercury(II) ions complex with dithizone
in solution and then can be enriched on the membrane surface
by ltration-enrichment giving a remarkably high quantication
limit. A good linear correlation in the range of 0.24.0g/L with a
squared correlation coefcient (R
2
) of 0.9944 and a detection limit
of 0.12g/L were obtained. The recovery was between 95.7% and
105.3% when tap water and river water samples were analyzed,
and the standard deviation (SD) was from 0.03g/L to 0.13g/L.
By comparing the results of various samples obtained fromthe pro-
posed method with the atomic uorescence mercury vapourmeter,
there were no signicant difference. The proposed method had
been successfully applied for the determination of trace mercury
in real water samples containing a large amount of interfering ions
by the addition of EDTA as a masking reagent.
Acknowledgement
The authors gratefully acknowledge the nancial support for
this project fromthe National Natural Science Foundation of China
(20975039).
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