Quantitative Determination of Fluorinated Alkyl Substances by Large-Volume-Injection Liquid Chromatography Tandem Mass SpectrometryCharacterization of Municipal Wastewaters

Abstract

A quantitative method was developed for the determination of fluorinated alkyl substances in municipal wastewater influents and effluents. The method consisted of centrifugation followed by large-volume injection (500 μL) of the supernatant onto a liquid chromatograph with a reverse-phase column and detection by electrospray ionization and tandem mass spectrometry. The fluorinated analytes studied include perfluoroalkyl sulfonates, fluorotelomer sulfonates, perfluorocarboxylates, and select fluorinated alkyl sulfonamides. Recoveries of the fluorinated analytes from wastewater treatment plant (WWTP) raw influents and final effluent were in the ranges of 82−100% and 86−100%, respectively. The lower limit of quantitation was 0.5 ng/L depending on the analyte. The method was applied to flow-proportional composites of raw influent and final effluent collected over a 24 h period from 10 WWTPs nationwide. Fluorinated alkyl substances were observed in wastewater at all treatment plants, and each plant exhibited unique distributions of fluorinated alkyl substances despite similarities in treatment processes. In 9 out of the 10 plants sampled, at least one class of fluorinated alkyl substances exhibited increased concentrations in the effluent as compared to the influent concentrations. In some instances, decreases in certain fluorinated analyte concentrations were observed and attributed to sorption to sludge.