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Perfluoroalkyl acids (PFAAs) are synthetic chemicals with a variety of industrial and consumer applications that are now widely distributed in the global environment. Here, we report the measurement of six perfluorocarboxylates (PFCA, C4–C9) in a firn (granular compressed snow) core collected from a non-coastal, high-altitude site in Dronning Maud Land in Eastern Antarctica. Snow accumulation of the extracted core dated from 1958 to 2017, a period coinciding with the advent, use, and geographical shift in the global industrial production of poly/perfluoroalkylated substances, including PFAA. We observed increasing PFCA accumulation in snow over this time period, with chemical fluxes peaking in 2009–2013 for perfluorooctanoate (PFOA, C8) and nonanoate (PFNA, C9) with little evidence of a decline in these chemicals despite supposed recent global curtailments in their production. In contrast, the levels of perfluorobutanoate (PFBA, C4) increased markedly since 2000, with the highest fluxes in the uppermost snow layers. These findings are consistent with those previously made in the Arctic and can be attributed to chlorofluorocarbon replacements (e.g., hydrofluoroethers) as an inadvertent consequence of global regulation.

Polar regions should be given greater consideration with respect to the monitoring, risk assessment, and management of potentially harmful chemicals, consistent with requirements of the precautionary principle. Protecting the vulnerable polar environments requires (i) raising political and public awareness and (ii) restricting and preventing global emissions of harmful chemicals at their sources. The Berlin Statement is the outcome of an international workshop with representatives of the European Commission, the Arctic Council, the Antarctic Treaty Consultative Meeting, the Stockholm Convention on Persistent Organic Pollutants (POPs), environmental specimen banks, and data centers, as well as scientists from various international research institutions. The statement addresses urgent chemical pollution issues in the polar regions and provides recommendations for improving screening, monitoring, risk assessment, research cooperation, and open data sharing to provide environmental policy makers and chemicals management decision-makers with relevant and reliable contaminant data to better protect the polar environments. The consensus reached at the workshop can be summarized in just two words: “Act now!” Specifically, “Act now!” to reduce the presence and impact of anthropogenic chemical pollution in polar regions by. •Establishing participatory co-development frameworks in a permanent multi-disciplinary platform for Arctic-Antarctic collaborations and establishing exchanges between the Arctic Monitoring and Assessment Program (AMAP) of the Arctic Council and the Antarctic Monitoring and Assessment Program (AnMAP) of the Scientific Committee on Antarctic Research (SCAR) to increase the visibility and exchange of contaminant data and to support the development of harmonized monitoring programs. •Integrating environmental specimen banking, innovative screening approaches and archiving systems, to provide opportunities for improved assessment of contaminants to protect polar regions.

Chemical pollution is hypothesized as one of the factors driving the strong decline of the critically endangered European eel population. Specifically the impact of contaminants on the quality of spawning eels and subsequent embryo survival and development has been discussed as crucial investigation point. However, so far only very limited information on potential negative effects of contaminants on the reproduction of eels is available. Through the combination of non-targeted ultra-high resolution mass spectrometry and multidimensional gas chromatography, combined with more conventional targeted analytical approaches, compounds of particular relevance and their maternal transfer in artificially matured European eels from the German river Ems have been identified. Substituted diphenylamines were, unexpectedly, found to be the primary organic contaminants in the eel samples, with concentrations exceeding 10 µg g-1 ww. Furthermore, it could be shown that these contaminants, as well as known contaminants in eel such as polychlorinated biphenyls (PCBs), organochlorine pesticides and polyaromatic hydrocarbons (PAHs), are not merely stored in lipid rich tissue of eels, but maternally transferred into gonads and eggs. The results of this study provide unpreceded information on both the fate and behavior of substituted diphenylamines in the environment as well as their relevance as contaminants in European eels.

Poly- and perfluoroalkyl substances are synthetic chemicals that are widely present in the global environment including the Arctic. However, little is known about how these chemicals (particularly perfluoroalkyl acids, PFAA) enter the Arctic marine system and cycle between seawater and sea ice compartments. To evaluate this, we analyzed sea ice, snow, melt ponds, and near-surface seawater at two ice-covered stations located north of the Barents Sea (81 °N) with the aim of investigating PFAA dynamics in the late-season ice pack. Sea ice showed high concentrations of PFAA particularly at the surface with snow-ice (the uppermost sea ice layer strongly influenced by snow) comprising 26–62% of the total PFAA burden. Low salinities (, Sea ice accumulates perfluoroalkyl acids (PFAAs) from seawater and from atmospheric deposition in snow. Subsequent melting of surface ice layers through seasonal changes later results in high PFAA concentrations in the under-ice seawater.

Only a few dozens of the several thousand existing per- and polyfluoroalkyl substances (PFAS) are monitored using conventional target analysis. This study employed suspect screening to examine patterns of emerging and novel PFAS in German and Chinese river water affected by industrial point sources. In total, 86 PFAS were (tentatively) identified and grouped into 18 structure categories. Homologue patterns revealed distinct differences between fluoropolymer production sites of the two countries. In the Chinese Xiaoqing River Basin, the C

We examined recent atmospheric mercury concentrations measured with a high temporal resolution of 15 min at Mace Head, a GAW station on the western coast of Ireland. We attributed a direct contribution of 34 % (0.44 ng m−3) to primary sources. Additionally, a steep decline (0.05 ng yr−1) in mercury concentrations was observed between 2013 and 2018. Using a stereo algorithm we reconstructed 99.9 % of the atmospheric mercury. A conservative analysis demonstrated no decrease in total gaseous mercury (TGM) associated with atmospheric species typically used as tracers for oceanic emissions. The results show that the atmospheric mercury mass is mainly loaded in a baseline factor with an ongoing decline. Moreover, we exploit temporal variation and wind pattern effects in the measured atmospheric species; the results show that the diurnal variation and seasonality in TGM observed in Mace Head are closely related to other species linked to primary sources and can be explained by transport from continental areas.

The presence of numerous emerging organic contaminants (EOCs) and remobilization of legacy persistent organic pollutants (POPs) in polar regions have become significant concerns of the scientific communities, public groups and stakeholders. This work reviews the occurrences of EOCs and POPs and their long-range environmental transport (LRET) processes via atmosphere and ocean currents from continental sources to polar regions. Concentrations of classic POPs have been systematically monitored in air at several Arctic stations and showed seasonal variations and declining trends. These chemicals were also the major POPs reported in the Antarctica, while their concentrations were lower than those in the Arctic, illustrating the combination of remoteness and lack of potential local sources for the Antarctica. EOCs were investigated in air, water, snow, ice and organisms in the Arctic. Data in the Antarctica are rare. Reemission of legacy POPs and EOCs accumulated in glaciers, sea ice and snow may alter the concentrations and amplify their effects in polar regions. Thus, future research will need to understand the various biogeochemical and geophysical processes under climate change and anthropogenic pressures.

Systemic insecticides like neonicotinoids and the phenylpyrazole insecticide fipronil are the most widely applied insecticides around the world. Multiple studies analyzed insecticide residues in freshwater systems, but data on seawater contamination levels are scarce. This study investigates the spatiotemporal distribution and ecological risk assessment of fipronil, neonicotinoids, sulfoxaflor and selected transformation products (TPs) in the Chinese Bohai Sea and its surrounding rivers. Well-established neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam) and TPs of fipronil and imidacloprid were frequently detected (detection frequency (DF): 42-100%) in freshwater. The median total insecticide concentration in freshwater was significantly higher in summer (72.4 ng•L-1) than in fall (23.4 ng•L-1), with major contributions from neonicotinoids, suggesting that pollution originates mostly from diffuse sources. In 2018, acetamiprid, desnitro-imidacloprid, fipronil-desulfinyl and thiacloprid were abundant in seawater (DF: 47-100%), indicating a high stability of acetamiprid and thiacloprid and a rapid photodegradation of fipronil and imidacloprid in surface waters. These results indicate that the continued use of these parent compounds may lead to their accumulation and/or of their TPs in shallow coastal seas. Consequently, this may lead to their transport to open seas, increasing their potential risk to marine organisms. Similarities between contaminant fingerprints in freshwater and seawater strongly suggest riverine discharges as main pollution source of adjacent coastal areas. This is the first study to perform an ecological risk assessment of fipronil, neonicotinoids, sulfoxaflor and selected TPs on marine ecosystems. Fipronil and its TPs demonstrated to be environmentally relevant with potential high risks for aquatic species. Our study provides novel insights into the fate and ecological risk of fipronil, neonicotinoids, sulfoxaflor and their TPs to marine species in shallow coastal seas.

The Global Monitoring Plan of the Minamata Convention on Mercury was established to generate long-term data necessary for evaluating the effectiveness of regulatory measures at a global scale. After 25 years monitoring (since 1995), Mace Head is one of the atmospheric monitoring stations with the longest mercury record, and has produced sufficient data for the analysis of temporal trends of Total Gaseous Mercury (TGM) in Europe and the Northern Atlantic. Using concentration-weighted trajectories for atmospheric mercury measured at Mace Head as well as other five locations in Europe, Amderma, Andøya, Villum, Waldhof and Zeppelin we identify the regional probabilistic source contribution factor and its changes for the period of 1996 to 2019. Temporal trends indicate that concentrations of mercury in the atmosphere in Europe and the Northern Atlantic have declined significantly over the past 25 years, at a non-monotonic rate averaging of 0.03 ng m-3 year-1. Concentrations of TGM at remote marine sites were shown to be affected by continental long-range transport, and evaluation of reanalysis back-trajectories display a significant decrease of TGM in continental air masses from Europe in the last two decades. In addition, using the relationship between mercury and other atmospheric trace gases that could serve as a source signature, we perform factorization regression analysis, based on positive rotatable factorization of non-singular matrix to solve probabilistic mass function. We reconstructed atmospheric mercury concentration and accessed the contribution of the major natural and anthropogenic sources. The positive matrix factorization (PMF) reveals that the downward trend is mainly associated with a factor with a high load of long-lived anthropogenic species.

Poly- and perfluoroalkyl substances (PFAS) are contaminants of emerging Arctic concern and are present in the marine environments of the polar regions. Their input to and fate within the marine cryosphere are poorly understood. We conducted a series of laboratory experiments to investigate the uptake, distribution, and release of 10 PFAS of varying carbon chain length (C4–C12) in young sea ice grown from artificial seawater (NaClsolution). We show that PFAS are incorporated into bulk sea ice during ice formation and regression analyses for individual PFAS concentrations in bulk sea ice were linearly related to salinity (r2 = 0.30 to 0.88, n = 18, p < 0.05). This shows that their distribution is strongly governed by the presence and dynamics of brine (high salinity water) within the sea ice. Furthermore, long-chain PFAS (C8–C12), were enriched in bulk ice up to 3-fold more than short-chain PFAS (C4–C7) and NaCl. This suggests that chemical partitioning of PFAS between the different phases of sea ice also plays a role in their uptake during its formation. During sea ice melt, initial meltwater fractions were highly saline and predominantly contained short-chain PFAS, whereas the later, fresher meltwater fractions predominantly contained long-chain PFAS. Our results demonstrate that in highly saline parts of sea ice (near the upper and lower interfaces and in brine channels) significant chemical enrichment (ε) of PFAS can occur with concentrations in brine channels greatly exceeding those in seawater from which it forms (e.g., for PFOA, εbrine = 10 ± 4). This observation has implications for biological exposure to PFAS present in brine channels, a common feature of first-year sea ice which is the dominant ice type in a warming Arctic., Poly- and perfluoroalkyl substances (PFAS) are contaminants of emerging Arctic concern yet their fate and behavior in the marine cryosphere is poorly understood. Here, laboratory experiments show that PFAS are incorporated into bulk sea ice during ice formation leading to significant chemical enrichment in brine. This has implications for biological exposure to PFAS in first-year sea ice which is the dominant ice type in a warming Arctic.

Along with the phase-out of legacy long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their precursors, attention has been drawn to emerging per- and polyfluoroalkyl substances (PFASs). This study is aimed at investigating the importance of selected emerging PFASs as pollutants in European coastal environments and a possible transition from legacy long-chain PFCAs and PFSAs to replacement compounds. Therefore, the spatial distribution of 29 PFASs was analysed in surface water and sediment of the North and Baltic Seas sampled in 2017. Levels of the replacement compound HFPO-DA were approximately three times higher than those of its predecessor PFOA in surface water from the North Sea, which is characterised by the influence of point sources and constant exchange with open water. Reanalysis of sample extracts from the last decade showed that HFPO-DA had already been present in 2011, when it had not yet been in focus. In the Baltic Sea with a limited water exchange and dominance of diffuse sources, the proportion of HFPO-DA was negligible, whereas long-chain PFCAs and PFSAs still contributed to ∑PFASs with about 30%. The emerging cyclic compound perfluoro-4-ethylcyclohexanesulfonate (PFECHS), which has not yet been reported in European coastal environments, was detected in 86% of the Baltic Sea samples. Influenced by sediment characteristics in addition to source-specific contributions, the spatial distribution of PFASs in surface sediments was more variable than for water samples. The linear isomer of the long-chain legacy substance PFOS was the predominant compound found over the entire study area. Of the emerging PFASs, 6:6 and 6:8 perfluoroalkyl phosphinic acids (PFPiAs) were identified close to potential industrial inputs and in sedimentation areas. The results show that particular emerging PFASs play a relevant role in the investigated coastal environments and that a shift to replacements is dependent on sources and geographical conditions.

Phthalate esters (PEs) are a class of synthetic chemicals that have been widely used as plasticizers in industrial products and households. The occurrence of PEs in the marine environment has been a concern for many years because of their adverse impacts on marine organisms and human health. In this study, six major PEs, i.e. diethyl phthalate (DEP), di‑isobutyl phthalate (DiBP), di‑n‑butyl phthalate (DnBP), benzylbutyl phthalate (BBP), dicyclohexyl phthalate (DCHP) and di‑(2‑ethylhexyl) phthalate (DEHP), were analyzed in sediment samples collected in the Bohai and Yellow seas. The sum concentrations of the six PEs ranged from 1.4 to 24.6 ng/g and the average was 9.1 ng/g. The highest concentrations of PEs in the sediment samples were those of DEHP with a median concentration of 3.77 ng/g, followed by DiBP (median, 1.60 ng/g), DnBP (0.91 ng/g), DEP (0.32 ng/g), BBP (0.03 ng/g) and DCHP (0.01 ng/g). Generally, concentrations of PEs in the Bohai Sea are higher than those in the Yellow Sea. The varying spatial distributions of the individual PEs can be the result of discharge sources, regional ocean circulation patterns, and mud areas in the Bohai and Yellow seas. Significant positive correlations were found between total organic carbon content and the concentrations of DiBP, DnBP, and DEHP. It is estimated that the inventories of the ∑6PEs were 20.73 tons in the Bohai Sea and 65.87 tons in the Yellow Sea. Both riverine discharge and atmospheric deposition are major input sources for the PE sedimentation, while massive plastic litter and microplastics sinking to the ocean floor can directly release PEs into sediment. This study provides an appropriate data set for the assessment of the risk of PEs to the marine ecosystem.

Neonicotinoid insecticides (NNs) and the herbicide glyphosate are systemic pesticides widely used in agriculture and urban environments. They are the most used pesticides worldwide. Their extensive use has led to great social concerns regarding their environmental fate and toxicity to non-target organisms and to human health. Consequently, glyphosate is at risk of being banned in the EU and 3 NNs (imidacloprid, clothianidin and thiamethoxam) have recently been permanently banned for outdoor applications. Nevertheless, their use is still permitted in China. Moreover, NNs have been incorporated in the watch list of substances for the EU monitoring program in surface waters (2015/495/EU) due to possible threats to aquatic organisms. Therefore, these compounds are emerging environmental contaminants of concern.This study investigates the temporal and spatial occurrence of 7 NNs, as well as other insecticides (fipronil, imidaclothiz, cycloxaprid and sulfoxaflor), the herbicide glyphosate and several of their transformation products in the Chinese Bohai Sea and its surrounding rivers. Water samples were collected in the summer and fall of 2018 from 36 rivers and 47 stations in the Bohai Sea. All samples were immediately stored at -20°C until analysis. All samples were extracted by solid-phase extraction (1L water sample was used for the insecticides, whereas 20 mL water sample was used for glyphosate and its main metabolite AMPA (aminomethylphosphonic acid)), eluted with methanol and further enriched by evaporation. For glyphosate and AMPA, the water samples were first derivatized with FMOC-Cl (9-Fluorenylmethoxycarbonyl chloride). All samples were analyzed by HPLC-MS/MS.The results show that, from the 18 compounds analyzed, 15 were detected in river samples and 12 in seawater samples. Acetamiprid was detected in all river- and seawater samples. Much higher concentrations were observed in the rivers (-1) as compared to the Bohai Sea (-1). AMPA was the compound detected at the highest concentration for both river- (4487 ng.L-1 – Xiaoqinglong River) and seawaters (120.5 ng.L-1), followed by glyphosate (Xiaoqing River = 463.6 ng.L-1; seawater = 27.4 ng.L-1) and then by acetamiprid (Duliujian River = 127.4 ng.L-1; seawater = 1.7 ng.L-1). Except for AMPA, all compounds were found at higher concentrations during the summer season.In conclusion, the ubiquitous presence of acetamiprid and the high concentrations and detection frequencies of AMPA in the sampled waters suggest a high persistence and stability of these compounds in surface waters. Therefore, these compounds may accumulate in aquatic/marine environments and may pose a risk to aquatic/marine organisms. The Bohai and Laizhou Bays presented the highest contamination status, to where most contaminated rivers were flowing, indicating that riverine discharges are important contributors to the pollution status of the marine environment. The higher detection frequencies and concentrations of the transformation products of imidacloprid, fipronil and glyphosate in the marine environment indicate the rapid degradation of their parent compounds during their “journey” from the contaminated rivers to the Bohai Sea. Since evidence shows that these transformation products have similar or even higher persistence and toxicity to non-target organisms, it is important to further monitor these compounds in the marine environment.

The spatial distribution of 29 per- and polyfluoroalkyl substances (PFASs) in seawater was investigated along a sampling transect from Europe to the Arctic and two transects within Fram Strait, located between Greenland and Svalbard, in the summer of 2018. Hexafluoropropylene oxide-dimer acid (HFPO-DA), a replacement compound for perfluorooctanoic acid (PFOA), was detected in Arctic seawater for the first time. This provides evidence for its long-range transport to remote areas. The total PFAS concentration was significantly enriched in the cold, low-salinity surface water exiting the Arctic compared to warmer, higher-salinity water from the North Atlantic entering the Arctic (260 ± 20 pg/L versus 190 ± 10 pg/L). The higher ratio of perfluoroheptanoic acid (PFHpA) to perfluorononanoic acid (PFNA) in outflowing water from the Arctic suggests a higher contribution of atmospheric sources compared to ocean circulation. An east-west cross section of the Fram Strait, which included seven depth profiles, revealed higher PFAS concentrations in the surface water layer than in intermediate waters and a negligible intrusion into deep waters (>1000 m). Mass transport estimates indicated a net inflow of PFASs with ≥8 perfluorinated carbons via the boundary currents and a net outflow of shorter-chain homologues. We hypothesize that this reflects higher contributions from atmospheric sources to the Arctic outflow and a higher retention of the long-chain compounds in melting snow and ice.

This study aimed at comparing source-specific fingerprints of per- and polyfluoroalkyl substances (PFASs) in river water from China and Germany, selected as countries with different histories of PFAS production. Samples were collected from up- and downstream of seven suspected point sources in autumn 2018. Amongst the 29 analyzed legacy and emerging PFASs, 24 were detected, with a sum ranging from 2.7 ng/L (Alz River) to 420,000 ng/L (Xiaoqing River). While mass flow estimates for the Xiaoqing River and Yangtze River (mean: 20 and 43 t/y, respectively) indicated ongoing high emissions of the legacy compound PFOA in China, its ether-based replacements HFPO-DA and DONA showed the highest contribution downstream of a German fluoropolymer manufacturing site (50% and 40% of ΣPFASs measured, respectively). In river water impacted by manufacturing sites for pharmaceutical and pesticide intermediates, the short-chain compound PFBS was the most prevalent substance in both countries. The German Ruhr River, receiving discharges from the electroplating industry, was characterized by the PFOS replacement 6:2 FTSA. Isomer profiling revealed a higher proportion of branched isomers in the Chinese Xi River and Xiaoqing River than in other rivers. This points to different synthesis routes and underlines the importance of differentiating between linear and branched isomers in risks assessments. Upon oxidative conversion in the total oxidizable precursor (TOP) assay, the increase of the short-chain compound PFBA was higher in German samples than in Chinese samples (88 ± 30% versus 12 ± 14%), suggesting the presence of a higher proportion of unknown precursors to PFBA in the German environment. Amongst the ether-based replacements, DONA and 6:2 Cl-PFESA were fully or partially degraded to non-targeted oxidation products, whereas HFPO-DA showed no degradation. This indicates that the inclusion of ether-based PFASs and their oxidation products in the TOP assay can help in capturing a larger amount of the unknown PFAS fraction.

Concentrations of 9 organophosphate esters (OPEs), 16 perfluoroalkylated substances (PFASs) and 17 polycyclic aromatic hydrocarbons (PAHs) were investigated in surface snow samples collected at Dome C on the Antarctic Plateau in summer 2016. Tris(1-chloro-2-propyl) phosphate (TCPP), tris-(2-chloroethyl) phosphate (TCEP) and tri-n-butylphosphate (TnBP) were the dominant compounds of OPEs, with mean concentrations of 8157 ± 4860, 1128 ± 928 and 1232 ± 1147 pg/L. Perfluorooctanoic acid (PFOA, mean: 358 ± 71 pg/L) was the dominant compound of PFASs, and following by perfluoro-n-hexanoic acid (PFHxA, mean: 222 ± 97 pg/L), perfluoro-n-heptanoic acid (PFHpA, 183 ± 60 pg/L) and perfluoro-n-pentanoic acid (PFPeA, 175 ± 105 pg/L). 2-(Heptafluoropropoxy)propanoic acid (HFPO-DA, mean: 9.2 ± 2.6 pg/L) was determined in the Antarctic for the first time. Significantly positive correlations were observed between HFPO-DA and the short-chain PFASs, implying they have similar emission sources and long-range transport potential. High levels of 2-methylnaphthalene and 1-methylnaphthalene, as well as the ratios of PAH congeners indicated PAHs were attributable mostly to combustion origin. Occurrence and profiles of the indicators of OPEs, PFASs and PAHs, as well as air mass back-trajectory analysis provided direct evidences of human activities on Concordia station and posed obvious impacts on local environments in the Antarctic. Nevertheless, the exchange processes among different environmental matrices may drive the long-range transport and redistribution of the legacy and emerging Organic contaminants from coast to inland in the Antarctic.

The role of polar regions increases in terms of megatrends such as globalization, new transport routes, demography and use of natural resources consequent effects of regional and transported pollutant concentrations. We set up the ERA-PLANET Strand 4 project iCUPE – integrative and Comprehensive Understanding on Polar Environments to provide novel insights and observational data on global grand challenges with an Arctic focus. We utilize an integrated approach combining in situ observations, satellite remote sensing Earth Observations (EO) and multi-scale modeling to synthesize data from comprehensive long-term measurements, intensive campaigns and satellites to deliver data products, metrics and indicators to the stakeholders concerning the environmental status, availability and extraction of natural resources in the polar areas. The iCUPE work consists of thematic state-of-the-art research and provision of novel data in atmospheric pollution, local sources and transboundary transport, characterization of arctic surfaces and their changes, assessment of concentrations and impacts of heavy metals and persistent organic pollutants and their cycling, quantification of emissions from natural resource extraction and validation and optimization of satellite Earth Observation (EO) data streams. In this paper we introduce the iCUPE project and summarize initial results arising out of integration of comprehensive in situ observations, satellite remote sensing and multiscale modeling in the Arctic context.

9H-carbazole is generated from incomplete combustion of diverse fossil fuels and biomass, in tobacco smoke and from industrial processes, while halogenated carbazoles have natural and anthropogenic sources. We analyzed 9H-carbazole and 14 halogenated carbazoles in dust samples from 14 schools, 13 daycare centers, and 13 residences, as well as 5 indoor air samples from residences in Munich, Germany. Overall, we present first data of various carbazoles in different indoor environments without visible combustion sources. The median (95th percentile) values of the halogenated analytes mainly detected in the entire study group were 10.3ng/g (308ng/g) for 9H-carbazole, 13.3ng/g (735ng/g) for 3,6-dichloro-9H-carbazole, 6.2ng/g (159ng/g) for 1,3,6-tribromo-9H-carbazole, and 1.2ng/g (21.1ng/g) for 2,7-dibromo-9H-carbazole. For most of the target analytes, the highest concentrations were observed in dust samples from schools, and the lowest were found in residences. In the air samples, all analytes were found only at low levels, with median values of 7.7pg/m3 for 9H-carbazole and 6.1pg/m3 for 2,3,6,7-tetrachloro-9H-carbazole. For 9H-carbazole, "typical" and "high" non-dietary intake of children through dust ingestion using median and 95th percentile values were calculated to be 0.03ng/kg b.w. and 1.1ng/kg b.w. daily, respectively. Due to limited toxicological information and exposure data for other relevant pathways (e.g., dietary intake), the risk assessment is inconclusive. Nevertheless, there are indications that 9H-carbazole has carcinogenic properties and that halogenated carbazoles have dioxin-like toxicities. Therefore, further research is essential.

Polyfluoroalkyl and perfluoroalkyl substances (PFASs), in the forms of neutral polyfluoroalkyl substances in the gas phase of air and ionic perfluoroalkyl substances in the dissolved phase of surface water, were investigated during a sampling campaign in the Bohai Sea, Yellow Sea, and Yangtze River estuary in May 2012. In the gas phase, the concentrations of neutral Sigma PFASs were within the range of 76-551 pg/m(3). Higher concentrations were observed in the South Yellow Sea. 8:2 fluorotelomer alcohol (FTOH) was the predominant compound as it accounted for 92%-95% of neutral Sigma PFASs in all air samples. Air mass backward trajectory analysis indicated that neutral Sigma PFASs came mainly from the coast of the Yellow Sea, including the Shandong, Jiangsu, and Zhejiang provinces of China, and the coastal region of South Korea. The fluxes of gas phase dry deposition, were simulated for neutral PFASs, and neutral Sigma PFASs fluxes varied from 0.37 to 23 pg/m(2)/s. In the dissolved phase of the surface water, concentrations of ionic Sigma PFASs ranged from 1.6 to 118 ng/L, with the Bohai Sea exhibiting higher concentrations than both the Yellow Sea and the Yangtze River estuary. Perfluorooctanoic acid (PFOA) was the predominant compound accounting for 51%-90% of the ionic Sigma PFAS concentrations. Releases from industrial and domestic activities as well as the semiclosed geographical conditions increased the level of ionic Sigma PFASs in the Bohai Sea. The spatial distributions of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs) were different significantly. The Laizhou Bay was the major source region of PFCAs and the Yangtze River estuary was the major source of PFSAs. (C) 2017 Elsevier B.V. All rights reserved.

Several eel species of the genus Anguilla are considered endangered due to a severe decline in recruitment. Up to now, the reasons for this threatening development are not fully understood. The eel's highly specialized biology can lead to explicitly high accumulation of globally distributed organic lipophilic contaminants during its continental life. Because of this and due the particular toxicological sensitivity of early life stages of oviparous organisms towards dioxin-like compounds, it is crucial to improve our understanding concerning toxicokinetics and maternal transfer of organic contaminants in eels. This study presents analytical data on maternal transfer of dioxin-like (dl) compounds in relevant tissue samples taken from artificially matured and non-matured European silver eels (Anguilla anguilla) from German inland waters using gas chromatography coupled with mass spectrometry (GC/MS) and high-resolution mass spectrometry (GC/HRMS). Detected concentrations revealed a lipid-driven transfer of targeted compounds from muscle-fat-reserves to gonads and eggs respectively, with no distinct preferences concerning the chlorination degree of targeted compounds. Dl-PCBs were shown to contribute the major share of toxicity equivalents found in analysed eel tissues. Maternal muscle tissue to egg concentration ratios in wet weight–based samples had a mean of 6.95 ± 1.49 in accordance with the differences in total lipid content in the respective body matrices. Dioxins and furans in analysed samples were (from a toxicological point of view) of less relevance. Furthermore it was shown that muscle concentrations in silver eels could be used in future assessments to make conservative predictions for expected egg concentrations in female eels.

Long-term measurements of gaseous elemental mercury (GEM) concentrations at Cape Point, South Africa, reveal a downward trend between September 1995 and December 2005 and an upward one from March 2007 until June 2015, implying a change in trend sign between 2004 and 2007. The trend change is qualitatively consistent with the trend changes in GEM concentrations observed at Mace Head, Ireland, and in mercury wet deposition over North America, suggesting a change in worldwide mercury emissions. Seasonally resolved trends suggest a modulation of the overall trend by regional processes. The trends in absolute terms (downward in 1995–2004 and upward in 2007–2015) are highest in austral spring (SON), coinciding with the peak in emissions from biomass burning in South America and southern Africa. The influence of trends in biomass burning is further supported by a biennial variation in GEM concentration found here and an El Niño–Southern Oscillation (ENSO) signature in GEM concentrations reported recently.

Increasing population and expansion of urban areas are often associated with degradation of aquatic ecosystems. Although water quality is a major concern for worldwide authorities, several emerging contaminants can threaten long term status of aquatic ecosystems and human health. UV filters are widely used in industrial products such as plastics, paints and coatings, to enhance their photo protective properties. Personal care products, such as shampoos, body creams, make-up and sunscreens, used in humans’ daily routine, also comprise a wide variety of chemicals, such as organic UV filters and parabens. Some UV filters are persistent, bioaccumulative and toxic. Parabens prevent bacterial growth and extend products shelf-lives, but they can have endocrine disruption properties. Wastewater is a potential vehicle of UV filters and parabens to the aquatic ecosystems, where they tend to accumulate in suspended sediments. This study investigates the presence of organic UV filters and parabens in Ribeira dos Covoes peri-urban catchment, in central mainland Portugal. The catchment has been deeply urbanized over the last decades, due to its proximity to Coimbra city center. Urban areas cover 40% of the catchment land-use and include several health services, such as a hospital, and a relatively large pharmaceutical company. Wastewater is piped and transported into a treatment plant (WWTP) located outside the catchment. The sewer system, however, is sometimes subject to failure, leading to leakages which affect local streams. In September 2018, fluvial sediment samples (0-3 cm depth) were collected in 10 sites across Ribeira dos Covoes stream network. The freeze-dried sediment samples were extracted using an accelerated solvent extractor (ASE-350, DIONEX, Germany) method, and analysed for 17 UV filters, 5 parabens and 2 synthetic musks, using an Agilent UHPLC-MS/MS system operating with dopant-assisted atmospheric pressure photoionization (DA-APPI). The results show the presence of methylparaben (10.3 ng/g dw) at the catchment outlet. UV filters were found in sediments from several sites in Ribeira dos Covoes. Compounds revealing highest concentrations were octocrylene, quantified in 8 of the 10 sampling sites and reaching 286.3 ng/g dw, and ethylhexyltriazone, quantified in half of the monitored sites in concentrations up to 67.7 ng/g dw. The largest number of compounds and with highest concentrations, were recorded in two stream sections that received wastewater, based on reports from local citizens about sewer pipe leakages. Wastewater contamination can represent a major problem for the good status of aquatic ecosystems in urban environments.

In this study a target analysis approach with method detection limits down to 0.01 ng L−1 was developed in order to determine ultra-trace pharmaceuticals in seawater of the German coast and their estuaries. The selection of target analytes based on a prioritisation commissioned by the German Environmental Agency considering occurrence in German surface waters, production volumes and ecotoxicological data. Using ultra-high pressure liquid chromatography coupled to a triple quadrupole mass spectrometer equipped with an electrospray ionisation source 21 prioritised pharmaceuticals out of seven therapeutical classes (antibiotics, iodinated X-ray contrast media (ICM), analgesics, lipid reducers, antiepileptics, anticonvulsants, beta-blockers) have been detected in the low to medium ng L−1-range. The most frequently measured substance groups in the German Baltic Sea and German Bight are the ICM, represented by the non-ionic ICM iomeprol (German Bightmax: 207 ng L−1; Baltic Seamax: 34.5 ng L−1) and the ionic ICM amidotrizoic acid (German Bight: 86.9 ng L−1), respectively. The same pattern of substance distribution could be detected in the German Bight, the German Baltic Sea and their inflows with lower concentrations in the offshore region that are partly a result of dilution with marine water. Pharmaceuticals entering the estuaries and coastal regions are an environmental issue since data on the ecotoxicological effects on aquatic marine organisms is limited. Especially the antibiotics clarithromycin and sulfamethoxazole could be ecotoxicologically/environmentally critical.

This study reports the occurrence and distribution of organophosphor esters (OPEs), used as flame retardants and plasticizer, in the marine atmosphere of the German Coast. From August 2011 to October 2012, 58 high volume air samples (gas/particle phase separately) were collected at the German North Sea coast town Büsum. With the use of a GC-MS/MS System for instrumental analysis, detection limits for OPEs in air samples could be significantly improved compared to the previously used single GC-MS method. The concentration (gas + particle phase) of total OPEs was on average 5 pg/m3, with eight of the nine investigated compounds detectable in over 50% of the samples. A focus of this investigation concerned the partioning of OPEs between the particle and the gas phase. The observed partitioning of OPEs in this study was distinguished from previous studies. While previous studies reported OPEs exclusively in the particle phase, a significant part of the sum OPE concentration (55%) was detected in the gas phase. The contribution of the gas phase even reached up to as high as 88% for individual compounds such as tri-iso-butyl phosphate.

Neutral Polyfluoroalkyl substances (PFASs) in the atmosphere were measured during a cruise campaign over the northern South China Sea (SCS) from September to October 2013. Four groups of PFASs, i.e., fluorotelomer alcohols (FTOHs), fluorotelomer acrylates (FTAs), fluorooctane sulfonamides (FOSAs) and fluorooctane sulfonamidoethanols (FASEs), were detected in gas samples. FTOHs was the predominant PFAS group, accounting for 95.2-99.3% of total PFASs (Sigma PFASs), while the other PFASs accounted for a small fraction of Sigma PFASs. The concentrations of PFASs ranged from 18.0 to 109.9 pg m(-3) with an average of 54.5 pg m(-3). The concentrations are comparable to those reported in other marine atmosphere. Higher concentrations of PFASs were observed in the continental-influenced samples than those in other samples, pointing to the substantial contribution of anthropogenic sources. Long-range transport is suggested to be a major pathway for introducing gaseous PFASs into the atmosphere over the northern SCS. In order to further understand the fate of gaseous PFASs during transport, the atmospheric decay of neutral PFASs under the influence of reaction with OH radicals and atmospheric physical processes were estimated. Concentrations of 8:2 FTOH, 6:2 FTOH and MeFBSE from selected source region to the atmosphere over the SCS after long-range transport were predicted and compared with the observed concentrations. It suggests that the reaction with OH radicals may play an important role in the atmospheric decay of PFAS during long-range transport, especially for shorted-lived species. Moreover, the influence of atmospheric physical processes on the decay of PFAS should be further considered. (C) 2016 Elsevier Ltd. All rights reserved.

Mercury measurements were concurrently made in air (Gaseous Elemental Mercury, i.e. GEM) as well as in precipitation samples (Total mercury, i.e. TotHg) over a seven year period (2007–2013) at Cape Point, South Africa, during the rainy seasons (May–October). Eighty-five rain events, almost exclusively associated with cold fronts, have been identified of which 75% reached the Cape Point observatory directly across the Atlantic Ocean from the south, while 19% moved in to the measuring site via the Cape Town metropolitan region. In statistic terms the GEM, TotHg, CO and 222Rn levels within the urban-marine events do not differ from those seen in the marine rain episodes. Over the 2007–2013 period, the May till Oct averages for GEM ranged from 0.913 ng m−3 to 1.108 ng m−3, while TotHg concentrations ranged from 0.03 to 52.5 ng L−1 (overall average: 9.91 ng L−1). A positive correlation (R2 = 0.49, n = 7) has been found between the average annual (May till October) GEM concentrations in air and TotHg concentration in rainwater suggesting a close relationship between the two species. The wetter years are normally associated with higher GEM and TotHg levels. Both GEM and TotHg annual means correlate positively with total annual (May till October) rain depths. If one or two outlier years are removed from the data set, the R2 values increase from 0.23 to 0.10 for GEM and TotHg to 0.97 (n = 5) and 0.89 (n = 5), respectively. The relationship between annual mean GEM and annual precipitation depth also holds for the period 1996–2004 (R2 = 0.6, n = 8) when GEM was measured manually (low resolution data). A positive correlation was also seen between annual average GEM concentrations and the El Nino Southern Oscillation (ENSO) Index (SOI), for the 1996–2004 period (R2 = 0.7, n = 8). For the 2007–2013 periods this relationship was also positive but less pronounced. The relationship between annual precipitation depth and annual SOI suggests that the inter-annual variations of GEM (Hg0) concentration might be caused by large-scale meteorological processes.

An international sampling campaign was carried out to comprehensively investigate the occurrence of polycyclic aromatic hydrocarbons (PAHs) in the marine sediments from the European Baltic and North Seas, Chinese Bohai and Yellow Seas. The concentrations of ∑18PAHs in the samples from these four seas were in the range of 0.91–5361 ng/g dry weight (dw), 0.46–227 ng/g dw, 25.0–308 ng/g dw and 4.3–659 ng/g dw, respectively. 4-rings PAHs, e.g., fluoranthene, pyrene and benzo(b)fluoranthene, were commonly the dominant compounds in all the samples. The PAH sources were identified via composition patterns, diagnostic ratios, principal component analysis (PCA) and positive matrix factorization (PMF). Coal combustion, vehicular emission, coke plant and petroleum residue were apportioned as the main sources in these marine sediments. However, through PMF modeling, different contributions of these sources were quantified to the deposited PAHs in the seas, suggesting distinct anthropogenic impacts on the adjacent marine system. It is note-worthy that biomass combustion may not be the main source of PAHs in the majority of sediments from these seas. This was evidenced by the ratios of naphthalene against its methylated derivatives (i.e. 1-,2-methylnaphthalenes) other than the composition pattern in the samples, of which the approach is in prospect of developing in future studies.

UV absorbing compounds are of emerging concern due to their large production volumes, their persistence or pseudo-persistence, and their potential adverse effects. This is the first study investigating the environmental occurrence and potential hazard of organic UV stabilizers and UV filters in the North and Baltic Sea surface sediments, including the connecting Skagerrak and Kattegat straits. In total, nineteen substances were identified over the entire study area, including the rarely studied compounds ethylhexyl triazone (EHT) and bisoctrizole (UV-360). Octocrylene (OC) was the predominant compound in this study with regard to detection frequency (79%) and concentrations (up to 9.7 ng/g dw). OC accounted for more than 65% of UV stabilizer contamination in the German Bight. The triazine derivative EHT was quantified in the Rhine-Meuse-Delta and the German Bight in concentrations up to 2.0 ng/g dw. In the Baltic Sea, benzotriazole UV stabilizers accounted for 60% of the contamination, with UV-360 as the main substance. The estimated environmental hazard quotients indicated a negligible impact on benthic and sediment-dwelling organisms in the North and Baltic Seas. Region-specific contamination pattern and riverine influences were revealed. The results suggest that both direct and indirect sources contribute to the UV stabilizer and UV filter contamination in the study area.

This study reports the occurrence and distribution of organophosphorus flame retardants and plasticizer (OPEs) in sediments of eight large river basin estuaries and deltas across Europe. A robust and sensitive OPE analysis method was developed through the application of an in-cell clean-up in an accelerated solvent extraction and the use of an GC-MSMS System for instrumental analyses. OPEs were detected in all sediment samples with sum concentrations of up to 181 ng g−1 dw. A fingerprinting method was used to identify river specific pattern to compare river systems. The estuaries and deltas were chosen to have a conglomerate print of the whole river. The results are showing very similar OPE patterns across Europe with minor differences driven by local industrial input. The European estuary concentrations and patterns were compared with OPEs detected in the Xiaoquing River in China, as an example for a region with other production, usage and legislative regulations. The Chinese fingerprint differed significant from the overall European pattern.

International audience; Anthropogenic mercury emissions are transported through the atmosphere as gaseous elemental mercury (Hg(0)) before they are deposited to Earth’s surface. Strong seasonality in atmospheric Hg(0) concentrations in the Northern Hemisphere has been explained by two factors: anthropogenic Hg(0) emissions are thought to peak in winter due to higher energy consumption, and atmospheric oxidation rates of Hg(0) are faster in summer. Oxidation-driven Hg(0) seasonality should be equally pronounced in the Southern Hemisphere, which is inconsistent with observations of constant year-round Hg(0) levels. Here, we assess the role of Hg(0) uptake by vegetation as an alternative mechanism for driving Hg(0) seasonality. We find that at terrestrial sites in the Northern Hemisphere, Hg(0) co-varies with CO$_2$, which is known to exhibit a minimum in summer when CO$_2$ is assimilated by vegetation. The amplitude of seasonal oscillations in the atmospheric Hg(0) concentration increases with latitude and is larger at inland terrestrial sites than coastal sites. Using satellite data, we find that the photosynthetic activity of vegetation correlates with Hg(0) levels at individual sites and across continents. We suggest that terrestrial vegetation acts as a global Hg(0) pump, which can contribute to seasonal variations of atmospheric Hg(0), and that decreasing Hg(0) levels in the Northern Hemisphere over the past 20 years can be partly attributed to increased terrestrial net primary production.

Organic UV stabilizers and UV filters are applied to industrial materials and cosmetics worldwide. In plastics they prevent photo-induced degradation, while in cosmetics they protect human skin against harmful effects of UV radiation. This study reports on the occurrence and distribution of organic UV stabilizers and UV filters in the surface sediment of the Chinese Bohai and Yellow Seas for the first time. In total, 16 out of 21 analyzed substances were positively detected. Concentrations ranged from sub-ng/g dw to low ng/g dw. The highest concentration of 25 ng/g dw was found for octocrylene (OC) in the Laizhou Bay. In the study area, characteristic composition profiles could be identified. In Korea Bay, the dominating substances were OC and ethylhexyl salicylate (EHS). All other analytes were below their method quantification limit (MQL). Around the Shandong Peninsula, highest concentrations of benzotriazole derivatives were observed in this study with octrizole (UV-329) as the predominant compound, reaching concentrations of 6.09 ng/g dw. The distribution pattern of UV-329 and bumetrizole (UV-326) were related (Pearson correlation coefficient r > 0.98, p « 0.01 around the Shandong Peninsula), indicating an identical input pathway and similar environmental behavior.

The stock of European Eel (Anguilla anguilla L.) has reached an all-time low in 2011. Spawner quality of mature eels in terms of health status and fitness is considered one of the key elements for successful migration and reproduction. Dioxin-like Polychlorinated Biphenyls (dl-PCBs) are known persistent organic pollutants potentially affecting the reproductive capability and health status of eels throughout their entire lifetime. In this study, muscle tissue samples of 192 European eels of all continental life stages from 6 different water bodies and 13 sampling sites were analyzed for contamination with lipophilic dl-PCBs to investigate the potential relevance of the respective habitat in light of eel stock management. Results of this study reveal habitat-dependent and life history stage-related accumulation of targeted PCBs. Sum concentrations of targeted PCBs differed significantly between life stages and inter-habitat variability in dl-PCB levels and -profiles was observed. Among all investigated life stages, migrant silver eels were found to be the most suitable life history stage to represent their particular water system due to habitat dwell-time and their terminal contamination status. With reference to a possible negative impact of dl-PCBs on health and the reproductive capability of eels, it was hypothesized that those growing up in less polluted habitats have a better chance to produce healthy offspring than those growing up in highly polluted habitats. We suggest that the contamination status of water systems is fundamental for the life cycle of eels and needs to be considered in stock management and restocking programs.

The production and use of long-chain perfluoroalkyl substances (PFASs) must comply with national and international regulations. Driven by increasingly stringent regulations, their production has been outsourced to less regulated countries in Asia. In addition, the fluoropolymer industry started to use fluorinated alternatives, such as 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoic acid (HFPO-DA). Between August 2013 and September 2014, we investigated the occurrence and distribution of HFPO-DA and legacy PFASs in surface waters of the following river/estuary systems: the Elbe and Rhine Rivers in Germany, the Rhine-Meuse delta in The Netherlands, and the Xiaoqing River in China. Distinct differences were revealed among the study areas; notably, the Chinese samples were highly polluted by an industrial point source discharging mainly perfluorooctanoic acid (PFOA). This particular point source resulted in concentrations more than 6000 times higher than an industrial point source observed in the Scheur River, where HFPO-DA was the dominant compound with a concentration of 73.1 ng/L. Moreover, HFPO-DA was detected in all samples along the coastline of the North Sea, indicating that the compound may be transported from the Rhine-Meuse delta into the German Bight via the water current. To the best of our knowledge, the fluorinated alternative, HFPO-DA, was detected for the first time in surface waters of Germany and China.

Dry deposition fluxes of 12 neutral poly-/perfluoroalkyl substances (PFASs) were estimated at Büsum located in northern German coast, and their gas/particle partition coefficients were predicted by employing the polyparameter linear free energy relationships (PP-LFERs). The gas deposition flux, particle deposition flux and total (gas + particle) flux of the 12 PFASs during sampling periods were 1088 ± 611, 189 ± 75 and 1277 ± 627 pg/(m(2) d), respectively. The gas deposition of PFASs played a key role during deposition to marine ecosystem. Sensitivity analysis showed that wind speed was the most sensitive parameter for gas deposition fluxes. Good agreements (within 1 log unit) were observed between the measured gas/particle partitioning data of PFASs and the predicted partition coefficients using PP-LFERs, indicating the model can reliably predict the gas/particle partitioning behaviors of atmospheric neutral PFASs.

53 brominated and chlorinated flame retardants were investigated in sediment samples from the German rivers Elbe and Weser, the German Bight, Jadebusen, East Frisian Coast as well as the UK East coast. The aim of the presented study was to investigate the prevalence of different halogenated flame retardant groups as contaminants in North Sea sediments, identify determining factors for the distribution and levels as well as to identify area specific fingerprints that could help identify sources. In order to do that a fast and effective ASE extraction method with an on-line clean-up was developed as well as a GC-EI-MSMS and LC-ESI-MSMS method to analyse PBDEs, MeOBDEs, alternate BFRs, Dechloranes as well as TBBPA and HBCDD. A fingerprinting method was adopted to identify representative area-specific patterns based on detection frequency as well as concentrations of individual compounds. Concentrations in general were low, with

Persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), are frequently detected in biota from Antarctica, whereas no data are available for their replacements, such as novel flame retardants (N-FRs). This study presented the occurrence of several N-FRs, PBDEs, and PCBs in tissue samples of an Antarctic rock cod (Trematomus bernacchii), a young gentoo penguin (Pygoscelis papua), and a brown skua (Stercorarius antarcticus) collected from King George Island. The total concentrations of N-FRs (ΣN-FRs; mean: 931 pg/g dry weight (dw)) were comparable to PBDEs (Σ8PBDEs; 681 pg/g dw), which were much lower than PCBs (ΣDL-PCBs; 12,800 pg/g dw). Overall, skua contained two to three orders of magnitude higher contamination than penguin and fish. In the future, more attention should be focused on the fate of N-FRs in Antarctica, where usages have increased since PBDEs were banned. To our knowledge, this is the first report of N-FRs in biota from Antarctica.

We perform global-scale inverse modeling to constrain present-day atmospheric mercury emissions and relevant physiochemical parameters in the GEOS-Chem chemical transport model. We use Bayesian inversion methods combining simulations with GEOS-Chem and ground-based Hg[superscript 0] observations from regional monitoring networks and individual sites in recent years. Using optimized emissions/parameters, GEOS-Chem better reproduces these ground-based observations and also matches regional over-water Hg[superscript 0] and wet deposition measurements. The optimized global mercury emission to the atmosphere is ~ 5.8 Gg yr[superscript −1]. The ocean accounts for 3.2 Gg yr[superscript −1] (55% of the total), and the terrestrial ecosystem is neither a net source nor a net sink of Hg[superscript 0]. The optimized Asian anthropogenic emission of Hg[superscript 0] (gas elemental mercury) is 650–1770 Mg yr[superscript −1], higher than its bottom-up estimates (550–800 Mg yr[superscript −1]). The ocean parameter inversions suggest that dark oxidation of aqueous elemental mercury is faster, and less mercury is removed from the mixed layer through particle sinking, when compared with current simulations. Parameter changes affect the simulated global ocean mercury budget, particularly mass exchange between the mixed layer and subsurface waters. Based on our inversion results, we re-evaluate the long-term global biogeochemical cycle of mercury, and show that legacy mercury becomes more likely to reside in the terrestrial ecosystem than in the ocean. We estimate that primary anthropogenic mercury contributes up to 23 % of present-day atmospheric deposition., National Science Foundation (U.S.). Atmospheric Chemistry Program (1053648)

The oceanic scale occurrences of typical neutral poly/per-fluoroalkyl substances (PFASs) in the atmosphere across the Atlantic, as well as their air-snow exchange at the Antarctic Peninsula, were investigated. Total concentrations of the 12 PFASs (∑PFASs) in gas phase ranged from 2.8 to 68.8 pg m(-3) (mean: 23.5 pg m(-3)), and the levels in snow were from 125 to 303 pg L(-1) (mean: 209 pg L(-1)). Fluorotelomer alcohols (FTOHs) were dominant in both air and snow. The differences of specific compounds to ∑PFASs were not significant between air and snow. ∑PFASs were higher above the northern Atlantic compared to the southern Atlantic, and the levels above the southern Atlantic

The spatial distributions and seasonal variations of perfluoroalkyl substances (PFASs) in surface waters were investigated for the German rivers Elbe and lower Weser, and the North Sea. Sigma PFAS concentrations ranged from 4.1 to 250 ng L-1 in the River Elbe, from 3.8 to 16 ng L-1 in the lower Weser, and from 0.13 to 10 ng L-1 in the North Sea. The most abundant compound was perfluorobutanesulfonate (PFBS) with a proportion of 24% in river water and 31% in seawater samples. The concentrations of perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA) in Elbe River water showed significant seasonal variation in 2011. The seasonal variations might be related to the variations of water discharge. The highest concentrations of PFOA and PFHxA were detected in August. Pearson correlations showed that perfluorobutanoic acid (PFBA) and PFBS had different sources from other PFASs, and the current manufacturing and use of C-4-based products could explain the distinction. The estimated fluxes of individual substances and Sigma PFASs in the River Elbe showed no significant seasonal variation. The annual fluxes of PFASs to the North Sea were estimated to be 335 +/- 100 kg year(-1) from the River Elbe and 102 +/- 22 kg year(-1) from the River Weser. (C) 2014 Elsevier Ltd. All rights reserved.

Global and regional change clearly affects the structure and functioning of ecosystems in shelf seas. However, complex interactions within the shelf seas hinder the identification and unambiguous attribution of observed changes to drivers. These include variability in the climate system, in ocean dynamics, in biogeochemistry, and in shelf sea resource exploitation in the widest sense by societies. Observational time series are commonly too short, and resolution, integration time, and complexity of models are often insufficient to unravel natural variability from anthropogenic perturbation. The North Sea is a shelf sea of the North Atlantic and is impacted by virtually all global and regional developments. Natural variability (from interannual to multidecadal time scales) as response to forcing in the North Atlantic is overlain by global trends (sea level, temperature, acidification) and alternating phases of direct human impacts and attempts to remedy those. Human intervention started some 1000 years ago (diking and associated loss of wetlands), expanded to near-coastal parts in the industrial revolution of the mid-19th century (river management, waste disposal in rivers), and greatly accelerated in the mid-1950s (eutrophication, pollution, fisheries). The North Sea is now a heavily regulated shelf sea, yet societal goals (good environmental status versus increased uses), demands for benefits and policies diverge increasingly. Likely, the southern North Sea will be re-zoned as riparian countries dedicate increasing sea space for offshore wind energy generation — with uncertain consequences for the system's environmental status. We review available observational and model data (predominantly from the southeastern North Sea region) to identify and describe effects of natural variability, of secular changes, and of human impacts on the North Sea ecosystem, and outline developments in the next decades in response to environmental legislation, and in response to increased use of shelf sea space.

Observations of atmospheric mercury at the Mace Head Atmospheric Research Station on the Atlantic coast of Ireland made from February 1996 to December 2013 are analyzed. Using meteorological analysis and a sophisticated Lagrangian dispersion model, the hourly averaged mercury concentrations were attributed to four different air mass types: baseline, local, European polluted, and sub-tropical maritime. Monthly median Hg concentrations of all types decreased over the analyzed period but the trend for sub-tropical maritime air masses was with −0.016 ± 0.002 ng m−3 yr−1 in absolute terms significantly smaller than the trends for all other classes which varied between −0.021 and −0.023 ng m−3 yr−1. The seasonal variation for sub-tropical maritime air masses is also shallower than for all other classes. This is most likely due to shallower seasonal variation of oxidant concentrations at lower latitudes. The north-south gradient of the trend is qualitatively consistent with the GEOS-Chem model predictions based on decrease of mercury concentrations in surface waters of the North Atlantic but the trends are smaller than predicted. Tests for temporal change of the trends indicate that the decreasing trends of mercury concentrations are leveling off for all air masses with possible exception of the sub-tropical maritime air mass. Quantitative assessment of the trend changes, however, will require a longer time series of the mercury measurements at Mace Head.

Nine organophosphate esters (OPEs) were investigated in air samples collected over the Bohai and Yellow Seas (East Asia) during a research cruise between June 28 and July 13, 2016. These same OPEs were quantified at a research site (North Huangcheng Island, NHI) in the middle of the Bohai Strait from May 16, 2015, to March 21, 2016. The median total OPE (ΣOPE) concentration over the Bohai and Yellow Seas was 280 pg/m3. Tris(1-chloro-2-propyl) (TCPP) was the most abundant OPE, followed by tris(2-chloroethyl) phosphate (TCEP), tri-iso-butyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP). Particle-bound OPEs accounted for 51 ± 21% of the total OPEs. On NHI, the median ΣOPE concentration was 210 pg/m3, and the average particle-bound fraction was 82 ± 17%. For samples collected on NHI, significant negative linear correlations were found between the gaseous OPEs and 1/T (T: temperature (K)) (except TDCP, TPeP, and TCP). Among the 79 investigated samples, significant correlations between the measured OPE gas/particle partitioning coefficients (Kp,m) and subcooled liquid pressure (PL◦) (p < 0.05) were found for only 14 samples, suggesting that OPEs have low potential to achieve equilibrium or ascribe to the artificial sampling. The annual dry deposition input of OPEs into the Bohai and Yellow Seas is estimated to be 12 tons/year.

Concentrations and distribution characteristics of organophosphate esters (OPEs) in surface sediment samples were analyzed and discussed for the first time in the open Bohai Sea (BS) and Yellow Sea (YS). Three halogenated OPEs [tris-(2-chloroethyl) phosphate (TCEP), tris-(1-chloro-2-propyl) phosphate (TCPP), and tris-(1,3-dichloro-2-propyl) phosphate (TDCPP)] and five non-halogenated OPEs [tri-isobutyl phosphate (TiBP), tri-n-butyl phosphate (TnBP), tripentyl phosphate (TPeP), triphenyl phosphate (TPhP) and tris-(2-ethylhexyl) phosphate (TEHP)] were detected in this region. The concentrations of eight OPEs in total (Σ8OPEs) ranged from 83 to 4552 pg g− 1 dry weight (dw). The halogenated OPEs showed higher abundances than the non-halogenated ones did, with TCEP, TCPP, and TEHP the main compounds. Generally, concentrations of OPEs in the BS were higher than those in the YS. Riverine input (mainly the Changjiang Diluted Water (CDW)) and deposition effect in the mud areas might have influenced the spatial distributions of OPEs. Correlation between OPE concentrations and total organic carbon (TOC) indicated TOC was an effective indicator for the distribution of OPEs. Inventory analysis of OPEs implied that sea sediment might not be the major reservoir of these compounds.

Chemical pollution in the microplastics has been concerned worldwide as pollutants might potentially transfer from the environment to living organisms via plastics. Here, we investigate organophosphorus esters (OPEs) and phthalic acid esters (PAEs) in the beached microplastics collected from 28 coastal beaches of the Bohai and Yellow Sea in north China. The analyzed microplastics included polyethylene (PE) pellets and fragments, polypropylene (PP) flakes and fragments and polystyrene (PS) foams. The tris-(2-chloroethyl)-phosphate (TCEP), tris (1-chloro-2-propyl) phosphate (TCPP) and di-(2-ethylhexyl) phthalate (DEHP) were the three predominant compounds found overall. The maximum Σ4 OPEs concentration was 84,595.9ngg-1, almost three orders of magnitude higher than the maximum Σ9 PAEs concentration. The PP flakes and PS foams contained the highest concentrations of the additives in contrast to the PE pellets which contained the lowest. The high concentration level of carcinogenic chlorinated OPEs and DEHP with endocrine disrupting effects implied the suggested potential hazards to coastal organisms. Spatial differences and compositional variation of the additives among the different microplastics suggests different origins and residence times in the coastal environment. This indicates that the characteristics of chemical additives might be a useful approach when tracing sources of microplastics in the environment.