A Rapid Derivatization for Quantitation of Perfluorinated Car-boxylic Acids from Aqueous Matrices by Gas Chromatography-Mass Spectrometry

Ultrashort chain perfluorocarboxylic acids (PFCAs) are receiving more attention due to their ever-increasing presence in the environment. Methods have been established for the analysis of short and long-chain PFCAs, while robust quantitation of ultrashort chain species are scarce. Here we develop a novel derivatization method using diphenyl diazomethane for quantitation of C2-C14 PFCAs in aqueous matrices. The method is highlighted by rapid completion of derivatization (<1 min), and retention and separation of ultrashort chain (C2/C3) PFCA derivatives using H2 carrier gas (R > 1.5). A weak anion solid phase extraction procedure for analyte recovery from representative aqueous samples was developed and validated by spike and recovery from ultrapure water, synthetic ocean water, and simulated denuder extracts used for collecting gaseous PFCAs. Recoveries for C2-C9 PFCAs ranged from 83-130 % for the majority of analytes and matrices. The instrument detection limits (IDLs) range from 8-220 fg per injection, and method detection limits (MDLs) range from 0.06-14.6 pg/mL for 500 mL aqueous samples, which are within an order of magnitude to conventional LC-MS/MS methods. The method was applied to the analysis of real samples of tap water, rainwater, ocean water, and annular denuder extracts. The overall method provides a cost-effective alternative to conventional LC-MS/MS methods, overcoming the typical GC-MS drawbacks of high detection limits and long sample preparation times, while being able to simultaneously analyze the complete spectrum of environmentally relevant PFCAs.