Comparison of tetraethylborate and tetraphenylborate for selenite determination in human urine by gas chromatography mass spectrometry, after headspace solid phase microextraction.

Two different derivatizing reagents were tested for the development of a fast and sensitive method for the determination of selenites (Se(IV)) in human urine. The reagents were sodium tetraethylborate (NaBEt(4)) and tetraphenylborate (NaBPh(4)), respectively, and the procedure is based on in situ derivatization of selenites in aqueous medium. Selenite ions are converted to diethylselenide (DESe) or diphenylselenide (DPhSe) and subsequently collected from the headspace by solid phase microextraction using a silica fiber coated with polydimethylsiloxane (HS-SPME). Finally, they are quantitated by GC/MS in SIM mode. Ethylation over phenylation was proved preferable for the headspace extraction because of the higher volatility of the diethyl-derivative of selenites. The optimization of the HS-SPME conditions was performed both in aqueous and urinary solutions. Under the optimum conditions for HS-SPME, the gas chromatographic conditions were also optimized. Between the two alkylation reagents tetraethylborate was proved more efficient and the quantitation was satisfactory. Aqueous certified reference materials were analyzed to evaluate the accuracy of the method. The precision of the method was 4.2% and the calculated detection limit was 0.05microgL(-1) for human urine.