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Chemical Ionization GC/MS For The Analysis of Tributyltin Oxide

This document describes the use of chemical ionization gas chromatography/mass spectrometry (GC/MS) to analyze tributyltin oxide (TBTO) at low parts-per-trillion (ppt) levels in seawater and wastewater samples. GC/MS with methane chemical ionization provides high selectivity and sensitivity for tributyltin and allows quantitation down to 1-100 ppt levels. The method involves extracting TBTO from water samples, derivatizing the extract, and analyzing by GC/MS. Chromatograms of standards and samples show peaks for tributyltin, dibutyltin, and monobutyltin in the low ppt range.

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Rauzatun Nusyura VII
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44 views

Chemical Ionization GC/MS For The Analysis of Tributyltin Oxide

This document describes the use of chemical ionization gas chromatography/mass spectrometry (GC/MS) to analyze tributyltin oxide (TBTO) at low parts-per-trillion (ppt) levels in seawater and wastewater samples. GC/MS with methane chemical ionization provides high selectivity and sensitivity for tributyltin and allows quantitation down to 1-100 ppt levels. The method involves extracting TBTO from water samples, derivatizing the extract, and analyzing by GC/MS. Chromatograms of standards and samples show peaks for tributyltin, dibutyltin, and monobutyltin in the low ppt range.

Uploaded by

Rauzatun Nusyura VII
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chemical Ionization

GC/MS for the


Analysis of
Tributyltin Oxide
Number 57
J. K. Brandau
Newport News Shipbuilding, Newport News, Virginia
Key Words: TBTO, CI, Environmental, Saturn
Introduction Results and Discussion
Tributyltin Oxide (TBTO) is the active agent in a Benchtop GC/MS systems have a smaller capacity
class of antifoulant marine coatings used on vacuum system when compared to larger research
commercial and military ocean vessels. The units that are differentially pumped. The CI reagent
migration of TBTO through the paint provides gas pressure must be lower in benchtop units so as
surface concentrations sufficient to limit growth of to not exceed the capacity of the vacuum system.
flora and fauna on ship hulls. With time TBTO is The lower pressure means that the CI reaction does
leached from the paint into the sea water. An not proceed as far as with a higher pressure ion
analytical method that monitors TBTO in tidal rivers source. During the ionization period the column
and waste waters must be highly sensitive and effluent is ionized along with the CI reagent gas
selective. Detection limits in the 1-100 ppt range creating a spectrum containing a mixture of EI and
are necessary for marine water samples. Chemical CI ions. Normally the column effluent is negligible
ionization mass spectrometry is used for this and does not show up in the CI spectrum; however,
analysis to increase the signal intensity of the under the reduced pressure conditions in benchtop
quantitation ions and to increase the selectivity of GC/MS these EI artifacts are substantial. The
the analyte with respect to the matrix. Saturn GC/MS eliminates these artifacts by storing
Tributyltin species and associated dibutyltin and only those reagent gas ions and eliminating the EI
monobutyltin are hydrolyzed by the sea water to artifact ions as they are produced. In addition the
form various organotin hydroxides. These sensitivity of the CI process is increased
compounds are extracted, derivatized, and then substantially by allowing the analyte to react with the
quantitated by GC/MS. reagent gas ions for up to 25 milliseconds. GC/MS
systems that do not trap and store ions have
Procedure reaction times of microseconds which leads to
reduced sensitivity when low pressure is used.
Tributyltin is extracted form sea water or waste
1
water by the method proposed by Unger et al.
Acidify the water sample to pH 2 with concentrated
HCl. Extract the TBTO with three 40 ml aliquots of
0.2% tropolone in hexane collecting the extracts.
Reduce the volume to about 10 ml under dry
nitrogen at 40°C. Transfer this extract to a
centrifuge tube taking care not to transfer any water
present. Reduce this volume to about 1 ml with dry
nitrogen. Add 0.5 ml of hexyl magnesium bromide
solution and stopper the centrifuge tube. Agitate at
5 minute intervals for a total reaction time of 30
minutes. Dissolve precipitate with 2 ml HCl. Clean
the grignardized sample (top layer) on a Florisill
column eluting with hexane. The sample is
concentrated and analyzed by methane chemical
ionization GC/MS. Figure 1: Standard containing 2.5 ng/ul of tributyltin,
dibutyltin, monobutyl tin, and 10 ng/ul of tripentyl tin
internal standard.
NOTICE: Varian, Inc. was acquired by Agilent
Technologies in May 2010. This document is provided
as a courtesy but is no longer kept current and thus
will contain historical references to Varian. For more
varian
information, go to www.agilent.com/chem. GC/MS App Note 57 Page 1
Figure 1 shows the results of a typical standard of
several butyltin compounds. Pentyltin is the internal
standard used for quantitation.

Figure 2 shows an example of a typical water


sample analyzed for TBT (77 ppt), DBT (93 ppt),
and MBT (20 ppt). Figure 3 shows the typical CI
spectra obtained using methane as a reagent gas.
Figure 4 shows the calibration curve used for
quantitation.

Figure 4: Internal standard calibration curve for


tributyltin.

Instrumental
Gas Chromatograph
Column Oven: 70°C and hold 1 minute, then heat at
30°C/min. to 120°C, and then 5°C/min. to 260°C.
Injector: SPI 70°C and hold 1 minute, then heat at
40°C/min. to 285°C and hold for 5 min.

Figure 2: Chemical ionization GC/MS ion Mass Spectrometer


chromatograms of waste water sample containing
low ppt levels of butyltin. Mass Range 285-350
Sec/Scan 1.7
Filament 10 µ amps
Background Mass 150
CI ionize storage level 5
Reagent ion ejection 9 volts
CI reaction storage level 13
ARC ionization time 100 µ sec.
CI maximum ion time 2000 µ sec.
CI maximum reaction time 40 millisec.
ARC Target 5000
CI reagent gas methane

Conclusion
Chemical ionization GC/MS provides excellent
selectivity and sensitivity for monitoring tributyltin in
seawater and waste water. This procedure is
rugged, reliable and is used routinely in our
laboratory.
Figure 3: Typical chemical ionization spectra of
tributyltin and dibutyltin.
References
1
M. A. Unger, W. G. Macintyre, J. Graves, & R. J.
Hugget, Chemosphere, Vol. 15, No. 4 (1986): p.
462.

GC/MS App Note 57 Page 2

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