Determination of selected perfluorinated alkyl acids and persistent organic pollutants from a small volume human serum sample relevant for epidemiological studies

Abstract

A simple and fast method is presented for the determination of selected persistent organic pollutants (POPs) and perfluorinated alkyl acids (PFAAs), a subgroup of per- and polyfluorinated alkyl substances (PFAS) from a single 200μl aliquot of serum. Sample pretreatment starts with dispersive solid phase extraction of POPs to dichloromethane-hexane, which is immediately poured to cleanup column. POPs are eluted from column and concentrated for GC-MS/MS analysis. PFAAs are trapped to dispersant and are then extracted with ammonium acetate in methanol, concentrated and analysed with LC-MS/MS. For POPs, the limit of detection (LOD) ranged from 1.6 to 17pg/ml. Oxychlordane and dichlorodiphenyltrichloroethane had LODs in the upper end of this range as they were more labile and prone for interferences in the GC-MS/MS. For PFAAs, the LOD range from 0.027 to 0.068ng/ml. For POPs, the accuracy from Standard Reference Materials SRM 1589a and Arctic Monitoring and Assessment Programme (AMAP) intercalibration samples range from 74 to 127% and the repeatability (relative standard deviation, RSD%) from 2.0 to 15%. For PFAAs, the accuracy from AMAP samples ranged from 90 to 110% and from LOQ level spiked serum samples from 72 to 133%. Repeatability from AMAP and LOQ samples ranged from 1.6 to 7.3% and 5.5 to 15%, respectively. The presented method is useful in epidemiological studies where only limited amount of serum is available.

Keywords: Cardiovascular disease; Dispersive solid phase extraction; Human serum; Perfluorinated alkyl substances; Persistent organic pollutants; Type 2 diabetes.