Optimization of sample preparation and chromatography for the determination of perfluoroalkyl acids in sediments from the Yangtze Estuary and East China Sea

Perfluoroalkyl acids (PFAAs) are ubiquitous pollutants present in various environmental media, including marine sediments. A method was proposed for the determination of 17 target PFAA analytes in marine sediment samples (n = 49) collected from the Yangtze Estuary and East China Sea. The proposed method involves the use of an optimized pretreatment procedure and ultrahigh-performance liquid chromatography electrospray ionization-tandem mass spectrometry in dynamic multiple reaction monitoring mode. The method relied on extraction cycles using methanol followed by concentration, filtration, and small volume injection to UHPLC-MS/MS. The recovery, time efficiency, and detection limit of the proposed method are improved relative to those of traditional methods. Limits of detection varied from 0.003 to 0.045 ng/g, and spike recoveries to sediment ranged from 90% to 110% with suitable precisions (1.7%-14.6%). PFAAs were widely present in the samples, and ΣPFAAs ranged from 0.67 ng/g dw to 36.75 ng/g dw. Results indicated that terrigenous input strongly influences PFAA distribution in sediments from the study areas. Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) were identified as the dominant perfluorocarboxylic acid (PFCA) and perfluoroalkylsulfonate (PFSA) in sediment samples from the Yangtze Estuary and the East China Sea. Preliminary environmental risk assessment indicated that PFOS may pose a higher environmental risk than PFOA. Furthermore, risk quotient values indicated that PFOS poses a significant risk to the aquatic ecosystem of the study areas.