Microchemical Journal 98 (2011) 129134

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Microchemical Journal
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m i c r o c

Tartaric acid extraction of organotin compounds from sediment samples

Marcos Flores a,, Manuel Bravo b, Hugo Pinochet b, Paulette Maxwell c, Zoltn Mester c
a
b
c

Departamento de Ciencias Bsicas, Universidad Santo TomasTalca, Avenida Carlos Schorr 255, Talca, Chile
Laboratorio de Qumica Analtica y Ambiental, Instituto de Qumica, Ponticia Universidad Catlica de Valparaso, Avenida Brasil 2950 Valparaso, Chile
Institute for National Measurement Standard, National Research Council Canada, Ottawa, Ontario, Canada K1A 0R6

a r t i c l e

i n f o

Article history:
Received 10 December 2010
Accepted 14 December 2010
Available online 29 December 2010
Keywords:
Focused microwave extraction
Butyltin compounds
Sulfur interferences
Selective extraction
Solid environmental samples

a b s t r a c t
A new extraction method for the determination of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) in
sediments based on extraction with tartaric acid and methanol has been developed. Tin species were extracted
from sediment samples using focused microwave technology, then ethylated with sodium tetraethylborate
(NaBEt4) and analyzed by isotope dilution (ID) gas chromatographymass spectrometry (GC-MS). The
advantages of such methodology in comparison with other established extraction methods for the routine
speciation analysis of organotin compounds are discussed with respect to sulfur interferences co-extracted from
complex matrices.
Interferences from elemental sulfur are normally found with acetic acid extraction, but with tartaric acid
extraction these interferences were eliminated, demonstrating selective extraction.
The accuracy of the analytical procedure was established by analyzing a certied reference material (CRM)
(PACS-2, marine sediment) and comparing the results to the certied values. Good agreement between
determined and certied values for butyltin compounds was obtained. Finally, some complex sediment samples
collected from San Vicente's Bay, Chile, were analyzed with the proposed methodology, demonstrating its
potential value for monitoring butyltins in environmental samples with high concentrations of sulfur
compounds.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Aquatic pollution by organic compounds of Sn (IV) (OTCs) is a
serious concern in many countries, because OTCs are toxic and persist
in aquatic ecosystems particularly in sediments where they are
concentrated [1]. The use of OTCs, particularly tributyltin (IV) (TBT),
as an additive in antifouling paints has been mainly responsible for
their widespread introduction into the aquatic environment [2].The
toxicity of organotin compounds depends on the number and nature
of the organic groups. Trialkyltin compounds (R3SnX) are much more
toxic to mammals and aquatic organisms than monoalkyltin compounds (RSnX3) [3].
Many analytical procedures have been reported over the years for
the determination of TBT and its degradation products [4]. Most of
them combine a separation technique such as gas chromatography
(GC), with selective detectors such as atomic absorption spectrometry
(AAS), atomic emission spectrometry (AES), mass spectrometry (MS),
ame photometric detection (PFD), or pulsed ame photometric
detection (PFPD) [5,6].
For less specic detectors, such as PFPD or PFD, high concentrations of
sulfur and/or organosulfur compounds present in some environmental

Corresponding author. Tel.: +56 71 342418.

E-mail address: marcosores@santotomas.cl (M. Flores).
0026-265X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2010.12.006

samples such as sediments can produce interferences which inuence

organotin determination [710]. Cai et al. [11] reported alkyl sulde
interferences in the determination of OTCs by Grignard alkylation and gas
chromatographymass spectrometry (GC-MS) in the scan mode. It is
clear that an effective method to eliminate and/or decrease elemental
sulfur and organosulfur compounds would benet these analyses.
Extraction is usually performed by mechanical agitation/shaking
[12], reux [13], sonication [14], accelerated solvent extraction (ASE)
[15] or microwave assisted methods [16].
Major efforts to decrease the presence of sulfur interferences have
been focused on the development of desulfurization procedures,
including the use of activated copper, oxidation by dimethyldioxirane
(DMD), absorption by Al2O3 and the addition of a derivatization step
[1722]. The elimination of sulfur compounds can be accomplished
during the extraction step using pressurized liquid extraction (PLE)
[23] but this is an expensive technique for many laboratories and low
recoveries for MBT have been observed.
Over the last 20 years, extraction methods using non-polar solvents,
non-polar solvents plus acid, polar solvents, and supercritical uids [6]
have been reported. Typically, the extraction studies have been focused
on the improvement of extraction efciency for the various organotin
compounds; however, little effort has been dedicated to improving the
selectivity of the extraction process.
The objective of this work was to develop a simple selective
extraction method based on tartaric acid and methanol for butyltin

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M. Flores et al. / Microchemical Journal 98 (2011) 129134

compounds in complex sediment samples to be used as a routine

procedure and compare it with traditional acetic acid extraction. A
National Research Council of Canada (Ottawa, Ontario, Canada) PACS-2
Sediment certied reference material (CRM), certied for mono-, di-,
and tributyltin content, was analyzed to assess the accuracy, precision
and utility of the extraction method. The new extraction protocol was
then applied to sulfur-containing sediment samples collected in San
Vicente's Bay, Chile.
2. Experimental section
2.1. Instrumentation
For the analysis of organotin compounds. A Hewlett Packard HP
6890 (Agilent Technologies Canada Inc., Mississauga, ON, Canada) gas
chromatograph tted with a DB-5MS capillary column from Agilent
J&W Scientic (30 m 250 m i.d. 0.25 m coating) was used for the
separation of the organotin species. Detection was achieved with a
mass selective detector (MS) HP model 5973 (Agilent Technologies
Canada Inc., Mississauga, ON, Canada). Typical GC/MS operating
conditions are presented in Table 1.
A Discover focused microwave system, with an Explorer autosampler
system (CEM, Matthews, NC, USA) was used to extract the organotin
species from the solid samples.
2.2. Reagents and standard solutions
The organotin standards, monobutyltin trichloride (MBT, 95%),
dibutyltin dichloride (DBT, 97%), tributyltin chloride (TBT, 96%) and
tripropyltin chloride (TPrT, 98%) were purchased from Alfa Aesar (Ward
Hill, USA). Organotin standard stock solutions (5000 mg L1 as Sn) were
prepared in methanol and kept refrigerated until used. Working
standard solutions (5 mg L 1 as Sn) were prepared from stock standard
solutions by dilution in high-purity deionized water (DIW) obtained
from a Nanopure mixed bed ion exchange system fed with reverse
osmosis domestic feedwater (Barnstead/Thermolyne Corp., IA, USA). All
standards were stored in the dark at 4 C.
Methanol, ammonia, elemental sulfur (S8, 97%), acetic acid, and
tartaric acid were purchased from Sigma-Aldrich (Oakville, ON,
Canada). Tartaric acid solutions (0.5 M) containing 20% methanol
were prepared weekly by dilution in DIW. Optimization of the tartaric
acid/methanol extraction was previously developed for mechanical
shaking and later adapted for the microwave system [24].
Sodium tetraethylborate (NaBEt4) was purchased from Strem
Chemicals (Newburyport, USA). NaBEt4 was dissolved in DIW daily to
provide a 2% (wt/v) ethylating solution. A 2 M sodium acetate (Fisher
Scientic, Nepean, ON, Canada) buffer was prepared by dissolving
65 g of sodium acetate in 400 mL DIW and 25 mL glacial acetic acid.
The pH was adjusted to 5 with glacial acetic acid.
117
Sn-enriched for TBT and DBT stock solution (97% purity) with
isotopic composition and uncertainties provided at a nominal concentration of 100 mg kg1 in methanol was provided by LGC Inc.
Table 1
GC-MS operating conditions.
Column

DB-5MS: 30 m 0.25 mm i.d, 0.25 m df

Injector system
Injector temperature
Carrier gas: ow rate
Transfer line temperature
MS
SIM parameters

Split/splitless injector, splitless mode

250 C
Helium: 1.2 mL min1
290 C
HP model 5973 mass selective detector
Measured ions: m/z 179, 263 and 291; dwell times:
100 ms for each m/z
150 C
250 C

MS quad temperature
MS source temperature

(Teddington, UK). A working standard solution containing 0.79 mg L1

(as Sn) of TBT and 0.91 mg L1 (as Sn) of DBT were prepared by
volumetric dilution of the stock in methanol. The concentrations of the
117
Sn-enriched spike were quantied by reverse-spike isotope dilution
(ID) against high-purity natural abundance of TBT and DBT standards.

2.3. Analytical procedures

2.3.1. Sampling and sample treatment
The samples were collected on the coastline of Chile and consisted of
sediments. Surface sediments (10 cm depth) were acquired with a
BiergeEkman dredge (151515cm). Approximately 3 kg of sediment
was collected from each site and placed in a polycarbonate bottle. The
samples were stored frozen at 20 C and lyophilized. The dried samples
were sieved to 1 mm. The fractions b1 mm were stored at 20 C prior to
analysis.

2.3.2. Extraction from sediment samples

The focused microwave system operating conditions were as
follows [16]. Briey, 500 mg of sediment sample was placed in a glass
microwave vial and 5 mL of extractant solution, either acetic or
tartaric acid, was added. The vial was placed in the autosampler and
the focused microwave extraction was performed over 4 min.
Maximum irradiation power was set to 200 W, and the hold
temperature was 100 C. The sample was then cooled to room
temperature and the vials were centrifuged at 2000 rpm for 10 min.

2.3.3. Sample preparation for PACS-2 using a standard addition method

An internal standard, 100 L of 5 mg L1 TPrT, was added to each
500 mg subsample of PACS-2. Extractant (5 mL), either glacial acetic
acid or tartaric acid, was added to the sample. OTC standards were
added to one set of PACS-2 samples before extraction and to a second
set of PACS-2 samples after extraction, i.e., into the acetic acid or
tartaric acid extract. Focused microwave extraction was performed as
described previously for 4 min at a maximum power of 200 W.
Following centrifugation, the acidic supernatant was transferred to a
sample vial for derivatization.

2.3.4. Sample preparation for PACS-2 using isotope dilution (ID)

The sample preparation for PACS-2 using isotope dilution was
carried out as reported elsewhere [25]. In this experiment three
blanks and six samples of PACS-2 were prepared at the same time. The
PACS-2 sediments were spiked with solutions containing di- and
tributyltin enriched in 117Sn. Acetic or tartaric acid was added and the
samples were placed in the microwave system at a maximum power
of 200 W for 4 min. After derivatization, isotope ratios were measured
by GC-MS and the ratios of intensities at m/z 235 and 232 were used
for quantication of TBT and DBT in PACS-2. The equations used for
these calculations are reported elsewhere [2628].

2.3.4.1. Derivatization and extraction by isooctane prior to analysis. All

samples were derivatized prior to analysis. The derivatization step
involves the ethylation of organotin compounds to obtain thermally
stable volatile tetra-substituted species for GC separation [29]. Briey,
2 mL of sediment extract was placed in a glass vial. TPrT was added as
an internal standard (I.S.). The ethylation reaction was performed in
10 ml of buffer (pH 5), to which 5 mL of ammonia, 1 mL of NaBEt4
(2%), and 2 mL of isooctane were added. After manual shaking for
5 min, the vial was centrifuged for 10 min, allowing separation of
phases. The isooctane layer was then transferred to a 2 mL glass vial
and 2 L of the organic phase was injected onto the head of the GC
column for analysis.

M. Flores et al. / Microchemical Journal 98 (2011) 129134

3. Results and discussion

3.1. Selection of extractant solution
To develop a method for the extraction of organotin compounds
from sediments, several parameters which may affect performance
must be considered. These parameters include stability of the
analytes, extraction efciency, selectivity for the target analytes,
formation of stable complexes [30], and especially co-extraction of
interfering compounds from complex matrices such as the sediments
examined in this study.
No degradation products were observed when butyltin standards
were submitted to tartaric or acetic acid extraction procedures.
3.1.1. GC-MS study
The determination of OTCs in complex environmental matrices
following derivatization with NaBEt4 can suffer from the presence of
interferences such as sulfur and organosulfur compounds which are
often present in sediment samples. Such interferences may result in
unsatisfactory chromatographic resolution when non-element or mass
specic detectors are used [10]. In order to study this problem during
the derivatization procedure for sediment extracts, elemental sulfur was
added to both extracting liquids. Acetic and tartaric acids (5 mL) were
spiked with 1 mg each of elemental sulfur to mimic the extraction
procedure. The inuence of the added sulfur was evaluated to determine
the advantages of tartaric acid as compared to acetic acid for the
extraction of sediments with a high sulfur content. Each spiked
extracting liquid (2 mL) was subjected to the derivatization procedure.
Typical GC-MS chromatograms are shown in Fig. 1. Fig. 1A shows the
total ion chromatogram (TIC) of the derivatized acetic acid extract and
Fig. 1B shows the TIC of the derivatized tartaric acid extract. Several
compounds were identied by comparing the mass spectra with those
in the NIST library, as well as with the spectra recorded on the same

Fig. 1. Typical chromatograms obtained by GC-MS in full-scan mode of (A) an ethylated

sulfur spiked acetic acid extract and (B) a tartaric acid extract.

131

instrument by subjecting known standards to chromatography under

the same conditions. Four intense peaks due to sulfur compounds were
found in the chromatogram of the acetic acid extract.
Potential sulfur-containing molecular ions at m/z 154, 186, 256,
and 192 were found in the acetic acid extract by extracting the ions
from the full-scan chromatogram. Fig. 2 shows the extracted ion
chromatograms of m/z 154, shown in panel A and m/z 186, shown in
panel B. These ions are attributed to organosulfur compounds. The
intensity of these ions was dramatically decreased in the tartaric acid
extract, as compared to the acetic acid extract. For the rst three
molecular ions, identical mass spectra were previously found in
sediment extracts from San Vicente's Bay, Chile [10]. In Fig. 3A, the
peak eluting at 7.4 min can be attributed to diethyltrisulphide (Et2S3),
m/z 154. The peak eluting at 10.9 min in Fig. 3B is particularly
interesting because its retention time is very close to that of DBT. This
peak was attributed with high probability to diethyltetrasulde
(Et2S4) m/z 186. A third peak RT 13.5 min (m/z 192) was attributed
to the molecular ion of elemental sulfur (s6). The peak at RT 18.6 min
(m/z 256) was also attributed to the molecular ion of elemental sulfur
(s8). For elemental sulfur, an equilibrium exists among the forms
consisting of 6, 7 and 8 sulfur atoms and S6 is more stable in solvents
with a low value of the dielectric constant than in solvents with a high
value of the dielectric constant such as acetic acid [31].
High concentrations of these compounds could lead to misinterpretation of data, because the retention times for OTCs are close to them,
8.3 min for MBT, 9.2 min for TPrT, 10.5 min for DBT, and 12.3 min for
TBT. This is particularly true for DBT with a retention time of 10.5 min as
compared to 10.9 min for diethyltetrasulde (Et2S4).
Based on these results, the tartaric acid extraction method is the
most selective and it was therefore applied to the samples collected in
San Vicente's Bay, Chile (Fig. 4).

Fig. 2. Extracted ion GC-MS chromatograms of an ethylated acetic acid extract spiked
with elemental sulfur. Panel A shows the extracted ion chromatogram of m/z 154 and
panel B shows the extracted ion chromatogram of m/z 186.

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M. Flores et al. / Microchemical Journal 98 (2011) 129134

Fig. 3. EI-MS spectra obtained by GC-MS from elemental sulfur spiked acetic acid extract: (A) diethyltrisulphide and (B) diethyltetrasulphide.

3.2. Analytical gures of merit

It was observed that the extraction efciencies for the organotin
species MBT, DBT and TBT were 45, 73 and 50% for tartaric acid and 82,
100 and 60% for acetic acid, respectively. The comparison of the two
extraction methods shows that the acetic acid extraction resulted in a
more efcient extraction of the organotin, but the extraction
efciencies observed for tartaric acid for all three organotin species
are sufcient to obtain accurate quantitative results.
LOD, LOQ and precision were compared for the two extraction
methods. Precision was calculated from repeated measurements of
the relative integrated response for each OTC and TPrT (normalized to
the TPrT internal standard). The results are presented in Table 2.
The linear response for both extraction methods ranged from LOQ
to 50gL-1.
Generally, the analytical performances (LOD or LOQ) of both
extraction methods are very similar, no statistically signicant
difference appears except for MBT. This is expected since MBT is the
most polar of the OTCs and is expected to have a lower solubility in

less polar solvents resulting in a higher LOD and LOQ for the method
based on tartaric acid. The LOD values obtained in this work are
acceptable for the determination of butyltin species in highly
contaminated sediments.
The repeatability (evaluated by relative standard deviation, RSD) of the
whole analytical process, i.e. from the extraction procedure to analysis,
ranges from 2 to 6% for acetic acid depending on the species and from 7 to
8% for tartaric acid. Both methods lead to satisfactory extraction
repeatability. However, the tartaric acid extraction was expected to
Table 2
Comparison of analytical performance as a function of extraction method (LOD and LOQ in
ng(Sn)L1).
Acetic acid

TBT
DBT
MBT

Tartaric acid

LOD

LOQ

R2

LOD

LOQ

R2

52
42
43

120
93
95

0.9998
0.9992
0.9990

55
36
116

138
80
270

0.9995
0.9995
0.960

M. Flores et al. / Microchemical Journal 98 (2011) 129134

exhibit poorer repeatability because it has a high water content and hence
the OTCs are less soluble in this extracting liquid. Finally in both methods
the highest value for repeatability was for DBT.
The quantication based on acetic acid extraction seems to have
better precision for the TBT and MBT species as estimated by R2.
3.3. Quantication of TBT, DBT and MBT in PACS-2 sediment CRM using
standard addition calibration and acetic and tartaric acids extractions
The accuracy of the analytical procedure has been evaluated by
analyzing a certied reference material.
The focused microwave extraction method using acetic or tartaric
acid and a GC/MS analytical method were applied to the determination
of OTCs in PACS-2 using a standard addition technique for quantication. TPrT was used as an internal standard. The mass selective detector
was used in single ion monitoring mode (SIM). Mass-to-charge ratios
179 for MBT, 249 for TPrT, 263 for DBT and 291 for TBT exhibited the best
signal-to-noise ratio and were monitored for all measurements. The
results are presented in Table 3. Excellent agreement with the certied
values for DBT and TBT was obtained for both extraction methods;
however, the acetic acid extraction for the MBT produced a signicantly
lower concentration than the certied value. This is might be due to low
extraction efciency.
3.4. Quantication of TBT and DBT in PACS-2 sediment CRM by isotope
dilution with acetic and tartaric acid extractions
Since the accuracy and precision provided by ID methods allows
control of every single speciation analysis step independently, even
possible loss of substance of the isotope-diluted sample will have no
inuence on the nal result [32]. The concentrations of TBT and DBT
are presented in Table 4. Good agreement with the certied values
was obtained for both TBT and DBT using both acetic acid and tartaric
acid extraction protocols.

133

Table 4
Concentration of TBT and DBT in certied reference material (PACS-2 marine sediment)
determined by isotope dilution using GC/MS in SIM mode for acetic acid (A) and tartaric
acid (B) extractions.
Concentration (g(Sn)g1 (dry mass) a)

A
B
Certied value
a

DBT

TBT

1.129 0.015
1.133 0.031
1.047 0.064

0.871 0.023
0.846 0.018
0.890 0.105

Standard deviation (n = 6).

Table 5
Determination of MBT, DBT and TBT in samples from San Vicente Bay by liquidliquid
extractionGCMS.
Sample

SA
S1
a

Concentration (g(Sn)g1 (dry mass) a)

MBT

DBT

TBT

0.301 0.04
0.09 0.02

0.447 0.03
0.139 0.03

1.024 0.17
0.291 0.05

Standard deviation (n = 4).

therefore, these procedures were applied to real samples with high

concentrations of sulfur and organosulfur compounds, as reported
earlier [10]. These samples were collected in San Vicente's Bay, Chile.
The sample quantied previously for butyltin species (SA) was
studied to evaluate the selective extraction for sulfur and organosulfur
compounds. The extractions were performed for tartaric and acetic
acid. Typical GC-MS chromatograms are shown in Fig. 4. Fig. 4A shows
the (TIC) of the derivatized acetic acid extract and Fig. 4B shows the
TIC of the derivatized tartaric acid extract.

3.5. Application
3.5.1. Quantication of OTCs in sediment samples
Butyltin species were measured in two surface sediment samples, SA
and S1, collected from Chile's San Vicente's Bay. Results obtained in this
study are presented in Table 5. All three OTCs were found in the analyzed
samples. In both samples, the TBT concentration was higher than that
observed for DBT and MBT. It may be that the higher TBT concentrations
are a result of the continuous discharge of this contaminant, especially
from the port on the bay. Concentration values (ppm range) obtained in
this work are in good agreement with the values reported by other
authors for the same bay [12]. Stuer-Lauridsen and Dahl [33] have
proposed that when the concentration ratio TBT/DBT is more than 1.5 the
site may be considered highly contaminated. Applying this criterion, both
sediments from San Vicente bay are highly contaminated.
3.5.2. Evaluation of complex matrix effects
The main advantage of the tartaric acid extraction method is the
selectivity of the extraction compared to the acetic acid extraction;
Table 3
Concentration of TBT, DBT and MBT in certied reference material (PACS-2 marine sediment)
determined by standard addition using GC/MS in SIM mode for acetic acid (A) and tartaric
acid (B) extractions.
Concentration (g(Sn)g1 (dry mass) a)

A
B
Certied
a
b

MBT

DBT

TBT

0.303 0.150
0.647 0.174
0.6b

1.079 0.240
1.018 0.124
1.047 0.064

0.846 0.018
0.865 0.038
0.890 0.105

Standard deviation (n = 4).

Certied value.

Fig. 4. Typical chromatogram obtained by GC-MS in full-scan mode of (A) an ethylated

acetic acid extract and (B) tartaric acid extract from sample SA.

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M. Flores et al. / Microchemical Journal 98 (2011) 129134

Note that the intensity of several signals is dramatically decreased

in the tartaric acid extract, as compared to the acetic acid extract of a
real sediment sample, SA.
Acknowledgements
M. Flores acknowledges the doctoral fellowship from the CONICYT
(Comision Nacional de Ciencia y Tecnologa, Gobierno de Chile).
References
[1] K. Fent, Crit. Rev. Toxicol. 26 (1996) 3.
[2] M. Hoch, Appl. Geochem. 16 (2001) 719.
[3] J. Kuballa, E. Jansen, R.D. Wilken, Organotin Compounds in Sediments of the Rivers
Elbe and Mulde, in: W. Calmano, U. Forster (Eds.), Sediments and Toxics
Substances, Springer Verlag, Berlin, Heidelberg, 1996, pp. 245270.
[4] J.L. Gomez-Ariza, E. Morales, I. Giraldez, D. Snchez-Rodas, A. Velasco, J.
Chromatogr. A 938 (2001) 211.
[5] R. Lobinski, F.C. Adams, Spectrochim. Acta B 52 (1997) 1865.
[6] M. Abalos, J.M. Bayona, R. Compa, M. Granados, C. Leal, M.D. Pratt, J.
Chromatogr. A 788 (1997) 1.
[7] C. Montigny, G. Lespes, M. Potin-Gautier, J. Chromatogr. A 819 (1998) 221.
[8] I.L. Marr, C. White, D. Ritsau, J.L. Wradell, J. Lomax, Appl. Organomet. Chem. 11
(1997) 11.
[9] P. Schubert, I. Fernandez-Escobar, E. Rosenberg, J.M. Bayona, J. Chromatogr. A
(1997) 245.
[10] M. Bravo, G. Lespes, I. De Gregori, H. Pinochet, M. Potin-Gautier, J. Chromatogr. A
1046 (2004) 217.
[11] Y. Cai, R. Alzaga, J.-M. Bayona, Anal. Chem. 66 (1994) 1161.
[12] H. Pinochet, C. Tessini, M. Bravo, W. Quiroz, I. De Gregori, Environ. Monit. Assess.
155 (2008) 341353.

[13] B. Lalere, J. Szpunar, H. Budzinski, P. Garrigues, O.F.X. Donard, Analyst 120 (1995)
26652673.
[14] M. Gallego-Gallegos, M. Liva, R.M. Olivas, C. Camara, J. Chromatogr. A 1114 (2006)
8288.
[15] A.M. Reid, C.A. Brougham, A.M. Fogarty, J.J. Roche, Anal. Chim. Acta 634 (2008)
197204.
[16] J. Pacheco-Arjona, P. Rodriguez-Gonzalez, M. Valiente, D. Barclay, O.F.X. Donard,
Int. J. Environ. Anal. Chem. 88 (2008) 923932.
[17] L.M. Smith, D.L. Stalling, J.L. Johnson, Anal. Chem. 56 (1984) 18301842.
[18] B. Lalere, J. Szpunar, H. Budzinski, P. Garrigues, O.F.X. Donard, Analyst 120 (1995)
26652673.
[19] O.F.X. Donard, B. Lalere, F. Martin, R. Lobinski, Anal. Chem. 67 (1995) 42504254.
[20] D.F. Goerlitz, L.M. Law, Bull. Environ. Contam. Toxicol. 6 (1971) 910.
[21] P. Schubert, I. Fernandez-Escobar, E. Rosenberg, J.M. Bayona, J. Chromatogr. A 810
(1998) 245251.
[22] I. Fernandez-Escobar, M. Gilbert, A. Messeguer, J.M. Bayona, Anal. Chem. 70
(1998) 37033707.
[23] A. Wasik, B. Radke, J. Bolalek, J. Namiesnik, Chemosphere 68 (2007) 19.
[24] M. Flores, M. Bravo, W. Quiroz, Z. Mester, in preparation.
[25] V. Colombini, C. Bancon-Montigny, L. Yang, P. Maxwell, R. Sturgeon, Z. Mester,
Talanta 63 (2004) 555560.
[26] L. Yang, J.W.H. Lam, J. Anal. At. Spectrom. 16 (2001) 724731.
[27] L. Yang, Z. Mester, R. Sturgeon, Anal. Chem. 74 (2002) 29682976.
[28] L. Yang, Z. Mester, R. Sturgeon, J. Anal. At. Spectrom. 17 (2002) 944949.
[29] C. Carlier-Pinasseau, G. Lespes, M. Astruc, Talanta 44 (1997) 1163.
[30] C.G. Arnold, A. Ciani, S.R. Mller, A. Amirbahman, R.P. Schwarzenbach, Environ.
Sci. Technol. 32 (1998) 29762983.
[31] F. Tebbe, E. Wasserman, W. Peet, A. Vatvars, A. Hayman, J. Am. Chem. Soc. 104
(1982) 49714972.
[32] J. Ruiz Encinar, P. Rodriguez-Gonzalez, J. Garca-Alonso, A. Sanz-Medel, Trends
Anal. Chem. 22 (2003) 2.
[33] F. Stuer-Lauridsen, B. Dahl, Chemosphere 30 (1995) 831845.