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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
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
130
Injector system
Injector temperature
Carrier gas: ow rate
Transfer line temperature
MS
SIM parameters
MS quad temperature
MS source temperature
131
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.
132
Fig. 3. EI-MS spectra obtained by GC-MS from elemental sulfur spiked acetic acid extract: (A) diethyltrisulphide and (B) diethyltetrasulphide.
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
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
Table 5
Determination of MBT, DBT and TBT in samples from San Vicente Bay by liquidliquid
extractionGCMS.
Sample
SA
S1
a
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
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
134
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