Method development for liquid chromatographic/triple quadrupole mass spectrometric analysis of trace level perfluorocarboxylic acids in articles of commerce

An analytical method to identify and quantify trace levels of C5–C12 perfluorocarboxylic acids (PFCAs) in articles of commerce (AOCs) was developed and rigorously validated. Solid samples were extracted in methanol, and liquid samples were diluted with a solvent consisting of 60:40 (v/v) methanol and 2 mM ammonium acetate (NH4Ac) aqueous solution. In both cases, the samples were spiked with an isotopically labeled recovery check standard. The samples were concentrated in a nitrogen atmosphere (solid samples only), filtered, and then analyzed by HPLC coupled with a tandem mass spectrometer. Method evaluation included selection of the extraction solvent and the sample preparation solvent used to facilitate sample injection into the analytical system, method comparison for extraction and sample concentration, determination of extraction efficiency, instrument and method detection limits, and determination of potential sample loss during filtration and sample storage. Results of consecutive extractions demonstrated that a single extraction step accounts for 70–100% of the “total” PFCAs in the AOCs with the exception of cookware. The instrument's detection limit was ≤0.05 ng/mL, and the method detection limit were 1.0–3.9 ng/g for solid AOCs and 1.1–6.8 ng/g for liquid AOCs. The method has been used to determine the PFCA content in a wide range of AOCs containing or treated with fluoropolymers and fluorotelomers.