Spectrochimica Acta Part B 105 (2015) 103–108

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Spectrochimica Acta Part B

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

Methylmercury in water samples at the pg/L level by online

preconcentration liquid chromatography cold vapor-atomic
fluorescence spectrometry☆
Christoph-Cornelius Brombach a, Bin Chen b, Warren T. Corns b, Jörg Feldmann a, Eva M. Krupp a,⁎
a
Trace Element Speciation Laboratory, Department of Chemistry, Meston Walk, University of Aberdeen, Aberdeen AB24 3UE, United Kingdom
b
PS Analytical, Arthur House, Crayfields Industrial Estate, Main Road, Orpington, Kent BR5 3HP, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: Ultra-traces of methylmercury at the sub-ppt level can be magnified in the foodweb and is of concern. In environ-
Received 30 May 2014 mental monitoring a routine robust analytical method is needed to determine methylmercury in water. The de-
Accepted 11 September 2014 velopment of an analytical method for ultra-trace speciation analysis of methylmercury (MeHg) in water
Available online 16 October 2014
samples is described. The approach is based on HPLC-CV-AFS with on-line preconcentration of water samples
up to 200 mL, resulting in a detection limit of 40 pg/L (ppq) for MeHg, expressed as Hg. The unit consists of an
Keywords:
Methylmercury speciation
optimized preconcentration column filled with a sulfur-based sorption material, on which mercury species are
Water preconcentrated and subsequently eluted, separated and detected via HPLC-CV-AFS (high performance liquid
Preconcentration chromatography–cold vapor atomic fluorescence spectrometry). During the method development a type of ad-
Atomic fluorescence spectrometry sorbate material, the pH dependence, the sample load rate and the carry-over were investigated using break-
Ultra-traces through experiments. The method shows broad pH stability in the range of pH 0 to 7, without the need for
buffer addition and shows limited matrix effects so that MeHg is quantitatively recovered from sewage, river
and seawater directly in the acidified samples without sample preparation.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Mercury is an environmental pollutant of global concern. It occurs in
nature in different chemical species, usually classified into inorganic
mercury, organic mercury and elemental mercury. All mercury species
have severe toxic effects on biota, but the toxicity and physiological me-
tabolism differs, with organic mercury known as the most toxic mercury
compound [1]. Methylmercury (MeHg) is the species of highest con-
cern, as it biomagnifies through the aquatic and marine food web. Typ-
ical bioaccumulation factors can reach up to one million or higher, with
typical water concentrations well below the ppt (ng/L) range, to MeHg
concentration in predatory fish like tuna or swordfish of several ppm
(mg/kg). MeHg can reach up to 95% of total Hg in the muscle of predator
fish and cetaceans, at concentration levels in the range of mg/kg [2,3].
Alleviated mercury and methylmercury pollution in water has therefore
a direct impact on human food [4]. Since MeHg is known to cause severe
brain damage, the EU and other authorities advise reduced fish con-
sumption for pregnant women and small children. A small increase of
mercury and especially MeHg in water has a huge effect on the living or-
ganisms in the aquatic system and the response is expressed only after
☆ This article is dedicated to Jim Holcombe, in recognition of his academic, mentoring
and scientific achievements, and his service to the spectroscopic community.
⁎ Corresponding author.
E-mail address: e.krupp@abdn.ac.uk (E.M. Krupp).
decades [5]. Typical concentrations of total mercury in water are in the
low ppt or ng/L range, with MeHg accounting only for a few percentages
of the total mercury, and speciation analysis at such low levels is ex-
tremely challenging.
The most common methods for low-level Hg speciation are GC-CV-
AFS [6] (gas chromatography–cold vapor atomic fluorescence spec-
trometry) and GC-ICP-MS [7,8] (gas chromatography–inductively
coupled plasma mass spectrometry), which require derivatization into
volatile mercury species. Ethylation, propylation and butylation are
common reactions to form volatile mercury species. A well defined pH
range is required for an optimal derivatisation yield, and the reaction
is often matrix dependant [7,9]. This can be prevented by the use of spe-
cies specific isotope dilution mass spectrometry (SSIDMS) when GC-
ICPMS is employed. This technique is however expensive and time
consuming. Another approach to overcome the matrix effect is the dis-
tillation of the HCl acidified water samples [9], this is however time con-
suming and it has shown to produce artifact MeHg [10].
Main challenge for Hg speciation in natural water samples are
the detection limits. Most techniques can detect MeHg in the ppb or
μg L−1 range, while water concentrations are several orders of magni-
tude lower, i.e. in the low ng/L [11]. An EPA method is the accepted
“gold standard” for ultra-trace level Hg speciation in water [12], howev-
er this method involves substantial sample preparation steps involving
water vapor distillation, derivatisation, purge and trap and detection via
GC-AFS, providing a detection limit of 40 pg/L for MeHg. Here, strategies

http://dx.doi.org/10.1016/j.sab.2014.09.014
0584-8547/© 2014 Elsevier B.V. All rights reserved.
104 C.-C. Brombach et al. / Spectrochimica Acta Part B 105 (2015) 103–108
using a preconcentration of the mercury species prior to analysis are
useful alternatives, when detection limits in the pg/L concentration
in water are requested. Solid-phase extraction (SPE) is a powerful ap-
proach for the preconcentration of mercury species, and a recent review
by Leopold et al. [13] highlights a variety of different techniques used
to date. The most common options are off-line preconcentration
(which could be done in the field) or on-line preconcentration prior
measurement.
The preconcentration materials commonly used for mercury contain
reduced sulfur dithizone [14], ammonium pyrrolidine dithicarbamate
[15], sulfydryl cotton [16] or silica gel modified with diethylenetriamine
and thiourea [17]. These substances utilize mercury's high affinity to re-
duced thiols, while other materials utilize ion exchange effects to bind
positively charged mercury species [18]. All these methods however op-
erate in a narrow pH range necessary for the preconcentration step, and
show some effects regarding the sample matrix.
Typical detection limits for MeHg in aqueous samples using
preconcentration-HPLC-CV-AFS based instrumentation are reported be-
tween 0.007 and 0.042 ng/L [18–20]. ICP-MS detection based systems
have recently been reported to deliver 0.016 ng/L with preconcentration
volumina in the range of 6 mL, however at high instrumental running
cost. Vermillion et al. used special home-made thiol material for
preconcentration followed by ion chromatography and CV-AFS. They re-
ported an LOD for MeHg of 0.007 ng/L with 40 mL preconcentration vol-
ume, which however requires an additional 2-h leaching step and is pH
dependent.
The aim of this study is the development of a method which is sensi-
tive enough to determine MeHg in the lower ppq (pg/L) range with high
selectivity and matrix independency, focused on robustness, cost-
efficiency and ease of operation with a view to automatization. Inorganic
mercury (Hg2+) is usually present in higher concentrations (often a
factor of 1000) in water samples, and is likewise preconcentrated and
retained in our analytical system; therefore, it is important to achieve a
clear separation between the two species so that MeHg quantification
is not compromised. In this work we employed CV-AFS with an online
preconcentration column containing sulfur based ligands anchored to a
silica backbone and subsequent separation using a C8 HPLC column.
The method has the potential to be fully automated, so that low MeHg
concentrations can be analyzed routinely.
2. Experimental
1. Instrumentation
The instrumental set-up is shown in Fig. 1. The preconcentration unit
consists of a six-port valve where the sample loop is substituted with the
preconcentration column (empty HPLC column, 2.1 × 30 mm, 2 μm frits,
Fig. 1. Set-up of the on-line preconcentration HPLC-CV-AFS system for ultra-trace MeHg and Hg2+ determination.
(Thames Restek, UK)). The preconcentration column is filled with a mix-
ture of thiolsilica and thioureasilica based material (40–63 μm, PS Analyt-
ical, UK, part no: L820K005). An HPLC pump (Spectra-Physics Analyical
P100, UK) loads the sample onto the preconcentration column at a con-
stant flow rate against a considerable backpressure. Once the sample is
loaded onto the preconcentration column, the 6 port valve switches
and elutes the sample from this column onto the separation column
(Eclipse XDB C8 (4.6 × 150 mm, 5 μm, Agilent, UK)), which is done by
a second HPLC pump (Kontron Instruments, UK). The mobile phase is
pumped with a flow rate of 1 mL/min. Post-column oxidation of MeHg
to Hg2+ is achieved by UV irradiation (UV-cracker S570U100 and cooling
module S570C100, P.S. Analytical Ltd., Orpington, UK) and addition of
bromide/bromate solution as oxidant at a flow rate of 3 mL/min. The re-
ductant is added with a flow rate of 5 mL/min to convert Hg2+ to Hg0.
Detection is performed by the PSA Millenium Merlin atomic fluorescence
spectrometric detector (P.S. Analytical Ltd., Orpington, UK).
One complete cycle (loading, elution and analysis) takes 12 min for
35 mL of sample volume for preconcentration. Sample loading takes
7 min using a flow-rate of 5 mL/min, after which the valve is switched
to elute the mercury species from the preconcentration column. The
valve is switched back after 3 min to allow the next sample to be loaded.
The calibration of the instrument is performed using MeHg solutions of
defined concentration acidified with 0.12 M hydrochloric acid which are
preconcentrated and analyzed like the samples.
Calibration standards were prepared in a range of 0–20 ng/L (blank,
0.5, 1, 5, 10 and 20 ng/L) MeHg, with a preconcentration volume of
35 mL (for 200 mL volume: Blank, 0.04, 0.1, 0.2, 0.4, 0.7, 1 and 3 ng/L)
for most of the experiments conducted in this study. Peak area was
used for quantitative evaluation of the data.
2. Methods and materials
1. Chemicals
Stock solution of inorganic mercury was purchased from Fluka Analyt-
ical (1000 mL/min, TraceCERT®, Sigma Aldrich, UK). The stock solution of
methylmercury chloride was prepared by dissolving the mercury com-
pound (Sigma Aldrich, UK) in methanol to 10,000 mg Hg/kg. Further di-
lutions were carried out in 1% (v/v) hydrochloric acid (HCl). Double-
distilled water was produced by an Aquatron water still A4000D (Bibby
Scientific Limited, UK). 1.5 mM ammonium pyrrolidine dithiocarba-
mate (APDC) (~ 99%, Sigma Aldrich, UK) and 75% (v/v) methanol
(AnalR grade, VWR, UK) were used for the mobile phase. A solution of
10% (v/v) Tritrisol® 0.1 M bromide/bromate solution (Merck, Darm-
stadt, Germany) and 3.7% HCl (v/v) (AnalR grade, VWR, UK) in
double-distilled water was used as the oxidant, a solution of 2% tin(II)
chloride (purchased as tin(II)chloride dihydrate from Alpha Aesar,
UK) and 3.7% hydrochloric acid (v/v) (AnalR grade, VWR, UK) in
 C.-C. Brombach et al. / Spectrochimica Acta Part B 105 (2015) 103–108 105

double-distilled water. 25% (w/w) tetramethylammonium hydroxide

(99.9999% (metal basis), Alpha Aesar, UK) were used for the digestion
of CRMs. For total mercury (T-Hg) analysis, the aqueous solution was
oxidized with Tritrisol® 0.1 M bromide/bromate solution (Merck,
Darmstadt, Germany), and the reaction quenched 0.2 mL of 10% (m/v)
ascorbic acid (Analytical reagent grade, Fisher Scientific, UK).

2. Certified reference materials

The human hair samples NIES CRM No. 13 and IAEA-085 were
purchased directly from NIES, Japan and IAEA, Monaco, respectively.
NIES CRM No. 13 is certified for 3.8 ± 0.4 mg/kg MeHg and 4.42 ±
0.20 mg/kg T-Hg, and IAEA-085 is certified for 22.9 ± 1.0 mg/kg
MeHg and 23.2 ± 0.8 mg/kg T-Hg.

3. Sample preparation

1. Water samples
Three different water samples were used in this work: Seawater
was collected at a local beach in Aberdeen, river water was collected
from River Don in Aberdeen and crude sewage was collected at a
sewage treatment plant (Persley, Aberdeen). The water samples
were filtered with 0.2 μm pore sized filter membranes and acidified
with 0.37% (v/v) HCl.

2. Extraction of certified reference materials

Human hair samples NIES CRM No. 13 and IAEA-085 are certified for
MeHg and were measured to illustrate the accuracy of the method. Two
different extraction methods were applied: MeHg was extracted from
10 mg hair sample into 5 mL 10 M HCl for 20 min at 55 °C and 20 min
at 60 °C in the microwave (CEM MARS 5, CEM Coop, USA). This acid
leaching process for MeHg was modified from literature [21,22]. The Fig. 2. Chromatogram of MeHg and Hg2+ in a river water sample spiked with 20 ng Hg/L
sample was ultra-centrifuged and 1 mL of this extract was diluted to MeHg (0.7 ng Hg as MeHg) using HPLC-CV-AFS.

50 mL with double-distilled water. The separate second extraction

was carried out in 5 mL TMAH (25% solution) for 20 min at 55 °C and
another 20 min at 60 °C in the microwave (open vessel digestion
mode). The extract was ultra-centrifuged and 1 mL of sample was dilut-
ed in water to a final volume of 50 mL and acidified with 0.55% HCl
(0.75 mL) to a pH of around 0.8.
3. Total Hg determination of spiked wastewater used for breakthrough
experiment
For the breakthrough experiment, mercury was determined in the
outflow of the preconcentration column after MeHg spiked wastewater
was passed though. These samples were analyzed for its total mercury
concentration and prepared according to the European Standard EN
13506:2001. Briefly, 15 mL water sample were oxidized with 0.5 mL bro-
mide/bromate solution (0.05 mol Br/L) and 1.25 mL HCl (37% v/v) to con-
vert all MeHg to inorganic Hg. The oxidation process was allowed to react
for at least 30 min and was then quenched by adding 0.25 mL ascorbic
acid (10% (m/v) in water). The solution was diluted to 25 mL and directly
measured with CV-AFS.
3. Results and discussion
The material used for pre-concentration is the crucial part in this in-
strumental set-up. The requirements are a specific and effective binding
to mercury, which implies that the mobile phase should elute the mercu-
ry from the material again in a considerable time for obtaining optimum
peak shape in the subsequent chromatogram. In this work, sulfur-based
materials (thioureasilica and thiolsilica) were used because sulfur is
known for a strong complex bonding to mercury. The mobile phase
1.5 mM APDC in 75% methanol was adopted from the literature [15],
but acetonitrile was replaced by methanol in order to achieve better sen-
sitivity for the AFS signal. Additionally to the elution, the mobile phase
enabled also the separation of MeHg and Hg2+ on the C8 column and a
typical chromatogram is shown in Fig. 2.
1. Recovery of MeHg as a function of pH and column material
The SPE column was filled with thiolsilica or thioureasilica respec-
tively and 1 ng Hg as MeHg as 10 mL of a 100 ng Hg/L as MeHg buffered
in a 0.1 M acetic acid/acetate (pH set using HCl) was loaded and subse-
quently eluted and the MeHg was measured. The intensities were nor-
malized and the highest intensity was set to 100%. The pH dependant
pre-concentration and elution is shown for thioureasilica and thiolsilica
in Fig. 3a, b. The highest recovery using thioureasilica was obtained for
pH 0 and the recovery dropped then linearly to a minimum at pH 3
(60 ± 13% (n = 3)). At higher pH the intensity reached up to 83 ± 1%
at pH 6. This result confirms that a breakthrough of MeHg was mea-
sured at pH 1–8 with the exception at pH 0. This means that the lower
intensity of MeHg at higher pH is the result of a lack of absorption rather
than non-elution of MeHg. The same experiment was repeated with the
thiolsilica material. Additionally, the untrapped MeHg was measured in
the waste as breakthrough. Between pH 1 and 5, no breakthrough oc-
curred and the recovery is stable within 98 ± 1%. This material showed
the lowest recovery of 21 ± 3% at pH 0 and has a broad maximum be-
tween pH 2 and 6, which however significantly decreases for pH 7
(Fig. 3b).
Both materials show complementary behavior with regards to the
pH dependant recoveries. The materials were therefore mixed in a
ratio 1:1 and the pH stability test was repeated. This mixture did not
show any breakthrough between pH 0 and 7. The recovery of MeHg
was 85 ± 2% between pH 1 to 7 of the recovery at pH 0 (Fig. 3c). The
1:1 mixture of thiolsilica and thioureasilica improves the recovery of
MeHg over a broad pH range of 0 to 7 and has one main advantage for
real samples: No buffering of water sample at a specific pH is required
and only some HCl is needed to acidify the sample slightly. Most of
the samples were prepared in 0.37% (v/v) HCl. The added chloride also
helps to prevent the adsorption of inorganic mercury (Hg2 +) since
106 C.-C. Brombach et al. / Spectrochimica Acta Part B 105 (2015) 103–108
Fig. 3a-c. Normalized intensities of 1 ng Hg as MeHg loaded as 10 mL of a 100 ng/L MeHg solution at different pHs for different absorption materials. Error bars represent ± SD (n = 3).
HgCl2−
4 is stable in solution and minimizes memory effects and carry-
over of inorganic mercury.
2. Carry-over and memory effect
A common problem with preconconcentration techniques is possi-
ble carry-over of the analyte from highly concentrated samples to low
concentrated samples. An experiment was carried out to determine
the threshold concentration at which carry-over occurs. This informa-
tion is important in order to determine when an additional blank run
should be inserted in the sample sequence. 10 mL of MeHg standards
with concentrations from 10 ng/L up to 2000 ng/L corresponding to an
amount of MeHg of 0.1 to 20 ng per were preconcentrated. After each
standard, a blank was analyzed and the peak area of MeHg in the
blank was calculated into a total amount of MeHg and plotted against
the total amount of MeHg preconcentrated in the previous run (see
Fig. 4).
Carry-over is determined above LOD only when more than 2.5 ng of
MeHg was adsorbed in the previous sample. Any acidification of the mo-
bile phase was unsuccessful for reducing this memory effect. If the sys-
tem would be automated then the sample concentration measured
0.2
0.15
Carry-over m(MeHg) / ng
0.1
0.05
-0.05
0 5 10 15
m(MeHg) / ng from previous run
Fig. 4. Carry-over of MeHg from MeHg standards into a blank, error bars represent (±SD),
n = 2.
should be used to determine whether the next sample is a new sample
or another blank or a rinsing solution such as 0.5% mercaptoethanol.
3. Optimisation of sample loading rate
Different flow rates of sample through the preconcentration column
were tested for their influence on the recovery. The recovery remained
within the method precision for flow rates from 2 to 10 mL/min
(Fig. 5). 10 mL/min is the maximum flow rate for preconcentration
with the current HPLC pump and is at the moment the limiting time fac-
tor for samples at ultra-trace level, where a preconcentration volume of
200 mL (or more) is needed. The flow-rate is limited by the backpressure
of about 20 bar at 5 mL/min. Hence, the use of an HPLC pump is manda-
tory here.
Samples of a volume up to 35 mL were routinely preconcentrated
with a flow-rate of 5 mL/min to keep the back pressure low. Sample
loading was therefore realized within 7 min. Since the elution of the
trapped mercury with the mobile phase is completed within 2 min,
the 6-port valve can be turned to the loading position after this time
and the next sample can be uploaded, while the MeHg and Hg2+ sepa-
ration is running for the next 12 min over the analytical column. This
procedure enhances the time efficiency of the method.
20 25
Fig. 5. Recovery of MeHg dependence versus the loading rate. 10 mL of a 100 ng/L MeHg
solution was preconcentrated at different flow rates and the peak area measured. Error
bars represent (±SD), n = 3.
 C.-C. Brombach et al. / Spectrochimica Acta Part B 105 (2015) 103–108 107

4. Figures of merit Table 1

Recovery ± SD (n = 3) for MeHg spiked into real water samples.

Linearity, preconcentration factors and limits of detection (LOD) Sample Recovery/%

were determined by performing a calibration in the range between Seawater spiked with 5 ng/L MeHg 98.1 ± 4.4
1 ng/L and 500 ng/L MeHg by loading a volume of 10 mL with a correla- River water spiked with 5 ng/L MeHg 92.3 ± 0.8
tion coefficient of typically 0.9998. The LOD was calculated as 8 pg Hg as Crude sewage spiked with 5 ng/L MeHg 98.6 ± 0.9
MeHg based on the 3 SD criterion of the signal noise. With 10 mL sample Seawater spiked with 10 ng/L MeHg 99.1 ± 5.5
River water spiked with 10 ng/L MeHg 97.0 ± 2.6
size, an LOD of 0.5 ng/L is achieved. The repeatability was at 2.1% (n =
Crude sewage spiked with 10 ng/L MeHg 92.5 ± 1.4
10) for a 10 mL solution of 100 ng Hg/L as MeHg. The LOD can be im- Seawater spiked with 100 ng/L MeHg 101.8 ± 4.0
proved with higher preconcentration factors; e.g. using 200 mL water River water spiked with 100 ng/L MeHg 95.9 ± 4.7
for preconcentration, a detection limit of 40 pg/L can be achieved. Fig. 6 Crude sewage spiked with 100 ng/L MeHg 91.4 ± 2.5
shows a measurement of MeHg in a water sample at ppq level
(0.04 ng/L).
All recoveries for MeHg are above 90% for the different water matri-
ces, which proves that the preconcentration is not matrix dependent. A
5. Recovery of MeHg in spiked real water samples recovery of up to 98.6% could be achieved for crude sewage, the most
challenging matrix of the three tested samples.
Three different water samples (seawater, river water and sewage
water) were chosen to test the matrix effect on the determination of
MeHg in water. Seawater is high in chloride, river water contains high 6. Validation of the method with certified reference materials
dissolved organic matter, e.g. humic acids, and crude sewage is a highly
challenging water matrix with its load of organic matter and particles. To our knowledge, no certified reference material for MeHg in water
All these matrices could possibly interfere with the preconcentration, is available. Certified reference material with certified concentrations
as these may either form complexes with mercury, or may interact for MeHg and Hg2+ to test the accuracy of the developed method was
with the preconcentration material, thus lowering the complexing effi- used instead. MeHg and Hg2+ of the two hair reference materials NIES
ciency. The different water samples were spiked with MeHg to concen- CRM No. 13 and IAEA-085 was extracted with two different methods:
trations of 5, 10 and 100 ng Hg/L and subsequently analyzed for Acid leaching and alkaline extraction with tetramethylammonium
recovery. MeHg in the unspiked samples was below the LOD for the hydroxide (TMAH). The samples were further diluted to a final concen-
preconcentrated volume of 35 mL. 35 mL sample was preconcentrated tration of approximately 300 ng/L MeHg. 10 mL of these samples were
for samples spiked with 5 and 10 ng/L MeHg while 10 mL sample for preconcentrated and compared to calibration standards for determina-
samples with 100 ng/L MeHg. The recoveries are shown in Table 1. tion of the recovery (Table 2).
The extraction of MeHg with TMAH showed better recoveries for
NIES CRM No. 13 than the acid leaching procedure. The recoveries for
the reference material IAEA-085 are around 100% for both extraction
methods, but it is worth to note that the concentration of MeHg in
this reference material is 7 times higher. These results prove the accura-
cy and efficiency of the method: A simple extraction, centrifugation, di-
lution, and acidification are the entire sample pre-treatment for the
speciation of samples.

4. Conclusion

A simple, robust on-line preconcentration method for the speciation

of mercury in water phase samples has been developed. Without
sample preparation, any acidified water sample can be measured for
its MeHg concentration in the ppq range within 20 min. The pre-
concentration is based on solid phase extraction of mercury on sulfur-
based ligands and the subsequent analysis via HPLC-CV-AFS. The meth-
od has a pH stability from 0 to 7 and acidified samples can be analyzed
directly without derivatization. The limit of detection of the method is
based on the preconcentrated volume of sample and is around 8 pg
for MeHg, which corresponds to a limit of detection of 0.04 ng/L MeHg
preconcentrated from 200 mL. Results from the validation study with
spiked water samples gave recoveries of 91–102% for different matrices.
For accuracy, the extracts of hair CRMs were analyzed and the certified
values of MeHg were determined quantitatively. In conclusion, this on-
line preconcentration HPLC-CV-AFS speciation approach for MeHg is a
simple and low cost approach which potentially can be modified for au-
tomated, ultra-trace routine analysis.

Acknowledgments

C.-Cornelius Brombach is grateful for financial support by

Fig. 6. Chromatogram of 200 mL of a blank (cyan) 0.04 ng/L MeHg (purple) is shown. It PSAnalytical, Kent, UK and the College of Physical Sciences (University
represents 8 pg Hg. of Aberdeen), to carry out his PhD project.
108 C.-C. Brombach et al. / Spectrochimica Acta Part B 105 (2015) 103–108
Table 2
Recoveries for MeHg in CRMs after 2 different digestion methods.
Human hair reference material Recovery/% after acid leaching
NIES CRM No. 13 88.6 ± 1.7
IAEA-085 97.1 ± 4.4
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