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Many legacy and emerging flame retardants (FRs) have adverse human and environmental health effects. This study reports legacy and emerging FRs in children from nine European countries from the HBM4EU aligned studies. Studies from Belgium, Czech Republic, Germany, Denmark, France, Greece, Slovenia, Slovakia, and Norway conducted between 2014 and 2021 provided data on FRs in blood and urine from 2136 children. All samples were collected and analyzed in alignment with the HBM4EU protocols. Ten halogenated FRs were quantified in blood, and four organophosphate flame retardants (OPFR) metabolites quantified in urine. Hex-abromocyclododecane (HBCDD) and decabromodiphenyl ethane (DBDPE) were infrequently detected (< 16% of samples). BDE-47 was quantified in blood from Greece, France, and Norway, with France (0.36 ng/g lipid) having the highest concentrations. BDE-153 and-209 were detected in < 40% of samples. Dechlorane Plus (DP) was quantified in blood from four countries, with notably high median concentrations of 16 ng/g lipid in Slovenian children. OPFR metabolites had a higher detection frequency than other halogenated FRs. Diphenyl phosphate (DPHP) was quantified in 99% of samples across 8 countries at levels similar to 5 times higher than other OPFR metabolites (highest median in Slovenia of 2.43 ng/g lipid). FR concentrations were associated with lifestyle factors such as cleaning frequency, employment status of the father of the household, and renovation status of the house, among others. The concentrations of BDE-47 in children from this study were similar to or lower than FRs found in adult matrices in previous studies, suggesting lower recent exposure and effectiveness of PBDE restrictions.

Polycyclic aromatic hydrocarbons (PAHs) and their alkylated (RPAHs), nitrated (NPAHs) and oxygenated (OPAHs) derivatives are air pollutants. Many of these substances are long-lived, can undergo long-range atmospheric transport and adversely affect human health upon exposure. However, the occurrence and fate of these air pollutants have hardly been studied in the marine atmosphere. In this study, we report the atmospheric concentrations over the Mediterranean Sea, the Red Sea, the Arabian Sea, the Gulf of Oman and the Arabian Gulf, determined during the AQABA (Air Quality and Climate Change in the Arabian Basin) project, a comprehensive ship-borne campaign in summer 2017. The average concentrations of ∑26PAHs, ∑19RPAHs, ∑11OPAHs and ∑17NPAHs, in the gas and particulate phases, were 2.99 ± 3.35 ng m−3, 0.83 ± 0.87 ng m−3, 0.24 ± 0.25 ng m−3 and 4.34 ± 7.37 pg m−3, respectively. The Arabian Sea region was the cleanest for all substance classes, with concentrations among the lowest ever reported. Over the Mediterranean Sea, we found the highest average burden of ∑26PAHs and ∑11OPAHs, while the ∑17NPAHs were most abundant over the Arabian Gulf (known also as the Persian Gulf). 1,4-Naphthoquinone (1,4-O2NAP) followed by 9-fluorenone and 9,10-anthraquinone were the most abundant studied OPAHs in most samples. The NPAH composition pattern varied significantly across the regions, with 2-nitronaphthalene (2-NNAP) being the most abundant NPAH. According to source apportionment investigations, the main sources of PAH derivatives in the region were ship exhaust emissions, residual oil combustion and continental pollution. All OPAHs and NPAHs except 2-nitrofluoranthene (2-NFLT), which were frequently detected during the campaign, showed elevated concentrations in fresh shipping emissions. In contrast, 2-NFLT and 2-nitropyrene (2-NPYR) were highly abundant in aged shipping emissions due to secondary formation. Apart from 2-NFLT and 2-NPYR, benz(a)anthracene-7,12-dione and 2-NNAP also had significant photochemical sources. Another finding was that the highest concentrations of PAHs, OPAHs and NPAHs were found in the sub-micrometre fraction of particulate matter (PM1).

International audience; For decades pesticides have been used in agriculture, however, the occurrence of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) is poorly understood in Africa. This study investigates air concentrations of OCPs and CUPs in three South African agricultural areas, their spatial/seasonal variations and mixture profiles.Between 2017 and 2018, 54 polyurethane foam-disks passive air-samplers (PUF-PAS) were positioned in three agricultural areas of the Western Cape, producing mainly apples, table grapes and wheat. Within areas, 25 CUPs were measured at two sites (farm and village), and 27 OCPs at one site (farm). Kruskal-Wallis tests investigated area differences in OCPs concentrations, and linear mixed-effect models studied differences in CUPs concentrations between areas, sites and sampling rounds.In total, 20 OCPs and 16 CUPs were detected. A median of 16 OCPs and 10 CUPs were detected per sample, making a total of 11 OCPs and 24 CUPs combinations. Eight OCPs (trans-chlordane, o,p’-/p,p’-dichlorodiphenyldichloroethylene (DDE)/dichlorodiphenyltrichloroethane (DDT), endosulfan sulfate, γ-hexachlorocyclohexane and mirex) and two CUPs (carbaryl and chlorpyrifos) were quantified in all samples. p,p’-DDE (median 0.14 ng/m3) and chlorpyrifos (median 0.70 ng/m3) showed the highest concentrations throughout the study. Several OCPs and CUPs showed different concentrations between areas and seasons, although CUPs concentrations did not differ between sites. OCPs ratios suggest ongoing chlordane use in the region, while DDT and endosulfan contamination result from past-use.Our study revealed spatial and seasonal variations of different OCPs and CUPs combinations detected in air. Further studies are needed to investigate the potential cumulative or synergistic risks of the detected pesticides.

Endocrine-disrupting chemicals (EDCs) in diet are a health concern and their monitoring in food has been introduced in the European Union. In developing countries, EDC dietary exposure data are scarce, especially from areas perceived as pollution hotspots, including industrialized countries like India. Several persistent organic pollutants (POPs) act as EDCs and pose a pressure to human health mainly through dietary exposure. In the present study, a range of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), dioxins and furans were measured in several food items collected from Indian urban (Delhi) and peri-urban (Dehradun) areas. Food basket contamination data were used to estimate EDC dietary exposure and compare it with that of the average European population estimated from available monitoring data. All the target contaminants were found in most food items, especially in dairies and meat products. OCPs were the main contributers to the measured EDC contamination. Food supplied to Delhi's markets had higher EDC contamination than that supplied to the peri-urban market in Dehradun. Despite lax compliance and control measures, Indian dietary exposure of OCPs and PBDEs were comparable with that of Europe and were lower for PCBs and dioxins. Higher meat consumption in Europe only partly explained this pattern which was driven also by the higher EDC residues in some European food items. A substantial part of endocrine disrupting potential in the diet derives from food and animal feeds internationally traded between developed and developing countries. With increasingly globalized food systems, internationally harmonized policies on EDC content in food can lead to better protection of health in both these contexts.

In this study, 10 polybrominated diphenyl ethers (PBDEs) and 19 alternative halogenated flame retardants (AFRs) were determined in >450 human milk samples across three European countries, representing northern, western and eastern Europe. This study provides first insights into the occurrence of selected AFRs in mother milk samples and compares them among three European countries. Sums of median concentrations of the most frequently detected PBDEs were 2.16, 0.88 and 0.45ngg−1 lipid weight (lw) in Norway, the Netherlands and Slovakia, respectively. The sum of the concentrations of AFRs ranged from 0.14 to 0.25ngg−1lw in all countries, which was 2 to 15 times less compared to Σ7PBDEs. The Penta-BDE replacement, bis(2-ethylhexyl) tetrabromophthalate, BEH-TEBP, was present at the greatest concentrations of any of the AFRs and in some samples exceeded concentrations of BDE 47 and BDE 153. Four AFRs including bromobenzenes (hexabromobenzene, pentabromobenzene, pentabromotoluene) and another Penta-BDE replacement (2-ethylhexyl-2,3,4,5-tetrabromobenzoate, EH-TBB) were detected in >42% of all human milk samples. Because of the potential developmental neurotoxicity of the halogenated flame retardants, infant dietary intakes via breastfeeding were estimated; in four cases the intakes of BDE 47 exceeded the reference dose indicating that the present concentrations may pose a risk for children. Keywords: Alternative flame retardants, Developmental neurotoxicants, Human milk, Infant exposure, Polybrominated diphenyl ethers

The increasing number of children suffering from developmental disorders has raised questions regarding their association with the presence of environmental contaminants in mothers and children. We therefore developed a new method for the determination of 78 proven and potential developmental neurotoxicants, including polychlorinated biphenyls, legacy pesticides, pyrethroids, and old and new halogenated flame retardants in breast milk. The essential part of sample preparation was dialysis as a non-destructive clean-up step which was newly used at 10 °C and showed more efficient lipid removal (up to 96%) than the conventional methods such as gel permeation chromatography or freezing-lipid filtration and thus ensured low limits of detection (LOD) by reducing the sample volume prior to injection. Next advantages were significant solvent reduction and no risk of sample cross-contamination. Gas chromatography coupled with high resolution mass spectrometry (GC-HRMS) was subsequently used for the separation and compound quantification. The method was validated using breast milk samples fortified with the analyzed compounds. Recoveries for most of the compounds ranged from 63 to 121% with a relative standard deviation of 2-25%, and LODs ranged between 0.001 and 0.87 ng g(-1) lipid weight. The method was applied to breast milk samples from a Dutch birth cohort where 35 out of the 78 compounds were quantified in more than 60% of the samples. For novel flame retardants, the method provides unique results regarding their occurrence in human matrices in Europe. Overall, the analysis of a complex mixture of developmental neurotoxicants could be useful for the assessment of the influence of the studied compounds to child health and development. Graphical abstract Flow diagram of the method and levels of the developmental neurotoxicants in Dutch human milk samples., Funding Agencies:"Employment of Best Young Scientists for International Cooperation Empowerment" - European Social Fund CZ.1.07/2.3.00/30.0037Sate budget of the Czech RepublicCzech Ministry of Education, Youth and Sports LO1214 LM 2015051

Near-ground air (26 substances) and surface seawater (55 substances) concentrations of persistent toxic substances (PTS) were determined in July 2012 in a coordinated and coherent way around the Aegean Sea based on passive air (10 sites in 5 areas) and water (4 sites in 2 areas) sampling. The direction of air–sea exchange was determined for 18 PTS. Identical samplers were deployed at all sites and were analysed at one laboratory. hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs) as well as dichlorodiphenyltrichloroethane (DDT) and its degradation products are evenly distributed in the air of the whole region. Air concentrations of p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) and o,p′-DDT and seawater concentrations of p,p′-DDE and p,p′-DDD were elevated in Thermaikos Gulf, northwestern Aegean Sea. The polychlorinated biphenyl (PCB) congener pattern in air is identical throughout the region, while polybrominated diphenylether (PBDE)patterns are obviously dissimilar between Greece and Turkey. Various pollutants, polycyclic aromatic hydrocarbons (PAHs), PCBs, DDE, and penta- and hexachlorobenzene are found close to phase equilibrium or net-volatilisational (upward flux), similarly at a remote site (on Crete) and in the more polluted Thermaikos Gulf. The results suggest that effective passive air sampling volumes may not be representative across sites when PAHs significantly partitioning to the particulate phase are included., Granting Agency of the Czech Republic (312334); Czech Ministry of Education (LO1214--LM2011028); European Social Fund (CZ.1.07/2.3.00/30.0037); European Commission FP7 (262254 ACTRIS)

Despite the fact that the occurrence of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric environment has been studied for decades the photochemistry, deposition and, consequently, the long-range transport potential (LRTP) are not well understood. The reason is gas-particle partitioning (GPP) in the aerosol, its sensitivity to temperature and particulate phase composition, and sampling artefacts', and reactivity's sensitivities towards particulate phase composition. Furthermore, most PAHs are subject to re-volatilisation upon deposition to surfaces (multihopping). Levels and sources of 2-6-ring unsubstituted PAHs were studied in remote environments of Europe, Africa and Antarctica. Global atmospheric transport and fate of 3-5-ring PAHs were simulated under various scenarios of photochemistry and GPP. GPP influences drastically the atmospheric lifetime, compartmental distributions and the LRTP of PAH. Mid latitude emissions seem to reach the Arctic but not the Antarctic.

Polycyclic aromatic hydrocarbon (PAH) concentration in air of the central and eastern Mediterranean in summer 2010 was 1.45 (0.30–3.25) ng m−3 (sum of 25 PAHs), with 8 (1–17)% in the particulate phase, almost exclusively associated with particles < 0.25 μm. The total deposition flux of particulate PAHs was 0.3–0.5 μ g m−2 yr−1. The diffusive air–sea exchange fluxes of fluoranthene and pyrene were mostly found net-depositional or close to phase equilibrium, while retene was net-volatilisational in a large sea region. Regional fire activity records in combination with box model simulations suggest that seasonal depositional input of retene from biomass burning into the surface waters during summer is followed by an annual reversal of air–sea exchange, while interannual variability is dominated by the variability of the fire season. One-third of primary retene sources to the sea region in the period 2005–2010 returned to the atmosphere as secondary emissions from surface seawaters. It is concluded that future negative emission trends or interannual variability of regional sources may trigger the sea to become a secondary PAH source through reversal of diffusive air–sea exchange. Capsule: In late summer the seawater surface in the Mediterranean has turned into a temporary secondary source of PAH, obviously related to biomass burning in the region.

Air-sea exchange and gas particle partitioning of polycyclic aromatic hydrocarbons in the Mediterranean (vol 14, pg 8905, 2014)

Despite the fact that most persistent toxic substances have hardly been primarily emitted for several decades, their concentrations are only slowly decreasing in the global oceans. Surface seawater samples were collected along a 38°–24° N/28°–67° W transect in the subtropical North Atlantic Ocean. While the concentration levels of hexachlorobenzene (2.1–6.1 pg L−1), dichlorodiphenyltrichloroethane (DDT, up to 2.1 pg L−1) and polychlorinated biphenyls (PCB, 10.8–24.9 pg L−1) were in the same range as observed earlier in the North Atlantic, hexachlorocyclohexane (HCH, 90–627 pg L−1) was found elevated, partly also relative to previous measurements in the same sea region. Hereby, the ratio α-HCH/γ-HCH was very low, 0.09–0.13. Chlordane and endosulfan were found in the range

Background Air pollution, which represents a major environmental risk to human health, comprises a complex mixture of compounds where only little is known about its specific toxicities. Objectives This study examined the specific toxicities associated with ambient air pollutant mixtures with respect to gas/particle partitioning, particulate matter (PM) size, pollutant polarity and bioaccessibility from PM, and evaluated the contribution of PAHs and their oxygenated and nitrated derivatives (OPAHs, NPAHs). Methods Air samples (gas phase, PM10 and size-segregated PM), were collected at urban (in winter and summer) and background (winter) sites in the Czech Republic. The total and bioaccessible concentrations were addressed using organic solvent extraction and simulated lung fluid extraction, respectively. Organic extracts were also further fractionated according to polarity. Aryl hydrocarbon receptor (AhR)-mediated activity, anti-/estrogenicity, anti-/androgenicity, thyroid receptor (TR)-mediated activity and cytotoxicity for bronchial cells were determined by human cell-based in vitro bioassays. The contribution of studied compounds to observed effects was assessed by both modelling and reconstructing the mixtures. Results Significant effects were detected in the sub-micrometre size fraction of PM (estrogenicity, androgenicity, TR- and AhR-mediated activities) and in the gas phase (TR-mediated activity, antiandrogenicity). Compounds interacting with TR showed high bioaccessibility to simulated lung fluid. Relatively lower bioaccessibility was observed for estrogenicity and AhR-mediated activity. However, the toxicity testing of reconstructed mixtures revealed that the targeted pollutants are not the main contributors, except for urban PM air pollution in winter, where they accounted for 5–88% of several effects detected in the original complex environmental samples. Discussion Studied toxicities were mostly driven by polar compounds largely attributed to the easily inhalable PM1, which is of high relevance for human health risk assessment. Except of parent PAHs in some cases, the targeted compounds contributed to the detected effects mostly to a relatively low extent implying huge data gaps in terms of endocrine disruptive potencies of targeted substances and the significance of other polar compounds present in ambient air.