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      Hexabromocyclododecane diastereomers in fish and suspended particulate matter from selected European waters—trend monitoring and environmental quality standard compliance

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          Abstract

          The brominated flame retardant hexabromocyclododecane (HBCD) was monitored in fish and sediment (from one lake) or suspended particulate matter (SPM; from five rivers) at European freshwater sites to study the effects of reduction measures implemented by HBCD producers and users in recent years. Bream ( Abramis brama) were sampled annually between 2007 and 2013 in the rivers Götaälv/SE, Rhône/FR, Western Scheldt/NL, Mersey/UK, and Tees/UK and in Lake Belau/DE. Sediment/SPM was taken every second year between 2008 and 2014. HBCD was analyzed by LC/MS/MS allowing the determination of the alpha-, beta-, and gamma-diastereomers. For most sites, a decrease in ∑HBCD was observed in fish (e.g., in the Rhône and Western Scheldt by about 80 and 60%, respectively, with significantly decreasing trends, p < 0.01). In the Rhône, HBCD also decreased in SPM. At the sampling site in the Tees which was impacted by a former HBCD point source, fish HBCD levels decreased only after a major flood event in 2013. While fish data indicate a decline in environmental HBCD concentrations at most sites with diffuse emissions, SPM data were less conclusive. The European environmental quality standard for HBCD in fish of 167 μg kg −1 wet weight was met by all fish samples in 2013.

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          The online version of this article (doi:10.1007/s11356-017-9469-4) contains supplementary material, which is available to authorized users.

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          Technical basis for establishing sediment quality criteria for nonionic organic chemicals using equilibrium partitioning

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            Hexabromocyclododecanes (HBCDs) in the environment and humans: a review.

            Hexabromocyclododecanes (HBCDs) are brominated aliphatic cyclic hydrocarbons used as flame retardants in thermal insulation building materials, upholstery textiles, and electronics. As a result of their widespread use and their physical and chemical properties, HBCDs are now ubiquitous contaminants in the environment and humans. This review summarizes HBCD concentrations in several environmental compartments and analyzes these data in terms of point sources versus diffuse sources, biomagnification potential, stereoisomer profiles, time trends, and global distribution. Generally, higher concentrations were measured in samples (air, sediment, and fish) collected near point sources (plants producing or processing HBCDs), while lower concentrations were recorded in samples from locations with no obvious sources of HBCDs. High concentrations were measured in top predators, such as marine mammals and birds of prey (up to 9600 and 19 200 ng/g lipid weight, respectively), suggesting a biomagnification potential for HBCDs. Relatively low HBCD concentrations were reported in the few human studies conducted to date (median values varied between 0.35 and 1.1 ng/g lipid weight). HBCD levels in biota are increasing slowly and seem to reflect the local market demand. One important observation is the shiftfrom the high percentage of the gamma-HBCD stereoisomer in the technical products to a dominance of the alpha-HBCD stereoisomer in biological samples. A combination of factors such as variations in solubility, partitioning behavior, uptake, and, possibly, selective metabolism of individual isomers may explain the observed changes in stereoisomer patterns. Recommendations for further work include research on how HBCDs are transferred from products into the environment upon production, use, and disposal. Time trends need to be analyzed more in detail, including HBCD stereoisomers, and more data on terrestrial organisms are needed, especially for humans. Whenever possible, HBCDs should be analyzed as individual stereoisomers in order to address their fate and effects.
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              Levels and trends of brominated flame retardants in the European environment.

              In this paper, we review those data which have recently become available for brominated flame retardants (particularly the brominated diphenyl ethers (BDEs) and hexabromocyclododecane (HBCD)) in samples from the European environment. Environmental compartments studied comprise the atmosphere, sediments and soils, sewage sludges, and a variety of biological samples and food chains. This is currently a very active research area, and we cite over 70 studies reported in the literature during 2003-04. Findings include that the input of BDEs (especially BDE209) to the Baltic Sea by atmospheric deposition now exceeds that of PCBs by a factor of almost 40 times. Sewage sludge samples from both industrial and background locations show concentrations of BDEs, HBCD and tetrabromobisphenol-A (TBBP-A) that are of a similar order, indicating that the major source is from diffuse leaching from products into wastewater streams from users, households and industries generally. Point-sources from industries using BFRs (e.g. the textile industry) also generate local hot-spots. Sediment core studies identified the presence of two of the three PBDE formulations. The penta-mix formulation was clearly present from the beginning of the 1970s, but the deca-mix only appeared in the late 1970s. BDE183, BDE209 and HBCD were detected in peregrine falcons from Sweden and other birds feeding on terrestrial food chains. BDEs are found widely distributed in fish, including those from high mountain lakes in Europe, as a consequence of long-range atmospheric transport and deposition. A temporal trend study in archived freeze-dried mussels from the Seine estuary, France, indicated an exponential increase in BDE concentrations during the period 1982-1993, which levelled off in 1999 and 2001 and then began to decline after 2002. HBCD was detected in liver and blubber samples from harbour seals and harbour porpoises from the Wadden and North Seas, though very few animals yielded positive values for TBBP-A. There are difficulties in comparing data on summation operatorBDE from studies in which different suites of BDE congeners have been determined, and we suggest a common suite which will allow the study of all three commercial PBDE formulations.
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                Author and article information

                Contributors
                +49 2972 302 301 , heinz.ruedel@ime.fraunhofer.de
                Journal
                Environ Sci Pollut Res Int
                Environ Sci Pollut Res Int
                Environmental Science and Pollution Research International
                Springer Berlin Heidelberg (Berlin/Heidelberg )
                0944-1344
                1614-7499
                17 June 2017
                17 June 2017
                2017
                : 24
                : 22
                : 18048-18062
                Affiliations
                [1 ]ISNI 0000 0004 0573 9904, GRID grid.418010.c, Department Environmental Specimen Bank and Elemental Analysis, , Fraunhofer Institute for Molecular Biology and Applied Ecology (Fraunhofer IME), ; 57392 Schmallenberg, Germany
                [2 ]ISNI 0000 0004 0573 9904, GRID grid.418010.c, Department Environmental and Food Analysis, , Fraunhofer Institute for Molecular Biology and Applied Ecology (Fraunhofer IME), ; 57392 Schmallenberg, Germany
                [3 ]ISNI 0000 0000 9116 4836, GRID grid.14095.39, Department Earth Sciences, Anthropocene Research, Geochemistry, , Freie Universität Berlin, ; 12249 Berlin, Germany
                [4 ]ISNI 0000 0001 2289 1527, GRID grid.12391.38, Biogeography, , University of Trier, ; 54286 Trier, Germany
                Author notes

                Responsible editor: Philippe Garrigues

                Author information
                http://orcid.org/0000-0002-4175-4787
                Article
                9469
                10.1007/s11356-017-9469-4
                5554270
                28624943
                d3bce8aa-a25e-454b-b21b-fc22f75358c2
                © The Author(s) 2017

                Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.

                History
                : 12 February 2017
                : 5 June 2017
                Funding
                Funded by: EFRA, EXIBA, PlasticsEurope
                Categories
                Research Article
                Custom metadata
                © Springer-Verlag GmbH Germany 2017

                General environmental science
                hbcd,fish,suspended particulate matter,trend monitoring,compliance monitoring,environmental monitoring,bream,sole

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