Interpretation of butyltin mass spectra using isotope pattern reconstruction for the accurate measurement of isotope ratios from molecular clusters.
The fragmentation patterns of butyltin compounds (mono-, di-, and tributyltin) in an electron impact ion source were studied using an isotope pattern reconstruction algorithm with emphasis on isotope ratio measurements from molecular clusters. For this purpose, standards of natural tin isotope abundance and a (119)Sn-enriched mixture of the three compounds were both ethylated and propylated using sodium tetraalkylborates. The corresponding mass spectra of the various tetraalkyltin compounds prepared were obtained by GC/MS after their extraction with hexane. The results showed that pure interference-free molecular clusters were obtained only for certain R(3)Sn(+) ions where no isobaric overlap with R(2)SnH(+) ions occurred (e.g. BuEt(2)Sn(+) overlaps with Bu(2)SnH(+)). These ions are ideal candidates for accurate Sn isotope ratio measurements, while isotope pattern perturbing interferences are observed for other molecular fragments down to Sn(.)(+). Isotope pattern reconstruction algorithm thus can be used as an analytical tool to ensure the absence of molecular interferences--a requirement for accurate isotope ratio measurements from molecular clusters. The relevance of these studies for the determination of butyltin compounds in environmental samples by isotope dilution GC/MS is also discussed.
Meija
Juris
J
Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, USA.
Centineo
Giuseppe
G
Ignacio Garcia Alonso
J
J
Sanz-Medel
Alfredo
A
Caruso
Joseph A
JA
D004784:Environmental Monitoring / Q000379:methods*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D009947:Organotin Compounds / Q000032:analysis*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D014874:Water Pollutants, Chemical / Q000032:analysis*
D009947:Organotin Compounds; D014874:Water Pollutants, Chemical