An analytical method for trifluoroacetic acid in water and air samples using headspace gas chromatographic determination of the methyl ester

An analytical method has been developed for the determination of trace levels of trifluoroacetic acid (TFA), an atmospheric breakdown product of several of the hydrofluorocarbon (HFC) and hydrochlorofluorocarbon (HCFC) replacements for the chlorofluorocarbon (CFC) refrigerants, in water and air. TFA is derivatized to the volatile methyl trifluoroacetate (MTFA) and determined by automated headspace gas chromatography (HSGC) with electron-capture detection or manual HSGC using GC/MS in the selected ion monitoring (Srm) mode. The method is based on the reaction of an aqueous sample containing TFA with dimethyl sulfate (DMS) in concentrated sulfuric acid in a sealed headspace vial under conditions favoring distribution of MFTA to the vapor phase, Water samples are prepared by evaporative concentration, during which TFA is retained as the anion, followed by extraction with diethyl. ether of the acidified sample and then back-extraction of TFA (as the anion) in aqueous bicarbonate solution. The extraction step is required for samples with a relatively high background of other salts and organic materials, Air samples are collected in sodium bicarbonate-glycerin-coated glass denuder tubes and prepared by rinsing the denuder contents with water to form an aqueous sample for derivatization and analysis, Recoveries of TFA from spiked water, with and without evaporative concentration, and from spiked air were quantitative, with estimated detection limits of 10 ng/mL (unconcentrated) and 25 pg/mL (concentrated 250 mL:1 mL) for water and 1 ng/m(3) (72 h at 5 L/min) for air, Several environmental air, fogwater, rainwater, and surface water samples were successfully analyzed; many showed the presence of TFA.