Comprehensive target analysis and TOP assay of per- and polyfluoroalkyl substances (PFAS) in wild boar livers indicate contamination hot-spots in the environment.

The suitability of wild boar liver as a bioindicator of per- and polyfluoroalkyl substances (PFAS) in the terrestrial environment was investigated. Samples from 50 animals in three different areas associated with (1) contaminated paper sludges distributed on arable land (PS), (2) industrial emissions of PFAS (IE) and (3) background contamination (BC) were analyzed for 66 PFAS, including legacy PFAS, novel substitutes and precursors of perfluoroalkyl acids (PFAAs). Additionally, the Total Oxidizable Precursor (TOP) assay was performed to determine the formation potential of PFAAs from precursors. In total, 31 PFAS were detected with site-specific contamination profiles. PFAS concentrations in livers from area PS and IE (567 and 944 µg kg-1 wet weight, respectively) were multiple times higher than from area BC (120 µg kg-1). The dominating PFAS were the legacy compounds perfluorooctane sulfonic acid (PFOS) in areas PS and BC (426 and 82 µg kg-1, respectively) and perfluorooctanoic acid (PFOA) in area IE (650 µg kg-1). In area IE, the compounds 4,8-dioxa-3H-perfluorononanoic acid (DONA) and hexafluoropropylene oxide dimer acid (HFPO-DA) - which are used as substitutes for PFOA - were determined at 15 and 0.29 µg kg-1, respectively. The formation potential of PFAAs was highest in area PS, but generally lower than the contamination with PFAAs. The pattern of perfluoroalkyl carboxylic acids (PFCAs) in wild boar liver reflects the contamination of the local soil at the two hot-spot areas IE and PS. This first comparison of PFAS contamination between wild boars and soil suggests that wild boar livers are suitable bioindicators for PFAS contamination in the terrestrial environment. Moreover, in terrestrial samples from area IE, legacy PFAS were found to be retained for a longer period as compared to riverine samples (suspended particulate matter and chub filet).

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.

Combining target analysis with sum parameters-a comprehensive approach to determine sediment contamination with PFAS and further fluorinated substances.

Recent studies aiming at a fluorine mass balance analysis in sediments combined the determination of extractable organic fluorine (EOF) with target analysis. They reported high fractions of unidentified organic fluorine (UOF) compounds, as the target analysis covers only a limited number of per- and polyfluoroalkyl substances (PFAS). For this reason, in this study, a comprehensive approach was used combining target analysis with an extended PFAS spectrum, the EOF and a modified total oxidisable precursor (TOP) assay, which includes trifluoroacetic acid, to determine the PFAS contamination in sediments (n=41) and suspended solids (n=1) from water bodies in Northern Germany (Lower Saxony). PFAS are ubiquitous in the sediments (detected in 83% of the samples). Perfluorinated carboxylic acids (PFCAs) were found in 64% of the samples; perfluorinated sulfonic acids (PFSAs) were detected less frequently (21%), with the highest concentration observed for perfluorooctanesulfonic acid (PFOS). Levels of precursors and substitutes were lower. Applying the TOP assay resulted in an increase in PFCAs in 43% of the samples analysed. In most cases, target analysis and the TOP assay could not account for the EOF concentrations measured. However, as the fraction of UOF decreased significantly, the application of the TOP assay in fluorine mass balance analysis proved to be an important tool in characterising the PFAS contamination of riverine sediments.