Accumulation of Short-, Medium-, and Long-Chain Chlorinated Paraffins in Marine and Terrestrial Animals from Scandinavia.

Short-, medium-, and long-chain chlorinated paraffins (SCCPs, MCCPs, and LCCPs) have a wide range of physical-chemical properties, indicating their varying bioaccumulation tendencies in marine and terrestrial ecosystems. However, there are few empirical data to reveal such bioaccumulation tendencies. In this study, we analyzed SCCPs, MCCPs, and LCCPs in samples from 18 species at both low and high trophic levels of marine and terrestrial ecosystems from the Scandinavian region collected during the past decade. These included fish, seabirds, marine mammals, and terrestrial birds and mammals. SCCPs, MCCPs, and LCCPs were present in all the species, with concentrations ranging from 26-1500, 30-1600, 6.0-1200 ng/g lipid, respectively. Although MCCPs and SCCPs predominated in most species, many terrestrial species had generally higher concentrations of LCCPs than marine species. Terrestrial raptors in particular accumulated higher concentrations of LCCPs, including C24/25-which are predominant among very-long-chain components. LCCP concentrations were highest and predominated (55% of total CPs) in peregrine falcons in this study, which is the first report where concentrations of LCCPs surpass those of SCCPs and MCCPs in wildlife. The results also indicate biomagnification of SCCPs, MCCPs, and LCCPs in both marine and terrestrial food chains, but in-depth studies of specific food webs are needed.

White-Tailed Eagle (Haliaeetus albicilla) Body Feathers Document Spatiotemporal Trends of Perfluoroalkyl Substances in the Northern Environment.

We reconstructed the first long-term (1968-2015) spatiotemporal trends of perfluoroalkyl substances (PFAS) using archived body feathers of white-tailed eagles (Haliaeetus albicilla) from the West Greenland (n = 31), Norwegian (n = 66), and Central Swedish Baltic coasts (n = 50). We observed significant temporal trends of perfluorooctane sulfonamide (FOSA), perfluorooctane sulfonate (PFOS), and perfluoroalkyl carboxylates (∑PFCAs) in all three subpopulations. Concentrations of FOSA and PFOS had started decreasing significantly since the mid-1990s to 2000 in the Greenland and Norwegian subpopulations, consistent with the 3M phase-out, though in sharp contrast to overall increasing trends observed in the Swedish subpopulation. Moreover, ∑PFCA concentrations significantly increased in all three subpopulations throughout the study periods. These temporal trends suggest on-going input of PFOS in the Baltic and of ∑PFCAs in all three regions. Considerable spatial variation in PFAS concentrations and profiles was observed: PFOS concentrations were significantly higher in Sweden, whereas FOSA and ∑PFCA concentrations were similar among the subpopulations. PFOS dominated the PFAS profiles in the Swedish and Norwegian subpopulations, in contrast to the domination of FOSA and ∑PFCAs in the Greenland one. Our spatiotemporal observations underline the usefulness of archived bird of prey feathers in monitoring spatiotemporal PFAS trends and urge for continued monitoring efforts in each of the studied subpopulations.

Human exposure to PFOS and mercury through meat from baltic harbour seals (Phoca vitulina).

The overall aim of the present study was to assess human exposure to environmental contaminants from consumption of harbour seal (Phoca vitulina) meat in the southwestern Baltic Sea. For this purpose, muscle tissue from harbour seals (n = 27) was sampled from Danish locations in the period 2005-2015 and analysed for concentrations of total mercury (Hg), organochlorine contaminants such as polychlorinated biphenyls (PCBs) and organochlorine pesticides as well as perfluoroalkyl substances (PFAS) with particular focus on perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Hg, ∑PCB, PFOS and PFOA concentrations in the muscle tissue ranged between 0.27 and 4.76 µg g-1 wet weight (ww; mean: 1.38 µg g-1 ww, n = 27), 12.2-137 ng g-1 ww (mean: 47.5 ng g-1 ww, n = 10), 6.95-33.6 ng g-1 ww (mean: 15.8 ng g-1 ww, n = 10) and 0.16-0.55 ng g-1 ww (mean: 0.28 ng g-1 ww, n = 10), respectively. We compared the concentrations with literature-derived human tolerable weekly intake (TWI) values for mercury (1.3 µg kg-1 week-1), ∑PCB (2.1 µg kg-1 week-1), PFOS (0.013 µg kg-1 week-1) and PFOA (0.006 µg kg-1 week-1). The comparisons showed that the weekly consumption of harbour seal meat by children (weighing 30 kg), women (weighing 60 kg) and men (weighing 80 kg) should not exceed 28, 57 and 76 g (for Hg), 1.3, 2.7 and 3.5 kg (for ∑PCB), 25, 50 and 67 g (for PFOS) and 640, 1290 and 1720 g (for PFOA). In conclusion, Hg and PFOS are the contaminants of most importance in seal meat from this area with respect to existing tolerable intake rates and risks of adverse human health effects.

Isothiazolinones are still widely used in paints purchased in five European countries: a follow-up study.

BACKGROUND: An increasing incidence of contact allergy to methylisothiazolinone (MI) has been seen, caused, in particular, by cosmetic products and paints. A study from 2015 showed that 93.0% of paints bought in five European countries contained MI. New regulations have been discussed for paints in the EU, which may have influenced this market. OBJECTIVES: To re-evaluate the use and concentrations of MI and four other isothiazolinones in water-based wall paints. METHODS: Water-based white wall paints (n = 60) were purchased in retail stores in five European countries: Denmark, France, Germany, Sweden, and the United Kingdom. The paints were analysed for isothiazolione content by the use of high-performance liquid chromatography coupled to ultraviolet detection, and the results were confirmed with high-performance liquid chromatography-tandem mass spectrometry. RESULTS: MI was identified in 55 (91.7%) of the paints, with concentrations ranging from 1.1 to 142.7 ppm. The other isothiazolinones were identified in 20.0% [methylchloroisothiazolinone (MCI)] to 88.3% [benzisothiazolinone (BIT)] of the paints. BIT concentrations varied significantly between countries, whereas MI and MCI concentrations did not. There were no statistically significant differences in MI, MCI and BIT concentrations between the current study and the 2015 study. CONCLUSIONS: MI and other isothiazolinones are widely used in paints available in Europe. Their use does not seem to be decreasing.

Spring Melt and the Redistribution of Organochlorine Pesticides in the Sea-Ice Environment: A Comparative Study between Arctic and Antarctic Regions.

Complementary sampling of air, snow, sea-ice, and seawater for a range of organochlorine pesticides (OCPs) was undertaken through the early stages of respective spring sea-ice melting at coastal sites in northeast Greenland and eastern Antarctica to investigate OCP concentrations and redistribution during this time. Mean concentrations in seawater, sea-ice and snow were generally greater at the Arctic site. For example, α-HCH was found to have the largest concentrations of all analytes in Arctic seawater and sea-ice meltwater samples (224-253 and 34.7-48.2 pg·L-1 respectively compared to 1.0-1.3 and <0.63 pg·L-1 respectively for Antarctic samples). Differences in atmospheric samples were generally not as pronounced however. Findings suggest that sea-ice OCP burdens originate from both snow and seawater. The distribution profile between seawater and sea-ice showed a compound-dependency for Arctic samples not evident with those from the Antarctic, possibly due to full submersion of sea-ice at the former. Seasonal sea-ice melt processes may alter the exchange rates of selected OCPs between air and seawater, but are not expected to reverse their direction, which fugacity modeling indicates is volatilisation in the Arctic and net deposition in the Antarctic. These predictions are consistent with the limited current observations.

Temporal Shifts in Poly- and Perfluoroalkyl Substances (PFASs) in North Atlantic Pilot Whales Indicate Large Contribution of Atmospheric Precursors.

Poly- and perfluoroalkyl substances (PFASs) are persistent, bioaccumulative anthropogenic compounds associated with adverse health impacts on humans and wildlife. PFAS production changed in North America and Europe around the year 2000, but impacts on wildlife appear to vary across species and location. Unlike other mammal species, cetaceans lack the enzyme for transforming an important intermediate precursor (perfluorooctane sulfonamide: FOSA), into a prevalent compound in most wildlife (perfluorooctanesulfonate: PFOS). Thus, their tissue burden differentiates these two compounds while other mammals contain PFOS from both direct exposure and precursor degradation. Here we report temporal trends in 15 PFASs measured in muscle from juvenile male North Atlantic pilot whales (Globicephala melas) harvested between 1986 and 2013. FOSA accounted for a peak of 84% of the 15 PFASs around 2000 but declined to 34% in recent years. PFOS and long-chained PFCAs (C9-C13) increased significantly over the whole period (2.8% yr-1 to 8.3% yr-1), but FOSA declined by 13% yr-1 after 2006. Results from FOSA partitioning and bioaccumulation modeling forced by changes in atmospheric inputs reasonably capture magnitudes and temporal patterns in FOSA concentrations measured in pilot whales. Rapid changes in atmospheric FOSA in polar and subpolar regions around 2000 helps to explain large declines in PFOS exposure for species that metabolize FOSA, including seafood consuming human populations. This work reinforces the importance of accounting for biological exposures to PFAS precursors.

Persistent organic pollutants and related biological responses measured in coastal fish using chemical and biological screening methods.

The aim of this study was to investigate the spatial distribution, levels of dioxin-like compounds (DLC), and biological responses in two fish species. The viviparous eelpout (Zoarces viviparus) was collected from various locations in the Baltic Sea and in fjords of Kattegat and Skagerrak, while shorthorn sculpin (Myoxocephalus scorpius) was obtained at the polychlorinated biphenyl (PCB) polluted site in North West Greenland. Significant differences were detected both in contaminant levels and relative contributions from either polychlorinated dibenzodioxins (PCDD) or polychlorinated dibenzofurans (PCDF or furans) and mono-ortho- and non-ortho (coplanar) polychlorinated biphenyls (dl-PCB). Fish from the eastern Baltic Sea generally displayed higher contributions from PCDD/F compared to dl-PCB, whereas dl-PCB were generally predominated in fish from Danish, Swedish, and German sites. Levels of dl-PCB in muscle tissues were above OSPAR environmental assessment criteria (EAC) for PCB118, indicating a potential risk of adverse biological effects in the ecosystem, whereas levels of the total WHO-TEQs were below threshold for sea food suggesting limited risks for humans. No significant relationships between levels of DLC (expressed as WHO-TEQ), and biological responses such as the induction of CYP1A enzymatic activity and fry reproductive disorders were observed in eelpout. No marked relationship between WHO-TEQ and combined biological aryl hydrocarbon receptor-mediated transactivity (expressed as AhR-TEQ) was noted. However, there was a positive correlation between polycyclic aromatic hydrocarbon (PAH) metabolites and induction of CYP1A activity, suggesting that PAH exhibited greater potential than DLC to produce biological effects in eelpout from the Baltic Sea.

Endosulfan, Short-Chain Chlorinated Paraffins (SCCPs) and Octachlorostyrene in Wildlife from Greenland: Levels, Trends and Methodological Challenges.

Besides globally banned "legacy" persistent organic pollutants, other compounds might be present in Arctic wildlife, for which regulation was introduced recently (the insecticide endosulfan), is considered (short-chain chlorinated paraffins, SCCPs) or does not exist (octachlorostyrene, OCS, a byproduct of manufacturing and combustion processes involving chlorine). The purpose of this study was to analyze the time trend of endosulfan (1986-2012) in ringed seals and to address the levels of SCCPs and OCS in wildlife species from Greenland (black guillemot, glaucous gull, ringed seal, polar bear), while taking a critical standpoint to analytical methods typically applied. The metabolite endosulfan sulfate was the only endosulfan compound consistently above detection limits, with a median concentration of 0.23 ng/g lipid weight (lw) and a significant annual decrease of -5.6%. The low-resolution mass spectrometry (LRMS) method appeared accurate and sufficiently precise; however, the gel permeation chromatography had to balance lipid removal and analyte loss. SCCPs and OCS were present in all samples. OCS median concentrations were between 2.8 (ringed seal blubber) and 29 (glaucous gull liver) ng/g lw, determined by a straightforward dual column electron capture detection method. SCCPs were analyzed by LRMS, following removal of potential interferences, and had median concentrations of several 100 ng/g wet weight. While the method showed good precision and recovery rates as well as acceptable accuracy in control samples, the Greenland samples had high concentrations in an Arctic context, possibly indicating limited selectivity of the LRMS method.

Immunomodulatory effects of exposure to polychlorinated biphenyls and perfluoroalkyl acids in East Greenland ringed seals (Pusa hispida).

To better elucidate the potential immune-related health effects of exposure to environmentally persistent organic pollutants (POP), such as polychlorinated biphenyls (PCBs) and perfluoroalkyl substances (PFASs), in ringed seals (Pusa hispida), a sentinel Arctic species, we assessed 1) associations between mitogen-induced lymphocyte proliferation and in vivo tissue contaminant burdens, and 2) the concentration-response effects of in vitro exposure to PFASs and PCB congeners on mitogen-induced lymphocyte proliferation. Upon in vitro contaminant exposure, the non-coplanar PCB congeners CB 138, 153, and 180, but not the coplanar CB 169, significantly reduced lymphocyte proliferation between 10 and 20µgg-1 ww. The respective in vitro EC50 values for these congeners were 13.3, 20.7, 20.8, and 54.6µgg-1 ww. No modulation of lymphocyte proliferation was observed upon in vitro exposure to two individual PFASs, perfluorooctane sulphonic acid (PFOS) and perfluorooctanoic acid (PFOA), at concentrations up to 1000ngg-1. In addition, no significant correlations were found between lymphocyte proliferation and any blood or blubber contaminant measured. Taken together, these data suggest this population of ringed seals is not currently at high risk of altered lymphocyte proliferation from exposure to the POPs or PFASs in this study.

An Antarctic research station as a source of brominated and perfluorinated persistent organic pollutants to the local environment.

This study investigated the role of a permanently manned Australian Antarctic research station (Casey Station) as a source of contemporary persistent organic pollutants (POPs) to the local environment. Polybrominated diphenyl ethers (PBDEs) and poly- and perfluoroalkylated substances (PFASs) were found in indoor dust and treated wastewater effluent of the station. PBDE (e.g., BDE-209 26-820 ng g(-1) dry weight (dw)) and PFAS levels (e.g., PFOS 3.8-2400 ng g(-1) (dw)) in dust were consistent with those previously reported in homes and offices from Australia, reflecting consumer products and materials of the host nation. The levels of PBDEs and PFASs in wastewater (e.g., BDE-209 71-400 ng L(-1)) were in the upper range of concentrations reported for secondary treatment plants in other parts of the world. The chemical profiles of some PFAS samples were, however, different from domestic profiles. Dispersal of chemicals into the immediate marine and terrestrial environments was investigated by analysis of abiotic and biotic matrices. Analytes showed decreasing concentrations with increasing distance from the station. This study provides the first evidence of PFAS input to Polar regions via local research stations and demonstrates the introduction of POPs recently listed under the Stockholm Convention into the Antarctic environment through local human activities.

Serum perfluoroalkyl acids and time to pregnancy in nulliparous women.

BACKGROUND: Previous studies on the exposure to perfluoroalkyl acids (PFAAs) and female fertility have provided conflicting results. We aimed to investigate the association between several PFAAs and time to pregnancy among nulliparous women. METHODS: From 2008 to 2013, we included 1372 women from the Aarhus Birth Cohort, Aarhus University Hospital, Denmark, who provided data on time to pregnancy and a blood sample before 20 gestational weeks. We measured the levels of 16 PFAAs in maternal serum and report data for seven compounds with quantifiable values in at least 50% of samples. Fecundability ratios according to PFAA levels (quartiles or continuous levels) were estimated by discrete-time survival analyses, adjusted for potential confounders. We further investigated the association between PFAAs and infertility (time to pregnancy>12 months or infertility treatment prior to the studied pregnancy) by multivariable logistic regression. RESULTS: Median levels of perfluorooctane sulfonate and perfluorooctanoate were 8.3 and 2.0 ng/mL. Overall, no obvious associations were found between any PFAAs and fecundability or infertility. Adjusted fecundability ratios (95% confidence intervals) were 1.09 (0.92-1.29) for perfluorooctane sulfonate and 1.10 (0.93-1.30) for perfluorooctanoate (highest versus lowest quartile). CONCLUSIONS: We found no evidence of an association between present serum levels of PFAAs and longer time to pregnancy or infertility in nulliparous women. This study further adds to the sparse knowledge on PFAAs besides perfluorooctane sulfonate and perfluorooctanoate.

Chlorhexidine in cosmetic products - a market survey.

BACKGROUND: Chlorhexidine may cause type I and type IV allergy. Some chlorhexidine-allergic individuals have been exposed in the healthcare setting as patients or healthcare workers, but for others the source of sensitization is unknown. Chlorhexidine may be used as a preservative or an antimicrobial agent in cosmetic products at a concentration up to 0.3%, as set by the European Cosmetics Directive (now Regulations). OBJECTIVES: To identify cosmetic product types containing chlorhexidine, and to measure the concentration of chlorhexidine in selected products. METHODS: Between February 2013 and April 2013, we checked for chlorhexidine in cosmetic products in 14 supermarkets, one hairdressing salon and one beauty and retail store in Copenhagen, Denmark by reading the ingredient labels. The chlorhexidine concentration was measured in 10 selected products by high-performance liquid chromatography (HPLC) with an ultraviolet (UV) detector. RESULTS: Chlorhexidine was found in 80 of 2251 checked products (3.6%) in the following categories: hair products (57/760), creams (9/324), face washes (4/24), wet wipes (4/63), skin tonics (3/22), make-up removers (2/25), and mouth washes (1/17). Chlorhexidine concentrations were 0.01-0.15%. CONCLUSIONS: We found chlorhexidine in various cosmetic product types, predominantly aimed at females, and in hair products. The measured chlorhexidine concentrations were all within the permitted limit. The relevance for allergic sensitization should be further explored.

Methylisothiazolinone and benzisothiazolinone are widely used in paint: a multicentre study of paints from five European countries.

BACKGROUND: In view of the current epidemic of contact allergy to methylisothiazolinone (MI), it is important to clarify the extent of use of MI and related isothiazolinones in paints currently available for the consumer and worker in Europe. OBJECTIVES: To elucidate the use and concentrations of MI, methylchloroisothiazolinone (MCI) and benzisothiazolinone (BIT) in paints on the European retail market. METHODS: Wall paints (n = 71) were randomly purchased in retail outlets in five European countries. The paints were quantitatively analysed for their contents of MI, MCI and BIT by high-performance liquid chromatography coupled to tandem mass spectrometry. RESULTS: MI was found in 93.0% (n = 66) of the paints, with concentrations ranging from 0.7 to 180.9 ppm, MCI in 23.9% (n = 17), ranging from 0.26 to 11.4 ppm, and BIT in 95.8% (n = 68), ranging from 0.1 to 462.5 ppm. High concentrations of MI were found in paints from all five countries. Paints purchased in Denmark and Sweden contained especially high concentrations of BIT. CONCLUSION: The use of MI across European countries is extensive. In view of the ongoing epidemic of MI contact allergy, an evaluation of the safety of MI in paints is needed.

Prenatal exposure to perfluoroalkyl substances and the risk of congenital cerebral palsy in children.

Perfluoroalkyl substances (PFASs) are persistent pollutants and endocrine disruptors that may affect fetal brain development. We investigated whether prenatal exposure to PFASs increases the risk of congenital cerebral palsy (CP). The source population for this study includes 83,389 liveborn singletons and mothers enrolled in the Danish National Birth Cohort during 1996-2002. We identified 156 CP cases by linking the cohort to the Danish National Cerebral Palsy Register, and we randomly selected 550 controls using a case-cohort design. We measured 16 PFASs in maternal plasma collected in early or midpregnancy, and 6 PFASs were quantifiable in more than 90% of the samples. We found a higher risk of CP in boys with higher maternal PFAS levels; per 1-unit (natural-log ng/mL) increase, the risk ratios were 1.7 (95% confidence interval: 1.0, 2.8) for perfluorooctane sulfonate and 2.1 (95% confidence interval: 1.2, 3.6) for perfluorooctanoic acid. We also observed a dose-response pattern of CP risk in boys per quartile of maternal level of perfluorooctane sulfonate and perfluorooctanoic acid (P for trend < 0.01). PFASs were associated with both unilateral and bilateral spastic CP subphenotypes. No association between PFASs and CP was found in girls. Prenatal exposures to PFASs may increase the risk of CP in boys, but the finding is novel and replication is needed.

Breast cancer risk after exposure to perfluorinated compounds in Danish women: a case-control study nested in the Danish National Birth Cohort.

OBJECTIVE: Animal studies have indicated that perfluoroalkylated substances (PFAS) increase mammary fibroadenomas. A recent case-control study in Greenlandic Inuit women showed an association between the PFAS serum levels and breast cancer (BC) risk. The present study evaluates the association between serum levels of PFAS in pregnant Danish women and the risk of premenopausal BC during a follow-up period of 10-15 years using prospectively collected exposure data during the pregnancy. METHODS: Questionnaire and blood samples were taken during 1996-2002 and at the end of follow-up, all 250 BC cases and 233 frequency-matched controls were chosen for further analyses. Serum levels of ten perfluorocarboxylated acids, five perfluorosulfonated acids, and one sulfonamide (perflurooctane-sulfonamide, PFOSA) were determined by liquid chromatography-tandem mass spectrometry with electrospray ionization in negative mode. Computer-assisted telephone interviews taken during pregnancy provided data on potential confounders. RESULTS: Weak positive and negative insignificant associations were found between BC risk and levels of perfluorooctane sulfonamide (PFOSA) and perfluorohexanesulfonate (PFHxS), respectively. Grouped into quintile, the BC cases had a significant positive association with PFOSA at the highest quintiles and a negatively association for PFHxS. Sensitivity analyses excluding uncertain cases caused stronger data for PFOSA and weaker for PFHxS. No further significant associations were observed. CONCLUSIONS: This study does not provide convincing evidence for a causal link between PFAS exposures and premenopausal BC risks 10-15 years later.

Emission of isothiazolinones from water-based paints.

The isothiazolinone preservatives methylisothiazolinone (MI), methylchloroisothiazolinone (MCI), and benzisothiazolinone (BIT) are used in a wide variety of products including paint and cosmetics, and they are known to cause allergic contact dermatitis. Among painters they are one of the most common causes of contact dermatitis. Furthermore, they are all volatile, and severe reactions caused by emissions of especially MI from paint have been reported recently. In this study the concentrations of MI, BIT, and MCI in water-based paint were analyzed by LC-MS-MS, and the emissions from the paints were measured in climate chambers and in an apartment. Nineteen paints were analyzed for the content of MI, MCI, and BIT. All 19 paints contained MI, 16 contained BIT, and 4 contained MCI. In the chamber experiment emission of MI peaked within hours of application but then continued at a slow rate for more than 42 days. MCI was emitted more slowly and peaked after several days. BIT emissions were all around the limit of detection. In the apartment we were able to detect emission of MI several days after application. Long lasting evaporation and thus chronic exposure give credibility to the clinical observations that MI can be an important cause of airborne contact dermatitis among painters and consumers.

Endocrine-disrupting effects of compounds in Danish streams.

Effluents from municipal wastewater-treatment plants and scattered dwellings, as well as runoff from agricultural fields, are sources of endocrine-disrupting compounds (EDCs) in the aquatic environment. The present study investigated the correlation between the occurrence of EDCs in nine Danish streams using passive samplers (polar organic integrative samplers and silicone membranes) and determined their possible biological effects as assessed by mammal cell cultures and the mussel (Unio tumidus). The passive samplers and mussels were exposed simultaneously at the study sites. The extracts from the passive samplers were used to measure the concentrations of EDCs and the biological effects on the estrogen (ER), androgen (AR), and aryl hydrocarbon (AhR)-receptor transactivation. Male mussels were investigated for biomarkers of endocrine effects, such as the levels of vitellogenin-like proteins measured as alkali-labile phosphate (ALP). EDC concentrations, hormone-receptor transactivation (ER, AR, AhR), and level of ALP were greater downstream of wastewater-treatment plants compared with upstream sites and sites supposed to be relatively nonimpacted by wastewater. Furthermore, there was a significant positive correlation between in vitro AhR transactivation and frequency of ALP of male mussels. We conclude that wastewater effluent is an important source of endocrine-disrupting effects in the aquatic environment and that the combination of biological effect measurements and chemical analyses based on passive sampling is useful in the assessment of the ecological state of the aquatic environment.

Chemical threats for the sentinel Pygoscelis adeliae from the Ross Sea (Antarctica): Occurrence and levels of persistent organic pollutants (POPs), perfluoroalkyl substances (PFAS) and mercury within the largest marine protected area worldwide.

The Ross Sea Marine Protected Area (RS-MPA) hosts endemic species that have to cope with multiple threats, including chemical contamination. Adèlie penguin is considered a good sentinel species for monitoring pollutants. Here, 23 unhatched eggs, collected from three colonies along the Ross Sea coasts, were analysed to provide updated results on legacy pollutants and establish a baseline for newer ones. Average sum of polychlorinated biphenyls (∑PCBs) at the three colonies ranged 20.9-24.3 ng/g lipid weight (lw) and included PCBs IUPAC nos. 28, 118, 153, 138, 180. PCBs were dominated by hexachlorinated congeners as previously reported. Hexachlorobenzene (HCB) and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) ranged between 134 and 166 and 181-228 ng/g lw, respectively. Overall, ∑PCBs was exceeded by pesticides, contrary to previous studies from the Ross Sea. Sum of polybrominated diphenyl ethers (∑PBDEs) ranged between 0.90 and 1.18 ng/g lw and consisted of BDE-47 (that prevailed as expected, representing 60-80 % of the ∑PBDEs) and BDE-85. Sum of perfluoroalkyl substances (∑PFAS) ranged from 1.04 to 1.53 ng/g wet weight and comprised five long-chain perfluorinated carboxylic acids (PFCAs), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) and perfluorooctanoic acid (PFOA); perfluorooctane sulfonamide (PFOSA) was also detected. The PFAS profile was dominated by PFCAs as already observed in Arctic seabirds. Mercury ranged from 0.07 to 0.15 mg/kg dry weight similarly to previous studies. Legacy pollutants confirmed their ongoing presence in Antarctic biota and their levels seemed mostly in line with the past, but with minor variations in some cases, likely due to continued input or release from past reservoirs. PFAS were reported for the first time in penguins from the Ross Sea, highlighting their ubiquity. Although further studies would be useful to increase the sample size and accordingly improve our knowledge on spatial and temporal trends, this study provides interesting data for future monitoring programs within the RS-MPA that will be crucial to test its effectiveness against human impacts.

Suspect and non-target screening of chemicals of emerging Arctic concern in air, biota and human serum.

Contaminants of emerging concern receive increasing attention in the Arctic environment. The aim of this study was to screen for chemicals of emerging Arctic concern (CEACs) in different types of Arctic samples including biota, air and human serum. We used a combination of gas chromatography (GC) and liquid chromatography (LC) with high resolution mass spectrometry (HRMS) for suspect and non-target screening (NTS). Suspect screening of 25 CEACs was based on published in-silico approaches for the identification of CEACs and revealed tetrabromophthalic anhydride (TBPA) in pilot whale and air, albeit with low detection frequencies (17 and 33%, respectively). An NTS workflow detected a total of 112 contaminants, i.e. 49, 42, 31 and 30 compounds in pilot whale, ringed seal, air, and human serum respectively at confidence level 2 and 3. Although legacy POPs still dominated the samples, 64 CEACs were tentatively identified and further tentatively assessed for persistence (P), bioaccumulation (B), mobility (M), toxicity (T), and long-range transport potential (LRTP). While four PBT compounds were identified, 37 PMT substances dominated among these 64 contaminants. Our study indicated that many chemicals of potential risk might be present in Arctic samples that would benefit from confirmation and further studies of their transport to and accumulation in the Arctic environment.

In vitro-in vivo correlations for endocrine activity of a mixture of currently used pesticides.

Two pesticide mixtures were investigated for potential endocrine activity. Mix 3 consisted of bitertanol, propiconazole, and cypermethrin, and Mix 5 included malathion and terbuthylazine in addition to the three pesticides in Mix 3. All five single pesticides and the two mixtures were investigated for their ability to affect steroidogenesis in vitro in H295R cells. The pesticides alone and both mixtures affected steroidogenesis with both mixtures causing increase in progesterone and decrease in testosterone. For Mix 5 an increase in estradiol was seen as well, indicating increased aromatase activity. The two mixtures were also investigated in pregnant rats dosed from gestational day 7 to 21, followed by examination of dams and fetuses. Decreased estradiol and reduced placental testosterone were seen in dams exposed to Mix 5. Also a significant increase in aromatase mRNA-levels in female adrenal glands was found for Mix5. However, either of the two mixtures showed any effects on fetal hormone levels in plasma or testis, or on anogenital distance. Overall, potential aromatase induction was found for Mix 5 both in vitro and in vivo, but not for Mix 3, an effect likely owed to terbuthylazine in Mix 5. However, the hormonal responses in vitro were only partly reflected in vivo, probably due to some toxicokinetic issues, as the pesticide levels in the amniotic fluid also were found to be negatively affected by the number of compounds present in the mixtures. Nonetheless, the H295R assay gives hints on conceivable interference with steroidogenesis, thus generating hypotheses on in vivo effects.