Analysis of fluorotelomer alcohols in soils: Optimization of extraction and chromatography

Abstract

This article describes the development of an analytical method for the determination of fluorotelomer alcohols (FTOHs) in soil. The sensitive and selective determination of the telomer alcohols was performed by extraction with methyl tert-butyl ether (MTBE) and analysis of the extract using gas chromatography with detection and quantification by mass spectrometry operated in the positive chemical ionization mode. The protonated molecular ion, [M+H] + and a fragment ion (loss of HF + H 2O) m/ z 38 less than the molecular ion were monitored to identify tentatively FTOHs in MTBE extracts of contaminated soils. The FTOHs were confirmed by treatment of the extract with a silylation reagent and observing the disappearance of the FTOH response and the appearance of peaks attributable to the [M+H] + ions of the trimethylsilyl derivatives. Mass-labeled FTOHs were used as recovery and matrix internal standards. Recovery experiments on soils shown to be free of endogenous FTOHs at instrument detection limits (IDL) of 16 fg/μL for 6:2 FTOH, 10 fg/μL for 8:2 FTOH and 14 fg/μL for 10:2 FTOH yielded a limit of quantitation (LOQ) of 190, 100, and 160 fg/μL for 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH, respectively when 3 g samples of soil were extracted with 1 mL MTBE. The levels of the 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH in five soils contaminated with FTOHs by exposure to the laboratory atmosphere during air drying were determined. In these air-dried soils, concentrations of FTOHs ranged from non-detectable to 3600 fg/μL (0.6 ng/g) of the 6:2 FTOH in the extract of a commercial topsoil. This method was used to determine even and odd numbered FTOHs from 6:2 through 14:2 in soils from fields that had received applications of sewage sludge. Concentrations of FTOHs in these sludge-applied soils ranged as high as 820 ng/g of dry soil for the 10:2 FTOH.