High Concentrations of Unidentified Extractable Organofluorine Observed in Blubber from a Greenland Killer Whale (Orcinus orca)

Lara Schultes; Carmen van Noordenburg; Kyra M. Spaan; Merle M. Plassmann; Malene Simon; Anna Roos; Jonathan P. Benskin
2020 | Environ. Sci. Technol. Lett. | 7 (909-915)

It is generally accepted that per- and polyfluoroalkyl substances (PFASs) occur primarily in protein-rich tissues such as blood and liver, but few studies have examined the occurrence of legacy and novel PFASs in lipid-rich tissues such as blubber. Here we report the distribution of 24 PFASs, total fluorine, and extractable organic fluorine (EOF) in eight different tissues of a killer whale (Orcinus orca) from East Greenland. The sum of target PFAS concentrations was highest in liver (352 ng/g of wet weight) and decreased in the following order: blood > kidney ≈ lung ≈ ovary > skin ≈ muscle ≈ blubber. Most of the EOF consisted of known PFASs in all tissues except blubber, which displayed the highest concentration of EOF, almost none of which was attributed to targeted PFASs. Suspect screening using high-resolution mass spectrometry revealed the presence of additional PFASs but is unlikely to explain the high concentrations of EOF in blubber. While the identity of this unknown organofluorine and its pervasiveness in marine mammals require further investigation, this work suggests that exposure of killer whales to organofluorine substances may be underestimated by determination of legacy PFASs exclusively in liver or blood.

Fluorine Mass Balance and Suspect Screening in Marine Mammals from the Northern Hemisphere

K.M. Spaan; C. van Noordenburg; M.M. Plassmann; L. Schultes; S. Shaw; M. Berger; M.P. Heide-Jørgensen; A. Rosing-Asvid; S.M. Granquist; R. Dietz; C. Sonne; F. Rigét; A. Roos; J.P. Benskin
2020 | Environ. Sci. Technol. | 54 (7) (4046-4058)

There is increasing evidence that the ~20 routinely monitored per- and polyfluoroalkyl substances (PFASs) account for only a fraction of extractable organofluorine (EOF) occurring in the environment. To assess whether PFAS exposure is being underestimated in marine mammals from the Northern Hemisphere, we performed a fluorine mass balance on liver tissues from 11 different species using a combination of targeted PFAS analysis, EOF and total fluorine determination, and suspect screening. Samples were obtained from the east coast United States (US), west and east coast of Greenland, Iceland, and Sweden from 2000-2017. Of the 36 target PFASs, perfluorooctane sulfonate (PFOS) dominated in all but one Icelandic and three US samples, where the 7:3 fluorotelomer carboxylic acid (7:3 FTCA) was prevalent. This is the first report of 7:3 FTCA in polar bears (~1000 ng/g, ww) and cetaceans (<6-190 ng/g, ww). In 18 out of 25 samples, EOF was not significantly greater than fluorine concentrations derived from sum target PFASs. For the remaining 7 samples (mostly from the US east coast), 30-75% of the EOF was unidentified. Suspect screening revealed an additional 33 PFASs (not included in the targeted analysis) bringing the total to 59 detected PFASs from 12 different classes. Overall, these results highlight the importance of a multi-platform approach for accurately characterizing PFAS exposure in marine mammals.

Fluorine Mass Balance in Marine Mammals from the Northern Hemisphere – A combination of targeted, total (organo)fluorine, and non-targeted analysis

Kyra M. Spaan; Carmen van Noordenburg; Merle M. Plassmann; Lara Schultes; Susan Shaw; Michelle Berger; Mads Peter Heide-Jørgensen; Aqqalu Rosing-Asvid; Sandra M. Granquist; Rune Dietz; Christian Sonne; Frank Rigét; Anna Roos; Jonathan P. Benskin
2019 | Society of Environmental Toxicology and Chemistry (SETAC)

Society of Environmental Toxicology and Chemistry | November 4, 2019 | Toronto, Canada

There is increasing evidence that the ~20 routinely monitored per- and polyfluoroalkyl substances (PFASs) account for only a fraction of extractable organofluorine (EOF) occurring in the environment. To assess whether PFAS exposure is being underestimated in marine mammals from the Northern Hemisphere, we performed a fluorine mass balance on liver tissues from 11 different species using a combination of targeted PFAS analysis, EOF and total fluorine determination, and suspect screening. Samples were obtained from the east coast United States (US), west and east coast of Greenland, Iceland, and Sweden from 2000-2017. Of the 36 target PFASs, perfluorooctane sulfonate (PFOS) dominated in all but one Icelandic and three US samples, where the 7:3 fluorotelomer carboxylic acid (7:3 FTCA) was prevalent. This is the first report of 7:3 FTCA in polar bears (~1000 ng/g, ww) and cetaceans (<6-190 ng/g, ww). In 18 out of 25 samples, EOF was not significantly greater than fluorine concentrations derived from sum target PFASs. For the remaining 7 samples (mostly from the US east coast), 30-75% of the EOF was unidentified. Suspect screening revealed an additional 33 PFASs (not included in the targeted analysis) bringing the total to 59 detected PFASs from 12 different classes. Overall, these results highlight the importance of a multi-platform approach for accurately characterizing PFAS exposure in marine mammals.

Effects of 25 thyroid hormone disruptors on zebrafish embryos: A literature review of potential biomarkers

Kyra Spaan; Ann-Cathrin Haigis; Jana Weiss; Jessica Legradi
2018 | Sci. Total Environ. | 656 (1238-1249)

It is estimated that many organic compounds found in our environment can interfere with the thyroid system and act as thyroid hormone (TH) disruptor. Despite that, there is a clear lack of assays to identify TH disruptors. Recently zebrafish embryos were suggested as screening tool to identify compounds which impact thyroid synthesis. Effects on hormone level, gene transcript expression, eye development and swim bladder inflation are suggested as potential biomarker for TH disruptors. In order to assess the applicability of these biomarkers we performed a literature review. The effects of 25 known TH disrupting compounds were compared between studies. The studies were limited to exposures with embryos prior 7 days of development. The different study designs and the lack of standardized methods complicated the comparison of the results. The most common responses were morphological alterations and gene transcript expression changes, but no specific biomarker for TH disruption could be identified. In studies addressing TH disruption behavioral effects were more commonly monitored than in studies not mentioning the TH pathway. TH disruption in developing zebrafish embryosmight be caused by different modes of action e.g. disruption of follicle development, binding of TH, activation of TH receptors causing different effects. Timing of developmental processes in combination with exposure duration might also play a role. On the other side compound characteristics (uptake, stability, metabolization) could also cause differences between substances. Further studies are necessary to gain better understanding into the mechanisms of TH disruption in early zebrafish development.

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