Application of human biomonitoring data to support policy development, raise awareness and environmental public health protection among countries within the HBM4EU project.

Most countries have acknowledged the importance of assessing and quantifying their population's internal exposure from chemicals in air, water, soil, food and other consumer products due to the potential health and economic impact. Human biomonitoring (HBM) is a valuable tool which can be used to quantify such exposures and effects. Results from HBM studies can also contribute to improving public health by providing evidence of individuals' internal chemical exposure as well as data to understand the burden of disease and associated costs thereby stimulating the development and implementation of evidence-based policy. To have a holistic view on HBM data utilisation, a multi-case research approach was used to explore the use of HBM data to support national chemical regulations, protect public health and raise awareness among countries participating in the HBM4EU project. The Human Biomonitoring for Europe (HBM4EU) Initiative (https://www.hbm4eu.eu/) is a collaborative effort involving 30 countries, the European Environment Agency (EEA) and the European Commission (contracting authority) to harmonise procedures across Europe and advance research into the understanding of the health impacts of environmental chemical exposure. One of the aims of the project was to use HBM data to support evidence based chemical policy and make this information timely and directly available for policy makers and all partners. The main data source for this article was the narratives collected from 27 countries within the HBM4EU project. The countries (self-selection) were grouped into 3 categories in terms of HBM data usage either for public awareness, policy support or for the establishment HBM programme. Narratives were analysed/summarised using guidelines and templates that focused on ministries involved in or advocating for HBM; steps required to engage policy makers; barriers, drivers and opportunities in developing a HBM programme. The narratives reported the use of HBM data either for raising awareness or addressing environmental/public health issues and policy development. The ministries of Health and Environment were reported to be the most prominent entities advocating for HBM, the involvement of several authorities/institutions in the national hubs was also cited to create an avenue to interact, discuss and gain the attention of policy makers. Participating in European projects and the general population interest in HBM studies were seen as drivers and opportunities in developing HBM programmes. A key barrier that was cited by countries for establishing and sustaining national HBM programmes was funding which is mainly due to the high costs associated with the collection and chemical analysis of human samples. Although challenges and barriers still exist, most countries within Europe were already conversant with the benefits and opportunities of HBM. This article offers important insights into factors associated with the utilisation of HBM data for policy support and public awareness.

Quantitative relationships of perfluoroalkyl acids in drinking water associated with serum concentrations above background in adults living near contamination hotspots in Sweden.

Contaminated drinking water (DW) is a major source of exposure to per- and polyfluoroalkyl substances (PFAS) at locations around PFAS production/use facilities and military airports. This study aimed to investigate quantitative relationships between concentrations in DW and serum of nine perfluoroalkyl acids (PFAAs) in Swedish adult populations living near contamination hotspots. Short-chained (PFPeA, PFHxA, PFHpA, and PFBS) and long-chained PFAAs (PFOA, PFNA, PFDA, PFHxS and PFOS) were measured in DW and serum. We matched DW and serum concentrations for a total of 398 subjects living or working in areas receiving contaminated DW and in one non-contaminated area. Thereafter, linear regression analysis with and without adjustments for co-variates was conducted. This enabled to derive (i) serum concentrations at background exposure (CB) from sources other than local DW exposure (i.e. food, dust and textiles) at 0 ng/L DW concentration, (ii) population-mean PFAA serum:water ratios (SWR) and (iii) PFAA concentrations in DW causing observable elevated serum PFAA concentrations above background variability. Median concentrations of the sum of nine PFAAs ranged between 2.8 and 1790 ng/L in DW and between 7.6 and 96.9 ng/mL in serum. DW concentration was the strongest predictor, resulting in similar unadjusted and adjusted regression coefficients. Mean CB ranged from <0.1 (PFPeA, PFHpA, PFBS) to 5.1 ng/mL (PFOS). Serum concentrations increased significantly with increasing DW concentrations for all PFAAs except for PFPeA with SWRs ranging from <10 (PFHxA, PFHpA and PFBS) to 111 (PFHxS). Observed elevated serum concentrations above background variability were reached at DW concentrations between 24 (PFOA) and 357 ng/L (PFHxA). The unadjusted linear regression predictions agreed well with serum concentrations previously reported in various populations exposed to low and high DW levels of PFOA, PFHxS and PFOS. The quantitative relationships derived herein should be helpful to translate PFAA concentrations in DW to concentrations in serum at the population level.

Seasonal trends of per- and polyfluoroalkyl substances in river water affected by fire training sites and wastewater treatment plants.

Fire-fighting training areas and wastewater treatment plants (WWTPs) are potential sources of per- and polyfluoroalkyl substances (PFASs) to the nearby aquatic environment. This study investigated seasonal variations of PFAS levels in two river catchments in Sweden; one impacted by Stockholm Arlanda Airport (Sites 1 and 2), and the other by WWTPs and a military airport (Uppsala) (Sites 3 and 4). Æ©PFAS concentrations were up to 61 (Sites 1 and 2) and 4 (Sites 3 and 4) times higher compared to the reference site. Distinct different seasonal trends were observed in the two catchments with higher ∑PFAS concentrations during the high water flow season at Site 1 compared to the low water flow season, whereas Sites 3 and 4 showed an inverse seasonal trend. This demonstrates that the pollution is mobilized during periods of high flow in the first catchment (Stockholm Arlanda Airport), while it is diluted during high flow in the second catchment (Uppsala). Average annual loads for ∑PFASs were estimated at ∼5.2 and ∼3.7 kg yr-1 for the catchment in Uppsala and Stockholm Arlanda Airport, respectively. Thus, both catchments add PFASs to Lake Mälaren, which is Sweden's most important source area for drinking water production.

Serum Half-Lives for Short- and Long-Chain Perfluoroalkyl Acids after Ceasing Exposure from Drinking Water Contaminated by Firefighting Foam.

BACKGROUND: Firefighting foam-contaminated ground water, which contains high levels of perfluoroalkyl substances (PFAS), is frequently found around airports. In 2018 it was detected that employees at a municipal airport in northern Sweden had been exposed to high levels of short-chain PFAS along with legacy PFAS (i.e., PFOA, PFHxS, and PFOS) through drinking water. OBJECTIVES: In this study, we aimed to describe the PFAS profile in drinking water and biological samples (paired serum and urine) and to estimate serum half-lives of the short-chain PFAS together with legacy PFAS. METHODS: Within 2 weeks after provision of clean water, blood sampling was performed in all 26 airport employees. Seventeen of them were then followed up monthly for 5 months. PFHxA, PFHpA, PFBS, PFPeS, and PFHpS together with legacy PFAS in water and biological samples were quantified using LC/MS/MS. Half-lives were estimated by assuming one compartment, first-order elimination kinetics. RESULTS: The proportions of PFHxA, PFHpA, and PFBS were higher in drinking water than in serum. The opposite was found for PFHxS and PFOS. The legacy PFAS accounted for about 50% of total PFAS in drinking water and 90% in serum. Urinary PFAS levels were very low compared with serum. PFBS showed the shortest half-life {average 44 d [95% confidence interval (CI): 37, 55 d]}, followed by PFHpA [62 d (95% CI: 51, 80 d)]. PFPeS and PFHpS showed average half-lives as 0.63 and 1.46 y, respectively. Branched PFOS isomers had average half-lives ranging from 1.05 to 1.26 y for different isomers. PFOA, PFHxS, and linear PFOS isomers showed average half-lives of 1.77, 2.87, and 2.93 y, respectively. DISCUSSION: A general pattern of increasing half-lives with increasing chain length was observed. Branched PFOS isomers had shorter half-lives than linear PFOS isomers. https://doi.org/10.1289/EHP6785.

Historical usage of aqueous film forming foam: a case study of the widespread distribution of perfluoroalkyl acids from a military airport to groundwater, lakes, soils and fish.

Historical usage of aqueous film forming foams (AFFFs) at military airports is a potential source of perfluoroalkyl acids (PFAAs) to the nearby environment. In this study, the distribution of perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) in soil, groundwater, surface water, tap water well, and fish muscle was investigated at a closed down military airfield (F18) and its surroundings in Stockholm, Sweden. The presence of PFOS at AFFF training sites was inventoried. One major finding of the study is that a former airfield, abandoned since 1994, may still be a point source of PFAAs to nearby recipients. PFOS and PFOA were ubiquitous in the soil samples at former AFFF training sites with concentrations ranging from 2.18 to 8520ngg(-1) dry weight and <0.12-287ngg(-1) dry weight respectively. The sum of PFAAs in the groundwater and surface waters ranged from 738 to 51000ngL(-1) and

Stockholm Arlanda Airport as a source of per- and polyfluoroalkyl substances to water, sediment and fish.

Fire training facilities are potential sources of per- and polyfluoroalkyl substances (PFASs) to the nearby environment due to the usage of PFAS-containing aqueous fire-fighting foams (AFFFs). The multimedia distribution of perfluoroalkyl carboxylates (PFCAs), perfluoroalkyl sulfonates (PFSAs), perfluorooctanesulfonamide (PFOSA) and 6:2 fluorotelomer sulfonate (FTSA) was investigated near a fire training facility at Stockholm Arlanda Airport in Sweden. The whole body burden of PFASs in European perch (Perca fluviatilis) was 334±80µg absolute and was distributed as follows: Gonad>liver≈muscle>blood>gill. The bioconcentration factor (BCF) and sediment/water partition coefficient (Kd) increased by 0.6-1.7 and 0.2-0.5 log units, respectively, for each additional CF2 moiety for PFCAs and PFSAs. PFAS concentrations in water showed no significant decreasing trend between 2009 and 2013 (p>0.05), which indicates that Stockholm Arlanda Airport may be an important source for long-term contamination of the nearby environment with PFASs.

Polychlorinated biphenyls in the surficial sediment of Indiana Harbor and Ship Canal, Lake Michigan.

We report the results of the first intensive survey of polychlorinated biphenyls (PCBs) in the surficial sediment of the Indiana Harbor and Ship Canal (IHSC) in East Chicago, Indiana, a part of the Calumet River tributary of Lake Michigan that will be dredged to maintain depth for ship traffic. The tributary has previously been reported to be a large source of PCBs to Lake Michigan. PCB congeners were measured using tandem mass spectrometry in multiple reaction monitoring mode, a method that provides a high level selectivity and sensitivity for PCBs in complex environmental samples. The PCB concentrations (sum of 163 congeners or coeluting peaks) range from 53 to 35,000 ng g(-1) dry weight (d.w.) and are comparable to other PCB concentrations at contaminated tributaries in the United States, most of them (although not IHSC) established by law as Superfund sites. The PCB congener signal strongly resembles the original technical mixture Aroclor 1248 that has experienced a small amount of weathering--less than 2.5% by mass for the statistically different congeners--consistent with desorption, volatilization, and microbial dechlorination. The origin of the PCBs in IHSC is not known but Aroclor 1248 was used in hydraulic fluids, vacuum pumps, plasticizers and adhesives. Possible uses of this mixture in East Chicago included the equipment and auxiliary services for the adjacent steel mill and gas refinery and/or lubrication for the drawbridges spanning the canal.

External exposure and bioaccumulation of PCBs in humans living in a contaminated urban environment.

Humans are exposed to different mixtures of PCBs depending on the route of exposure. In this study we investigated the potential contribution of inhalation to the overall human exposure to PCBs in an urban area. For this purpose, the mechanistically based, non-steady state bioaccumulation model ACC-HUMAN was applied to predict the PCB body burden in an adult living in the Midwestern United States who eats a typical North American diet and inhales air contaminated with PCBs. Dietary exposure was estimated using measured data for eighteen PCB congeners in different food groups (fish, meat and egg, dairy products). Two scenarios for inhalation exposure were evaluated: one using air concentrations measured in Chicago, and a second using air measurements in a remote area on Lake Michigan, Sleeping Bear Dunes. The model predicted that exposure via inhalation increases the accumulated mass of PCBs in the body by up to 30% for lower chlorinated congeners, while diet is by far the dominant source of exposure for those PCB congeners that accumulate most in humans.

Oxidation of 4-chlorobiphenyl metabolites to electrophilic species by prostaglandin H synthase.

Hormonally sensitive tissues, like the prostate, ovary, and breast, increasingly studied as targets of environmental chemicals, are sources of an enzyme potentially capable of transforming and activating xenobiotics to highly reactive metabolites. Our study specifically addresses the question of whether prostaglandin H synthase (PGHS) can activate phenolic metabolites of polychlorinated biphenyls (PCBs). We found that human recombinant PGHS-2 catalyzed the oxidation of ortho (2',3'- and 3',4'-) and para (2',5'-) dihydroxy 4-chlorobiphenyl metabolites to their corresponding quinones. These were trapped in situ with N-acetyl cysteine, and the reaction products were isolated and characterized by liquid chromatography coupled mass spectrometry and (1)H and heteronuclear ((1)H-(13)C) nuclear magnetic resonance spectroscopy. Both mono- and di-N-acetyl cysteine Michael addition adducts were identified, with the 2',3'- and 2',5'-dihydroxy metabolites predominantly forming mono-N-acetyl cysteine adducts, while the 3',4'-dihydroxy predominantly formed disubstituted N-acetyl cysteine adducts. These studies clearly demonstrate that the phenolic metabolites of these environmental pollutants are activated by PGHS, as cosubstrates, to highly reactive electrophilic PCB quinones, with a potential for protein and DNA damage, especially in nonhepatic tissues where the enzyme is found.

Simultaneous extraction and clean-up of polychlorinated biphenyls and their metabolites from small tissue samples using pressurized liquid extraction.

A pressurized liquid extraction-based method for the simultaneous extraction and in situ clean-up of polychlorinated biphenyls (PCBs), hydroxylated (OH)-PCBs and methylsulfonyl (MeSO(2))-PCBs from small (<0.5 g) tissue samples was developed and validated. Extraction of a laboratory reference material with hexane-dichloromethane-methanol (48:43:9, v/v) and Florisil as fat retainer allowed an efficient recovery of PCBs (78-112%; RSD: 13-37%), OH-PCBs (46+/-2%; RSD: 4%) and MeSO(2)-PCBs (89+/-21%; RSD: 24%). Comparable results were obtained with an established analysis method for PCBs, OH-PCBs and MeSO(2)-PCBs.

Temporal trend of bis(4-chlorophenyl) sulfone, methylsulfonyl-DDE and -PCBs in Baltic guillemot (Uria aalge) egg 1971-2001--a comparison to 4,4'-DDE and PCB trends.

The dynamics of organohalogen contaminants and their metabolites are best studied over time by analysis of biota at high trophic levels. In this study, time trends, 1971-2001, of bis(4-chlorophenyl) sulfone (BCPS) and of methylsulfonyl-substituted metabolites of PCBs and 4,4'-DDE, were investigated in eggs of guillemot (Uria aalge) hatching in the Baltic Proper. Temporal trends of PCBs, trans-nonachlor, beta-HCH, 4,4'-DDT, and 4,4'-DDE were also assessed. Tris(4-chlorophenyl) methane (TCPMe), a 4,4'-DDT by-product, was detected in the eggs. The concentration of BCPS ranged between 2.6-0.76 microg/g on a lipid weight basis over the three decades and showed a significant 1.6% annual decrease. Three metabolites of PCBs, i.e. 3'-MeSO2-CB101, 4'-MeSO2-CB101 and 4-MeSO2-CB149, were quantified in all samples over time and showed an annual decrease of approximately 3% compared to MeSO2-DDE with a decrease of 8.9%. The methylsulfonyl-PCB and -DDE metabolites are eliminated more slowly than the persistent PCB congeners and 4,4'-DDE. Trans-nonachlor decreases by 16% compared to 19% and 9% for 4,4'-DDT and beta-HCH, respectively. The concentration of TCPMe in guillemot decreased by 8.2% per year. A linear relationship was found between TCPMe and 4,4'-DDE concentrations which supports the theory that TCPMe has an origin as a contaminant in commercial 4,4'-DDT products. The very slow decrease in BCPS concentrations is notable and remains to be explained. BCPS is still present at rather high concentrations in the guillemot eggs. The enantiomeric fraction varied between 0.27 and 0.67 which indicates less of a specific retention of the chiral MeSO2-PCBs in guillemot eggs than in grey seal tissues, for example. Independent of meta- or para-substitution of the sulfone group, the most accumulative atropisomer of each of four MeSO2-PCB pairs has been assigned an absolute R structure.

Enantioselective formation of methyl sulfone metabolites of 2,2',3,3',4,6'-hexachlorobiphenyl in rat.

Several nonsymmetric polychlorinated biphenyl (PCB) congeners form atropisomers due to steric hindrance of free rotation around the phenyl-phenyl bond. It is evident from the literature that both chiral PCB congeners and their atropisomeric methylsulfonyl-PCB metabolites, formed in higher animals and in humans, are present in biota as nonracemic mixtures. Chiral methylsulfonyl-PCBs are strongly dominated by one of the atropisomers in mammalian tissues. The aim of the present study is to examine enantioselective metabolism, retention, and excretion of 2,2',3,3',4,6'-hexachlorobiphenyl (CB-132) in rat by administration of a CB-132 racemate and pure atropisomers. Chemical analysis of liver, lung, and adipose tissue from the rats showed a strong retention of one of the CB-132 atropisomers and a similar, but even more pronounced, accumulation of one of the atropisomers of the meta- and para-methylsulfonyl-substituted CB-132 metabolites in these tissues. Metabolites with R structures were predominately formed from one of the atropisomers of CB-132. The slower metabolism of the other atropisomer of CB-132 and its pronounced excretion in feces suggest an enantioselective metabolism. The results indicate enantio-selective formation of the methylsulfonyl-CB132 metabolites and confirm the critical role of stereochemistry of chemicals for their metabolism.

Enantiomeric specificity of methylsulfonyl-PCBs and distribution of bis(4-chlorophenyl) sulfone, PCB, and DDE methyl sulfones in grey seal tissues.

PCB methyl sulfones (MeSO2-PCBs) are lipophilic PCB metabolites of which five of the environmentally relevant meta/para pairs are chiral (i.e., exist as atropisomeric pairs). Methylsulfonyl-DDE (MeSO2-DDE) is a DDE metabolite, while bis(4-chlorophenyl) sulfone (BCPS) is a commercial monomer used for thermoplastic production. All these sulfones are well-known environmental contaminants. In this study, liver, lung, and adipose tissue in grey seals (Halichoerus grypus) from the Baltic Sea, naturally exposed to organochlorines via their food, were analyzed for the compounds mentioned. MeSO2-PCBs, 3-MeSO2-DDE, and BCPS were all found in significantly higher concentrations in the liver than in lung and blubber. Their strong liver retention, represented by a median of 42 microg/g l.w. of sigmaMeSO2-PCBs, has previously been mainly neglected in assessments of exposure. The highest concentrations of PCBs and DDE were still found in the grey seal blubber. The atropisomeric composition of MeSO2-PCB congeners was determined, and their enantiomeric fractions were calculated and compared in blubber, liver, and lung tissues. The enantiomeric specificity was equal in all tissues. A notably high abundance (>94%) was observed for one atropisomer in each chiral MeSO2-PCB pair. The first eluting atropisomer (A1) was dominating for all para-substituted MeSO2-PCBs studied, while the second eluting atropisomers (A2) were as dominant in all meta-substituted MeSO2-PCBs in all samples analyzed. In the liver, as much as 50% of sigmaMeSO2-PCBs consisted of the second eluting atropisomer (A2) of 5-MeSO2-CB149. The results imply that the sulfone group is crucial for the specific liver retention of MeSO2-PCBs, 3-MeSO2-DDE, and BCPS.

Bis(4-chlorophenyl) sulfone (BCPS) in Swedish marine and fresh water wildlife-a screening study.

Bis(4-chlorophenyl) sulfone (BCPS) is a high production volume chemical (HPVC) applied in thermostable polymers. BCPS has been detected as an environmental contaminant both in Europe and in North America but it is still not a commonly studied pollutant. In this study, three Baltic Sea fish species; herring (Clupea harengus), salmon (Salmo salar) and perch (Perca fluviatilis) from the Swedish coast, and one inland fish species, arctic char (Salvelinus alpinus), were analysed to screen for the occurrence and distribution of BCPS. Salmon and arctic char, were sampled in the early 1970s as well as the late 1990s. Fish eating grey seal (Halichoerus gryphus) and guillemot (Uria aalge) from the Baltic Sea were included to screen for whether BCPS biomagnify or not. The representativeness of the analysed samples for studying bioaccumulation of environmental pollutants was compared through analysis of two well known persistent and bioaccumulating compounds, 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153), and 4,4'-DDE. Pooled muscle and blubber samples based on 4-10 individuals were used for analysis, as well as individual samples of grey seal blubber. 2,4,4'-Trichlorodiphenyl sulfone, was synthesised and applied as an internal standard. BCPS was detected in all marine samples but in only one of the fresh water fish samples. The highest BCPS concentrations detected, 1600 and 1900 ng/g lipid weighet (l.w.), were found in muscle from Baltic guillemot. The results indicate that BCPS is bioaccumulated in both grey seal and guillemot, and that the guillemot has higher concentrations of BCPS than the grey seal (50-500 ng/g l.w.). The concentrations found in different species of fish from the Baltic Sea ranged between 15-37 ng/g l.w. and lower concentrations were found in freshwater species (n.d.-1.8 ng/g l.w.). The present study shows that BCPS is found in all investigated species of wildlife but, in most species, still at low concentrations. However, the guillemot has levels in the low ppm range indicating a considerable biomagnification of BCPS in this species.