Application of in-source fragmentation to the identification of perfluoropentanoic acid and perfluorobutanoic acid in environmental matrices and human serum by isotope dilution liquid chromatography coupled with tandem mass spectrometry.

Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is the most common analytical technique for per- and polyfluoroalkyl substances (PFASs) research and monitoring. The PFAS identification requires a minimum of two multiple reaction monitoring (MRM) transition ions as quantifier transition ion and qualifier transition ion, respectively. The second transition ion abundance for perfluoropentanoic acid (PFPeA) and perfluobutanoic acid (PFBA) is too low for practical use. A method using the in-source fragment ions as the precursor ion for MRM or pseudo-MRM has been developed and evaluated for PFPeA and PFBA identification in various environmental abiotic and biotic samples including water, soil, sediment, WWTP sludge, fruits, vegetables, egg, macrophytes, fish, dolphin liver and human serum. The PFPeA qualifier MRM transition ion (m/z = 219 > 69) has been successfully applied in all the matrices with spike recoveries (90-125%), signal to noise ratios (>10) and transition ions ratio variation (80-120%). The PFBA qualifier pseudo-MRM transition ion (m/z = 169 > 169) works well in all the matrices except dolphin liver sample. The interpretation of pseudo-MRM results should be with cautions due to lower specificity compared to MRM. In addition, this project indicated under typical chromatographic conditions the MRM isobaric interference does happen frequently to PFPeA quantifier transition ion (m/z = 263 > 219) in serum and fish composite samples, and to PFBA quantifier transition ion (m/z = 213 > 169) in macrophytes, fish composite and dolphin liver samples.

Per and polyfluoroalkyl substances (PFAS) at high concentrations in neonatal Australian pinnipeds.

Per and polyfluorinated substances (PFAS) exposure was investigated in Australian pinnipeds. Concentrations of 16 PFAS were measured in the livers of Australian sea lion (Neophoca cinerea), Australian fur seal (Arctocephalus pusillus doriferus) and a long-nosed Fur Seal (Arctocephalus forsteri) pup sampled between 2017 and 2020 from colonies in South Australia and Victoria. Findings reported in this study are the first documented PFAS concentrations in Australian pinnipeds. Median and observed range of values in ng/g wet weight were highest for perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) in the liver of N. cinerea (PFOS = 7.14, 1.00-16.9; PFOA = 2.73, 0.32-11.2; PFNA = 2.96, 0.61-8.22; n = 28), A. forsteri (PFOS = 15.98, PFOA = 2.02, PFNA = 7.86; n = 1) and A. p. doriferus (PFOS = 27.4, 10.5-2119; PFOA = 0.98, 0.32-52.2; PFNA = 2.50, 0.91-44.2; n = 20). PFAS concentrations in A. p. doriferus pups were significantly greater (p < 0.05) than in N. cinerea pups for all PFAS except PFOA and were of similar magnitude to those reported in northern hemisphere marine animals. These results demonstrate exposure differences in both magnitude and PFAS profiles for N. cinerea in South Australia and A. p. doriferus in Victoria. This study reports detectable PFAS concentrations in Australian pinniped pups indicating the importance of maternal transfer of these toxicants. As N. cinerea are endangered and recent declines in pup production has been reported for A. p. doriferus at the colony sampled, investigation of potential health impacts of these toxicants on Australian pinnipeds is recommended.

Evaluation of Residues in Hen Eggs After Exposure of Laying Hens to Water Containing Per- and Polyfluoroalkyl Substances.

Per- and polyfluoroalkyl substances (PFAS) have been used in aqueous film-forming foams used in firefighting, resulting in soil and groundwater contamination and leading to human exposure via animal products grown in contaminated areas. The present study reports the relationship between PFAS intake by hens and the PFAS concentrations in the edible parts of eggs. Laying hens were exposed via drinking water to different concentrations of 4 PFAS compounds (perfluorooctane sulfonate [PFOS], perfluorohexane sulfonate [PFHxS], perfluorooctanoic acid [PFOA], and perfluorohexanoic acid) over 61 d. Egg PFAS residues were assessed for a further 30 d after exposure ceased. The target concentrations of PFAS were 0, 0.3, 3, 30, and 300 µg/L for the treatment groups T1-T5, respectively; and PFAS residues were determined from the eggs collected every second day. There was a linear correlation between the PFAS concentrations in the drinking water of hens and those detected in the egg, which could be useful in estimating PFAS concentrations in the egg by measuring water concentrations. Exposure of hens to drinking water with PFAS concentrations below the Australian Government Department of Health limits (PFOS and PFHxS, 0.07 µg/L; PFOA, 0.56 µg/L), and with no other sources of PFAS exposure, is unlikely to result in egg PFAS concentrations that would exceed the 10% limit set by Food Standards Australia New Zealand for human consumption. Environ Toxicol Chem 2021;40:735-743. © 2020 SETAC.

Utility of fur as a biomarker for persistent organic pollutants in Australian fur seals (Arctocephalus pusillus doriferus).

Persistent Organic Pollutants (POPs) can cause toxic effects in many species which include endocrine dysfunction, immunotoxicity, developmental defects and neoplasia. Species dominating the upper trophic level are vulnerable to these effects due to bioaccumulation. In Bass Strait, the Australian fur seal (Arctocephalus pusillus doriferus) is an important top order predator and sentinel species for ecosystem health. An alopecia syndrome is seen at high prevalence in juvenile, female Australian fur seals at Lady Julia Percy Island, Victoria, Australia. Previous investigations suggest causality could be due to an endocrine-like toxicant. The alopecia syndrome has significance for thermoregulation and is a likely risk factor for mortality. Fur collected from case (alopecic) and control (unaffected) seals sampled at Lady Julia Percy Island were analysed for POPs. To investigate the utility of fur for monitoring POPs concentrations in pinnipeds, a comparison of POPs concentrations in the fur and blubber of Australian fur seals stranded along the Victorian coast was undertaken. The concentration of selected POPs including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), polybrominated diphenyl ethers (PBDEs) and perfluorooctane sulfonate/perfluorooctanoic acid (PFOS/PFOA) were determined in fur using either High Resolution Gas Chromatography-Mass Spectrometry or Liquid Chromatography-Mass Spectrometry. Results indicate detectable, and in some individuals, elevated levels of dl-PCBs, PCDD/Fs and PBDEs in juvenile fur seals sampled on Lady Julia Percy Island, with significantly higher levels of dl-PCBs in case compared to control seals. Elevated levels of dl-PCBs and PCDD/Fs were found in blubber samples collected from stranded fur seals with significant correlations between blubber and fur concentrations seen, particularly for dl-PCBs. This study discusses the significance of POPs concentrations in relation to the causality of an alopecia syndrome in the Australian fur seal, and assesses the utility of fur as a non-invasive biomarker to monitor POPs exposure in this sentinel species.