Analytica Chimica Acta 505 (2004) 247–254

Method to reduce the memory effect of mercury in the analysis of

fish tissue using inductively coupled plasma mass spectrometry
Chris F. Harrington∗ , Sheila A. Merson, Tulay M. D’ Silva
University of Leicester, Department of Biochemistry, Biocentre, University Road, Leicester, LE1 7RH, UK

Received 9 September 2003; accepted 1 October 2003

Abstract

The routine determination of mercury (Hg) by inductively coupled plasma mass spectrometry (ICP-MS) is affected by a pronounced
memory effect in the sample introduction system. This results in long washout times for the analyte, which affects the accuracy and reliability
of the analytical procedure. By using a combination of flow injection sample introduction and a sulfur-containing compound in the carrier
solution, it was possible to decrease the memory effect of mercury to that for the internal standard (rhodium). The carrier solution contained
2-mercaptoethanol (2-ME) and the developed method was evaluated using three different fish tissue certified reference materials: CRM 464
(BCR, Brussels); DORM-1; and DORM-2 (NRC, Canada). The samples were mineralized using a combination of concentrated nitric acid and
hydrogen peroxide and heating in a closed microwave oven. The developed flow injection ICP-MS procedure gave values for total mercury
in all three CRM materials in agreement with the certified concentration range. Cold vapour atomic fluorescence spectrometry (CV-AFS)
confirmed the results from the developed method. The developed flow injection method had a detection limit (defined as three times the
standard deviation of the blank concentration) for mercury of 5.1 ␮g l−1 .
© 2003 Elsevier B.V. All rights reserved.

Keywords: Flow injection; Inductively coupled plasma mass spectrometry; Total mercury; Fish tissue; Certified reference materials; Memory effect

1. Introduction cury by reduction of inorganic mercury. Thus, cold vapour

Monitoring of mercury (Hg) in the tissue of edible fish is
extremely important because consumption of contaminated
fish has caused serious neurological damage to newborn ba-
bies and adults [1,2]. Mercury tends to accumulate in fish
tissue, particularly, in the form of methylmercury, which is
about 10 times more toxic than inorganic mercury [2]. The
consumption of fish is therefore a significant exposure route
for humans to mercury and a number of regulatory organi-
zations monitor mercury levels in fish tissue on sale to con-
sumers.
A number of analytical methods can be used to measure
total mercury concentrations in a variety of different sample
matrices. The best analytical methods, in terms of the lowest
detection limit, are based on determination of elemental mer-
∗ Corresponding author. Present address: Metal Speciation and Bio-
transformation Research Group, Leicester School of Pharmacy, De Mont-
fort University, The Gateway, Leicester LE1 9BH, UK.
Tel.: +44-116-2577121; fax: +44-116-2577135.
E-mail address: charring@dmu.ac.uk (C.F. Harrington).
(CV) generation coupled to atomic fluorescence spectrome-
try (AFS) [3], atomic absorption spectrometry (AAS) [4,5],
or inductively coupled plasma mass spectrometry (ICP-MS)
[6,7], are techniques that give low limits of detection and
can easily be automated. However, these methods are also
specific to a single species of mercury and affected by the
sample matrix. This is because organomercury compounds
are not amenable to the formation of elemental mercury (the
cold vapour), so the sample preparation steps must convert
all the organomercury present in the fish tissue to a single
inorganic form. This can be facilitated by bromination of
the sample digests prior to analysis, which converts all the
organomercury compounds present to inorganic mercury.
Inductively coupled plasma mass spectrometry using
conventional sample introduction with a peristaltic pump is
widely used for the determination of trace metals in a wide
variety of different sample matrices. However, a significant
and difficult problem to overcome when using ICP-MS for
total mercury analysis is the severe memory effect that is
apparent for mercury in the instrument, which has been
attributed to a combination of sample introduction, spray

0003-2670/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2003.10.046
248 C.F. Harrington et al. / Analytica Chimica Acta 505 (2004) 247–254
chamber and nebulisation effects [8]. The consequences
of these effects include non-linear calibration graphs, long
washout times, decreasing sensitivity with time, and signals
dependent on the matrix.
A number of different approaches have been used with
ICP-MS analysis to eliminate the mercury memory effect.
For the analysis of potable water, adding gold to the samples
and standards as a stabilising agent decreased the memory
effect [9]. Other work monitoring mercury in sediments
used a combination of flow injection sample introduction
and a Triton X-100/ammonia/ethylenediaminetetracetic
acid (EDTA) carrier solution to eliminate the memory ef-
fects associated with mercury determination and to obtain
reproducible linear calibration plots [8]. This type of carrier
solution was also used for total mercury analysis of hu-
man blood, urine and nitric acid fish digests using ICP-MS
with conventional sample introduction [10]. A similar mix-
ture of reagents were added to the standards and samples
measured by conventional ICP-MS during the certification
of a cod tissue CRM (BCR CRM 422 Cod Muscle) [3].
This study showed that aqueous calibration standards do
not produce linear calibrations, resulting in low results and
that isotope dilution calibration could give a low result if
the spike material was not added prior to digestion. Deter-
mination of the total mercury in human hair and sediment
CRMs by isotope dilution ICP-MS using hydrobromic
acid as a wash step after each standard and sample pro-
duced results in good agreement with the certified reference
values [11].
The sample preparation methods used for both methylmer-
cury and inorganic mercury have been detailed in a recent
European certification [12] of the two tuna reference mate-
rials, CRM 463 and CRM 464. The most commonly used
preparation method involved acid digestion, usually nitric
acid, with heating via reflux or in a microwave oven. The
majority of the analytical methods employed involved cold
vapour generation and either atomic absorption (CV-AAS)
or atomic fluorescence (CV-AFS) detection to determine
total mercury.
This paper describes the development of a rapid and
accurate method for the determination of total mercury in
fish tissue by flow injection coupled to inductively coupled
plasma mass spectrometry (FI-ICP-MS). Flow injection
analysis was assessed because it allows for the on-line addi-
tion of the internal standard and it can be used to introduce
small aliquots of solution into the instrument. This reduces
the possibility of experiencing signal stability problems due
to deposition of the matrix from the sample digests on the
cones and limits the amount of mercury entering the system,
which helps to control the potential memory effect. Two
sample digestion methods were investigated, both based on
the use of a closed microwave oven to reduce losses of mer-
cury by volatilization. The first used nitric acid/hydrogen
peroxide, the second employed tetramethylammonium hy-
droxide. Quantitation of the total mercury present was car-
ried out using three different flow injection carrier solutions,
to determine which could be used to overcome the memory
effect of mercury. A system utilizing 2-mercaptoethanol
(2-ME) provided linear calibration graphs, without the
need to use the standard additions approach, and was
validated using three fish tissue CRMs. The results were
confirmed by using CV-AFS, both with and without bromi-
nation, which confirmed that the sample digestion method
was effective in quantitatively converting the organomer-
cury compounds present into the required inorganic
form.
2. Experimental
2.1. Reagents, standard solutions and samples
Deionized water (>18 M
) was obtained from an Elga
Maxima water purification unit (Elga, Marlow, UK). Ni-
tric acid (Ultrapure, Baker, USA), hydrogen peroxide
(Ultrapure, Romil, UK) and 25% tetramethylammonium
hydroxide (TMAH) (GPR, Aldrich, Dorset, UK), were
used for tissue digestion. Nitric acid (Ultrapure, Baker),
2-mercaptoethanol (Aldrich), Triton X-100 (BDH, Poole
Dorset, UK), ammonia (AnalaR, BDH) and ethylenedi-
aminetetracetic acid (Aldrich), were used as carrier solu-
tions. Tin(II) chloride (Analytical Reagent, Fisher Scientific,
Loughborough, UK), potassium bromide (AnalaR), potas-
sium bromate (AnalaR), and hydroxylamine hydrochlo-
ride (99%, Aldrich) were used for cold vapour generation
and bromination. Mercury, rhodium and thallium stock
standards were obtained as 1000 mg l−1 solutions (Alfa,
Johnson–Matthey, Royston, UK) and diluted as required.
The accuracy of the method was evaluated using three fish
tissue CRMs: tuna fish CRM 424 (BCR, Brussels), and dog
fish tissue DORM-1 and DORM-2 (NRC, Ottawa).
2.2. Instrumentation
The FI-ICP-MS measurements were performed using
an Elan 5000A ICP-MS instrument (Perkin–Elmer (PE),
Beaconsfield, UK). The plasma was generated using a
forward power of 1050 W and gas flow rates of: coolant
15 l min−1 ; auxiliary 0.8 l min−1 ; and nebulizer 0.9 l min−1 .
A cross-flow nebulizer and nickel sampler and skimmer
cones were used throughout the study. The flow injection
apparatus comprised a PE AS90 auto-sampler and a PE
FIAS 400, made up of two peristaltic pumps, a five-port
switching valve, and a 500 ␮l sample loop.
The CV-AFS measurements were performed using a sys-
tem comprising an auto-sampler, a continuous flow vapour
generator, a Merlin fluorescence spectrometer and a control
computer (PS Analytical, Orpington, Kent, UK).
A closed microwave system (MSP 1000, CEM, Buck-
inghamshire, UK) was used for the TMAH and nitric
acid/hydrogen peroxide sample digestions. This particu-
lar system utilizes 100 ml polyethylene vessels and the
 C.F. Harrington et al. / Analytica Chimica Acta 505 (2004) 247–254
temperature and pressure were monitored throughout the
digestion.
2.3. Sample preparation
The samples (approximately 0.5 g dry weight) were oxi-
dized in a closed microwave oven using concentrated nitric
acid (6 ml) in the first step, followed by addition of hydro-
gen peroxide (4 ml) in the next. During the first stage the
samples were heated to 100 ◦ C for 10 min. The second step
used the same parameters for 5 min. Before opening the mi-
crowave oven, the solutions were fan cooled to 30 ◦ C and
opened when the internal pressure had dissipated. The di-
gests were filtered (0.45 ␮m) and made up to a final volume
of 100 ml giving the solutions a matrix of 7% HNO3 and
2% H2 O2 . The second digestion procedure involved heating
the samples (approximately 0.5 g) with 25% tetramethylam-
monium hydroxide (6 ml) in a microwave oven for 20 min.
Once cooled, the digests were filtered (0.45 ␮m) and diluted
to 100 ml with deionised (DI) water. Once prepared, the di-
gests were stored in a refrigerator until analysed, usually
within 5 days of preparation.
2.4. Flow injection inductively coupled plasma mass
spectrometry
A simple FI system, described previously for the multi-
elemental analysis of food digests [13,14], was employed
throughout the present work. The system comprised on-line
addition to the sample of rhodium (10 ␮g l−1 ) as inter-
nal standard, a carrier solution and a 500 ␮l injection
loop. The flow rates used were: 6.1 ml min−1 for the car-
rier; 4.4 ml min−1 for the sample; and 6.9 ml min−1 for the
internal standard. The FI unit was coupled to the ICP-MS
system via a piece of 830 mm × 0.5 mm i.d. PTFE tubing.
The three different carrier solutions investigated were nitric
acid (0.1 M), Triton X-100/EDTA/ammonia (0.1/0.1/0.1%
v/v) and 2-mercaptoethanol (0.05% v/v).
2.5. Cold vapour atomic fluorescence spectrometry
(CV-AFS)
The sample digests were diluted (1 + 9) with hydrochlo-
ric acid (3 M) and 1 g of brominating agent (0.1 M potas-
sium bromide, 0.02 M potassium bromate) was added to
each aliquot and the solutions left to stand for a minimum of
30 min (in this way the organic mercury is oxidized to inor-
ganic mercury). An excess of hydroxylamine hydrochloride
was added to remove the excess bromination reagent. The
solutions were analyzed using a continuous flow vapour gen-
eration atomic fluorescence detector, utilizing tin(II) dichlo-
ride as the reducing agent. Calibration standards in the range
1–5 ␮g l−1 were prepared in the same reagent as the sam-
ples and a water proficiency testing solution (Aquacheck,
WRc, UK) was analyzed concurrently with the samples, as
a quality control check.
249
3. Results and discussion
3.1. The mercury memory effect
To demonstrate exactly what form the memory effect takes
when nebulising a mercury solution through a double pass
Scott-type spray chamber, a 5 ␮g l−1 mercury(II) chloride
standard made up in water was continuously aspirated into
the ICP-MS instrument. The mercury response gradually in-
creases with time and does not achieve a maximum (Fig. 1).
A solution of mercury(II) chloride at the same concentration
was made up in 2-mercaptoethanol (0.05%) solution and as-
pirated for the same time period. The mercury signal in this
case does reach a maximum, before returning to the baseline
fairly rapidly after aspiration has ceased (Fig. 1). This clearly
illustrates how effective the addition of 2-mercaptoethanol
can be in eliminating the memory effect for mercury in the
ICP-MS sample introduction system at this concentration
level.
3.2. Choice of a suitable internal standard
The use of internal standardization can improve analyti-
cal figures of merit such as precision and accuracy, and its
implementation using a FI approach is simple and robust.
The element to use as an internal standard should behave
in the instrument as similarly as possible to the analyte
of interest. Two candidate internal standards, rhodium and
thallium were assessed by comparing calibration linearity
for the three candidate carrier solutions described below
(Section 3.3). Rhodium was considered because of its pre-
vious successful use by us in the multielemental analysis of
food samples [13,14] and thallium because of its similar-
ity in mass number to mercury, which has been shown to
improve precision [15].
The results from these studies (not reported) showed that
Rh gave better calibration linearity and short-term precision
than Tl, may be because Rh has a first ionisation potential
closer than Tl to that of Hg [16]. The internal standard used
in the evaluation of carrier solutions and for method vali-
dation was Rh at a concentration of 10 ␮g l−1 which was
added on-line to the samples and standards.
3.3. Evaluation of different carrier solutions
Triton X-100/ammonia/EDTA solution has been used pre-
viously as a carrier of analysis for total mercury in biofluids
by conventional ICP-MS [10] and as a diluent in the de-
termination of mercury in sediments by FI-ICP-MS [8] and
fish by conventional ICP-MS [3]. Nitric acid has been used
as a carrier solution for the determination of organomercury
in biological reference materials by FI-ICP-MS [17]. The
use of these two carrier systems was compared to the use of
2-mercaptoethanol (0.05% v/v) solution, to determine which
overcame the mercury memory effect most effectively. This
was assessed and compared for all three carrier systems by
250 C.F. Harrington et al. / Analytica Chimica Acta 505 (2004) 247–254
Fig. 1. Mercury signals for continuously aspirated 5 ng g−1 standards made up in deionised (DI) water or 2-mercaptoethanol (2-ME) solution.
evaluating the mercury and internal standard peak shapes,
the calibration linearity, the short-term precision and the
detection limit (defined as three times the standard devia-
tion of the blank concentration), for standards in the range
1–40 ␮g l−1 .
The highest peaks for mercury were obtained using the
nitric acid carrier. The detection limit was 0.8 ␮g l−1 , which
was the lowest for the three methods tested. However, the
calibration linearity was not so satisfactory (r 2 = 0.975,
n = 5) and the short-term precision for three injections
of a 40 ␮g l−1 standard was the poorest of the three sys-
tems investigated (CV = 9.5%). The mercury peak profiles
(Fig. 2a) for the three injections tailed badly, the signal did
not reach the baseline before the next injection, and each
subsequent injection showed greater signal intensity than the
previous one. The recovery for a 10 ␮g l−1 check standard
was repeatedly below the required quality control limit of
90%, indicating problems with calibration stability. These
observations are characteristic of the mercury memory ef-
fect and indicate that nitric acid is not a suitable carrier for
the determination of mercury at this concentration level.
Nitric acid has been reported previously as a carrier so-
lution for the determination of organomercury in biological
reference materials using FI-ICP-MS [17]. In that work no
memory effect was reported, or is evident in the peak profiles
presented, presumably because cysteine acetate is present in
the sample solutions as a residue from the sample extrac-
tion method used. However, a method for the determination
of mercury in potable water showed that conventional anal-
ysis of a potable water sample spiked at a concentration of
1 ␮g l−1 with mercury, gave a short-term precision (CV) of
22% for 10 replicate injections using nitric acid as the car-
rier [9]. The authors felt that this method did not satisfy
the analytical performance criteria of the United Kingdom
Drinking Water Inspectorate (DWI).
The use of Triton X-100/EDTA/ammonia (0.1/0.1/0.1%
v/v) solution as the FI carrier produced the peak profiles
shown in Fig. 2b. Tailing was observed for the mercury peaks
and the signal only just returns to the baseline before the
next replicate is added. In most cases, the figures of merit
are the same as with the nitric acid carrier: the calibration is
very close to a straight line (r 2 = 0.999, n = 5); the detec-
tion limit is higher (8.7 ␮g l−1 ); but the short-term precision
is about the same (CV = 9.1%). In previous work using
this solution as a diluent for the determination of mercury
in sediments [8] and fish tissue [3], the use of standard ad-
ditions combined with internal standardization was required
to overcome the matrix effects and provide linear calibration
graphs.
The use of 2-mercaptoethanol was suggested after it was
shown to improve the liquid chromatographic properties of
organomercury compounds and eliminate injection problems
encountered with liquid chromatography-ICP-MS [18]. A
0.05% (v/v) solution of 2-mercaptoethanol was used as the
carrier, it generated the smallest mercury peaks of the three
carrier solutions evaluated (Fig. 2c). The reason for this is
unclear at present. However, the peak profiles were more
acceptable for quantitation, because the analyte signal re-
turns to the baseline level at the same time as the internal
standard (rhodium 10 ␮g l−1 ). The figures of merit were sat-
isfactory for routine applications: the calibration was linear
(r2 = 0.999, n = 5); the detection limit was 5.1 ␮g l−1 ; and
the short-term precision was the lowest (CV = 6.7%) of the
three carriers.
 C.F. Harrington et al. / Analytica Chimica Acta 505 (2004) 247–254 251

Fig. 2. (a) Signal profile for three replicate injections of a 40 ng g−1 standard of inorganic mercury mixed on-line with rhodium internal standard, using
nitric acid (0.1 M) as carrier. (b) Signal profile for three replicate injections of a 40 ng g−1 standard of inorganic mercury mixed on-line with rhodium
internal standard, using Triton 100-X, EDTA and ammonia solution as carrier. (c) Signal profile for three replicate injections of a 40 ng g−1 standard of
inorganic mercury mixed on-line with rhodium internal standard, using 2-mercaptoethanol solution as carrier.
252 C.F. Harrington et al. / Analytica Chimica Acta 505 (2004) 247–254
Fig. 2. (Continued ).
The peak profile for the internal standard (Rh) using any
of the three of the different carriers shows a characteristic
negative response at the start and end of each peak. This
results from a segmented flow of Rh introduced into the
system when the two-way switching valve moves between
the open and closed positions. This has been observed in
other studies using the same FI set-up [13,14].
3.4. Development of a suitable sample digestion procedure
For quantitative recovery of the total mercury from the
fish tissue matrix, the material needs to be completely sol-
ubilized by the digestion reagent. Two different reagent
systems with closed microwave heating were evaluated. A
second requirement for full quantitative analysis is that all
the organomercury compounds present in the sample are
converted to the inorganic form. This is necessary because
it has been reported that the chemical form of mercury in
solution influences the final quantitative result when using
ICP-MS analysis [3]. This conversion was confirmed by
CV-AFS once the most appropriate digestion procedure
had been established. The use of a closed microwave sys-
tem allowed for rapid heating of the digestion vessels and
mitigated against any loss of volatile mercury containing
species during sample preparation.
Three fish tissue certified reference materials represent-
ing high and low total mercury content (DORM-2, TUNA
464 and DORM-1, respectively) and two different fish
species (dogfish (DORM-1 and 2) and tuna (TUNA 464))
were investigated using two reagent systems. The first sys-
tem evaluated used TMAH (25% v/v) solution and has
been successfully used by other workers for the quantitative
extraction of mercury and methylmercury from fish tissue
using open focused microwave assisted digestion [5]. The
second reagent system investigated forms part of the routine
analytical protocol in our laboratory for the determination
of trace metals in food and has also been used for the de-
termination of total mercury in sediments using an open
focused microwave assisted digestion [8]. In this two-step
approach, concentrated nitric acid is used initially followed
by hydrogen peroxide.
Digestion with TMAH and analysis by FI-ICP-MS
yielded recoveries of 75–91% (Table 1) for the three CRMs
compared to the certified mean values. Only the result for
DORM-2 was in agreement with the certified range. The
precision for the analysis of three replicate digests of the
same material was <10% for DORM-2 and TUNA 464, but
for the lower concentration DORM-1 material, the precision
was 15%. The exact reason for the low recovery for mercury
when analysing the TMAH digests using the FI-ICP-MS
method is not clear. Further analysis of the same digests
using the CV-AFS method gave acceptable results (not
shown), so the difference is unlikely to be due to inefficient
digestion. The probable cause is an interaction between the
TMAH in the digest and the 2-mercaptoethanol used as the
carrier, which either reduces the effectiveness of the carrier
 C.F. Harrington et al. / Analytica Chimica Acta 505 (2004) 247–254 253

Table 1
Analysis of fish tissue CRM digests by flow injection inductively coupled plasma mass spectrometry, after tetramethylammonium hydroxide digestion in
a closed microwave oven (n = 3)
CRM Mean concentration (mg kg−1 ) Standard deviation (mg kg−1 ) CV (%) Certified range (mg kg−1 ) Recovery (%)

DORM-1 0.60 0.09 15 0.724–0.872 75

DORM-2 4.24 0.20 5 4.38–4.90 91
TUNA 464 4.36 0.30 7 5.14–5.34 83

Table 2
Analysis of fish tissue CRMs by flow injection inductively coupled plasma mass spectrometry, after nitric acid/hydrogen peroxide digestion in a closed
microwave oven (n = 3)
CRM Mean concentration (mg kg−1 ) Standard deviation (mg kg−1 ) CV (%) Certified range (mg kg−1 ) Recovery (%)

DORM-1 0.73 0.05 7 0.724–0.872 91

DORM-2 4.46 0.18 4 4.38–4.90 96
TUNA 464 4.98 0.20 4 5.14–5.34 95

in decreasing the memory effect or facilitates formation of
a different mercury species, which behaves differently to
the standard.
The recoveries for all three CRM materials digested
by heating in a closed microwave oven with nitric acid/
hydrogen peroxide (Table 2), followed by analysis using
FI-ICP-MS, were between 91 and 96%, compared to the
mean certified values. All three of the determined mercury
concentrations agreed with the certified range for each ma-
terial, indicating complete recovery of the total mercury
present in the samples. The precision for three replicate di-
gests was better than 10% for each material. The signal peak
profiles for analysis of the DORM-1 digest using the devel-
oped FI-ICP-MS method are shown in Fig. 3. The profile
for mercury is similar to that for the internal standard and
the mercury signal returns to the baseline rapidly after each
of the three injections, indicating that the memory effect has
been eliminated. The three injection replicates also show
good short-term repeatability. Analysis of the same digests
using the CV-AFS system produced very similar recoveries
(Table 3) for the DORM-2 and TUNA 464 materials, but a
much higher recovery for the low-level DORM-1 CRM.

Fig. 3. Signal profile for a nitric acid/hydrogen peroxide digest of DORM-1 fish tissue CRM, with on-line addition of internal standard (Rh).
254 C.F. Harrington et al. / Analytica Chimica Acta 505 (2004) 247–254
Table 3
Analysis of fish tissue CRMs by cold vapour atomic fluorescence spectrometry after nitric acid/hydrogen peroxide digestion in a microwave oven
CRM Bromination Mean concentration Standard deviation
(mg kg−1 ) (mg kg−1 )
DORM-1 No 0.97 0.03
DORM-2 No 4.38 0.11
TUNA 464 No 5.06 0.15
DORM-1 Yes 0.99 0.04
DORM-2 Yes 4.68 0.18
TUNA 464 Yes 5.06 0.19
Digests brominated or unbrominated prior to analysis (n = 3).
3.5. Evaluation of the developed protocol
The nitric acid/hydrogen peroxide, closed microwave di-
gestion method was shown to be compatible with the devel-
oped FI-ICP-MS system and so was adopted for use. The
digestates were also brominated prior to CV-AFS analysis,
to check whether the digestion step had completely oxidized
the methylmercury present to inorganic mercury. The results
(Table 3) were exactly the same as without bromination, in-
dicating that the digestion step had fully converted all the
mercury species present to the inorganic form.
The developed FI procedure allows for the routine use
of ICP-MS for the determination of mercury in fish tis-
sue samples and requires no further sample manipulation
than that which is required for conventional trace metal
analysis of food samples. It could be possible to add
the sulfur-containing ligand directly to the samples and
standards and run the system as a conventional ICP-MS
method. However, this would require extra sample ma-
nipulation, would entail the continuous aspiration of the
sulfur-containing compound into the instrument and may
not overcome the memory effect of high concentrations of
mercury that could be present in some samples. The use
of FI allows for rapid sample analysis, on-line addition of
an internal standard and reduces the amount of mercury
entering the ICP-MS system.
The limit of detection (LOD, 5.1 ␮g l−1 ) established for
this method is in agreement with that reported for the deter-
mination of mercury in sediment (10 ␮g l−1 ) using FI and a
similar instrument [8]. This could be improved to an LOD of
0.1 ␮g l−1 using cold vapour generation and detection using
the same make and model of instrument [6]. The use of iso-
tope dilution in conjunction with cold vapour ICP-MS would
be expected to give the lowest LOD because of the measure-
ment of isotope ratios across the peak, and this approach
achieved a 70 times improvement in the LOD (0.07 ␮g l−1 )
[7].
4. Conclusions
A simple, fast and effective FI-ICP-MS method was devel-
oped, which allows for the production of linear calibration
graphs using only the on-line addition of an internal standard
CV (%) Certified range Recovery (%)
(mg kg−1 )
3 0.724–0.872 122
3 4.38–4.90 94
3 5.14–5.34 97
4 0.724–0.872 124
4 4.38–4.90 101
4 5.14–5.34 97
(rhodium; 10 ␮g l−1 ), rather than the more time-consuming
standard additions calibration method. The protocol used
2-mercaptoethanol (0.05% v/v) solution as the flow injec-
tion carrier and a nitric acid/hydrogen peroxide digestion
method, which was applicable to fish tissue samples contain-
ing low (DORM-1) and high (DORM-2, TUNA 464) levels
of total mercury.
Acknowledgements
The work described in this report was supported under
contract with the UK Department of Trade and Industry, as
part of the National Measurement System Valid Analytical
Measurement (VAM) Programme.
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