PFASs in the Nordic environment
2019; Linguagem: Inglês
10.6027/tn2019-515
ISSN0908-6692
AutoresAnna Kärrman, Thanh Wang, Roland Kallenborn, Anne Marie Langseter, Erik Magnus Ræder, Jan Ludvig Lyche, Leo W. Y. Yeung, Fangfang Chen, Ulrika Eriksson, Rudolf Aro, Felicia Fredriksson,
Tópico(s)Atmospheric chemistry and aerosols
ResumoThis report describes the screening of an extensive list of conventional and emerging perand polyfluoroalkyl substances (PFASs) in the Nordic environment.PFASs is a large class of substances that have become an environmental problem due to extreme persistence and potential toxic effects in biota and humans.More than 4 000 PFASs are estimated to be in circulation on the global market and the environmental distribution is poorly understood.This screening study covers in total ninety-nine (99) PFASs and analysis of extractable organic fluorine (EOF).The latter can provide the amount, but not identity, of organofluorine in the samples, which in turn can be used to assess the mass balance between known and unknown PFASs.The study was initiated by the Nordic Screening Group and funded by the Nordic Council of Ministers through the Chemicals Group as well as agencies and institutes represented in the Nordic Screening Group.A total of 102 samples were analyzed in this study, including bird eggs, fish, marine mammals, terrestrial mammals, surface water, WWTP effluents and sludge, and air.Samples were collected by institutes from the participating countries and self-governing areas; Denmark, Faroe Islands, Finland, Greenland, Iceland, Norway, and Sweden.The majority of samples were collected in 2017.PFASs were analyzed using liquid-, supercritical fluid-, and gas chromatography coupled to mass spectrometry.EOF was analyzed using combustion ion chromatography.The PFAS profile in seabird eggs and marine mammals was dominated by the perfluoroalkyl acids (PFAAs) that are perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs), and mainly perfluorooctane sulfonic acid (PFOS) and long chain PFCAs (>C8).The range of total PFAS concentrations in egg samples were 627 -707 ng/g w.w. for Sweden, 44.9 -99.9 ng/g w.w. for Iceland, and 56.9 -81.4 ng/g w.w. for Faroe Islands.Among the marine mammals, polar bear liver samples (Ursus maritimus) from Greenland showed the highest sum of PFASs (1426 -1890 ng/g) as well as highest EOF (1782 -2056 ng fluoride/g).The total PFASs in other marine mammal samples ranged between 35.1 ng/g in grey seal (Halichoerus grypus) from Denmark to 123 ng/g in harbour porpoise (Phocoena phocoena), also from Denmark.Reindeer (Rangifer tarandus) and freshwater fish livers from European perch (Perca fluviatilis), brown trout (Salmo trutta) and Arctic char (Salvelinus alpinus) also showed predominating PFCA and PFSA profiles with some minor contribution from PFCA precursor compounds.The total PFAS concentrations in the reindeer samples in descending order were 5.4 ng/g for Greenland, 3.3 ng/g for Sweden, 1.4 ng/g for Finland and 1.1 ng/g for Iceland.The brown bear sample (Ursus arctos) from Finland had a total PFAS concentration of 18.9 ng/g.Marine fish livers from Atlantic pollock (Pollachius pollachius), Greenland cod (Gadus ogac), Atlantic cod (Gadus morhua), European flounder (Platichthys flesus) and Atlantic herring (Clupea harengus), ranged from 10.6 ng/g to 18.2 ng/g.The average of total PFAS concentrations in the freshwater fish samples in 12 PFASs in the Nordic environment descending order were 154 (74.7 -302) ng/g for perch from Finland, 112 ng/g for perch from Norway,2) ng/g for trout and char from Faroe Islands, 24.5 (19.8 -29.1) ng/g for perch from Denmark, 5.9 (0.30 -11.47) ng/g for trout from Iceland, and 5.7 (5.2 -6.2) ng/g for perch from Sweden.Sludge samples were dominated by PFCA precursors, on average accounting for 75% of all identified PFASs, and mainly contributed by different isomers of polyfluoroalkyl phosphoric acid diesters (diPAPs).The PFASs in the sludge samples, in descending order, were 142 (136 -149) ng/g for Denmark, 103 (67.8 -180) ng/g for Sweden, 100 (74.9 -126) ng/g for Finland, 75.2 (64.1 -86.2) ng/g for Norway and 36.8 (34.9 -38.8) ng/g for Faroe IslandsEffluent samples contained a mix of PFAS classes including PFCAs, PFSAs, ultrashort PFASs (mainly perfluoropropionic acid, PFPrA) and PFCA precursors.The average total PFAS concentrations in the effluent samples were 113.3 ng/L for Sweden, 75.4 ng/L for Greenland, 55.4 ng/L for Iceland, 49.7 ng/L for Finland, 48.2 ng/L for Denmark, 44.0 ng/L for Norway and 34.2 ng/L for Faroe Islands.The PFASs in surface water mainly ranged between 1 and 10 ng/L, with one exception of 61 ng/L in Helsinki which could indicate strong influence from point source(s).PFCAs dominated the profile with the highest concentration for perfluorohexanoic acid (PFHxA) followed by perfluorobutanoic acid (PFBA).Air was collected using glass fiber filters (GFF) and PUF/XAD-2/PUF and analyzed for conventional PFASs and a suite of novel PFASs.Conventional PFASs detected in air included PFOA, perfluorobutane sulfonic acid (PFBS), perfluorohexane sulfonic acid (PFHxS), and PFOS.Novel PFAS such as 1,3-Bis(trifluoromethyl)-5-bromo-benzene (BTFBB) was frequently detected although their levels need to be further confirmed.Another novel PFAS that was detected in this study was perfluoroethylcyclohexane sulfonic acid (PFECHS).PFECHS was detected in fish liver, marine mammal liver, and also in surface water and WWTP effluent.The target analysis of PFASs could explain between 2% and 102% of the measured EOF.The average explanation degree for detected samples was 8% for surface water, 9% for WWTP sludge, 11% for WWTP effluents, 18% for reindeer, 26% for fresh water fish, 28% for bear, 37% for marine mammals, 42% for marine fish and 68% for bird eggs.This study demonstrates the need to include more PFAS classes in environmental assessments.Shorter chain PFASs with carbon chain lengths of 2-4 were frequently detected in surface water and WWTP effluent.Although having low bioaccumulation potential, they are likely as persistent as their longer chain homologues, and their long term effects on the environment and humans are unknown.Precursor compounds also contributed to the total PFASs in the present study and were frequently detected in many matrices.It is therefore important to include a comprehensive set of PFAS besides the stable end-products in environmental monitoring and to support regulatory discussions aiming at reducing PFAS exposure sources.The large proportion of unknown extractable organofluorine in most environmental samples in the Nordic environment also calls for further studies.The identity of substances contributing to the measured extractable fluorine in environmental samples also needs to be elucidated to further assess environmental and human health risks.d no no 5 PFPHP d no no Thermal decomposition in injector expected 6 DTFMP d no no Thermal decomposition in injector expected 7 TDFMS d no no Thermal decomposition in injector expected 8 ETDFHS d no no Thermal decomposition in injector expected 9 MNFBS d no no Thermal decomposition in injector expected 10 UDFBC d no no Thermal decomposition in injector expected 11 TCHFB d no no Thermal decomposition in injector expected 12 PFA d no no Thermal decomposition in injector expected 13 MNFBSA d yes 10-900 14 TDFMSA d yes
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