Trace Determination of Perfluorooctane Sulfonate and Perfluorooctanoic Acid in Environmental Samples (surface Water, Wastewater, Biota, Sediments, and Sewage Sludge) Using Liquid Chromatography - Orbitrap Mass Spectrometry

An analytical method was established and validated for the analysis of the most frequently monitored representatives among the group of perfluorinated compounds (PFAS), namely, perfluorooctanoic acid (PFOA) and prefluorooctane sulfonate (PFOS) in environmental samples (surface water, wastewater, sediments, sewage sludge, and biota). High performance liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap-MS) employing a heated electrospray ionization (HESI) interface operated in negative mode was used for the quantitative determination of these contaminants. HPLC separation of analytes was achieved using a reversed phase C18 (RP-C18) analytical column. The efficiency of various solid phase extraction (SPE) columns for the pre-concentration and clean-up as well as the performance of different ionization sources and detection modes for the instrumental determination were evaluated. The validation results indicate recoveries of analytes between 88 and 116%, while the intra-day and inter-day precision parameters in terms of relative standard deviations (RSDs) were in the range of 1.0-5.9% and 1.5-7.3%, respectively. The measured values for certified reference material (CRM) agreed with the provided reference values, revealing the accuracy of obtained concentrations in the range of 107-108%. The trueness of the method was verified by a successful participation in a proficiency testing (PT) program. These performance characteristics of the method permit reliable monitoring of PFOS and its derivatives in environmental samples according to the environmental quality standard (EQS) criteria regarding the maximum allowable concentrations and taking into account the annual average concentrations stated in Directive 2013/39/EU. The elaborated method was applied for the routine analysis of selected PFAS in environmental samples from the Baltic region.