On-line solid-phase extraction coupled with liquid chromatography/electrospray ionization mass spectrometry for the...

On-line solid-phase extraction (SPE) for pre-concentration and sample cleanup is one strategy to reduce matrix effects and to simultaneously improve detection sensitivity in liquid chromatography/mass spectrometry (LC/MS). This paper describes an on-line SPE-LC/MS method for the determination of tributyltin (TBT) and triphenyltin (TPhT) at trace levels in water samples. The direct coupling of an on-line C18 pre-column to LC/MS was used to pre-concentrate TBT and TPhT at trace levels from waters and to remove interfering matrix effects. Pre-concentration was followed by separation of TBT and TPhT on a C18 column using a mobile phase containing 0.1% (v/v) HCOOH/5 mM HCOONH4 and methanol. While both electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) can be interfaced with MS for the detection of TBT and TPhT, ESI-MS was preferred for this application. The calibration curve for the targets was linear in the concentration range 0.1-30 microg L(-1). The detection limit (signal-to-noise (S/N) ratio = 3) was 0.02 microg L(-1) when 3.0 mL of sample was enriched on the C18 pre-column. The recoveries of TBT and TPhT in spiked waters were from 81.0 to 101.9%. The reproducibilities for the analysis of the standard mixture (10 microg L(-1)) for TBT and TPhT were 13.1 and 5.0%, respectively. The developed method was an easy and fast way to analyze TBT and TPhT in water samples.