Differences in the internal PFAS patterns of herbivores, omnivores and carnivores - lessons learned from target screening and the total oxidizable precursor assay.

Per- and polyfluorinated alkyl substances (PFAS) are a group of anthropogenic chemicals, which are not (fully) biodegradable and accumulate in different environmental compartments worldwide. A comprehensive, quantitative analysis - consisting of target analysis (66 different analytes, including e. g. ultrashort-chain perfluorinated carboxylic acids (PFCAs), precursor compounds and novel substitutes) and the Total Oxidisable Precursor (TOP) assay (including trifluoroacetic acid (TFA)) - were conducted to analyse the PFAS concentrations and patterns in 12 mammalian and two bird species from different areas of Germany and Denmark. The PFAS contamination was investigated in dependance of the trophic class (herbivores, omnivores, carnivores), ecological habitat (terrestrial, (semi-) aquatic) and body tissue (liver, musculature). PFAS concentrations were highest in carnivores, followed by omnivores and herbivores, with ∑PFAS concentration ranging from 1274 μg/kg (Eurasian otter liver) to 22 μg/kg (roe deer liver). TFA dominated in the herbivorous species, whereas perfluorooctanesulfonic acid (PFOS) and the long-chain PFCAs covered the majority of the PFAS contamination in carnivorous species. Besides trophic class, ecological habitat also affected the PFAS levels in the different species, with terrestrial herbivores and omnivores showing higher PFAS concentration than their aquatic counterparts, whereas for carnivores this relationship was reversed. The TOP assay analysis indicated similar trends, with the PFCA formation pattern differing significantly between the trophic classes. TFA was formed predominantly in herbivorous and omnivorous species, whereas in carnivorous species a broad spectrum of PFCAs (chain-length C2-C14) was formed. Musculature tissue of six species exhibited significantly lower PFAS concentrations than the respective liver tissue, but with similar PFAS patterns. The comprehensive approach applied in the present study showed, that primarily the trophic class is decisive for the PFAS concentration, as herbivores, omnivores and carnivores clearly differed in their PFAS concentrations and patterns. Additionally, the TOP assay gave novel insights in the PFCA formation potential in biota samples.