Organophosphorus flame retardants and plasticizers in water samples of the Rhine, Ems and Elbe Rivers in 2013

This study reports the occurrence and distribution of organophosphorus flame retardants and plasticizers (OPEs) in the Elbe and Rhine rivers. A special focus of this investigation concerns the potential impacts of a major flood event in 2013 on the OPE patterns and levels in the Elbe River. In this river, 6 of 13 OPEs were detected, with tris-ethyl-phosphate (TEP, 168 ± 44 ng/L), tris-1,3-dichloro-2-propyl-phosphate (TDCPP, 155 ± 14 ng/L) and tris-1-chloro-2-propyl phosphate (TCPP, 126 ± 14 ng/L) identified as the dominant compounds. Relative to previous studies, an increase in the concentrations and relative contributions of TDCPP to the total level of OPEs was observed, which was likely caused by its increased use as a replacement for the technical pentaBDE formulation. During the flood event, the concentrations of OPEs were similar to the normal situation, but the mass fluxes increased by a factor of approximately ten (~16 kg/d normal versus ~160 kg/d flood peak). No input hotspots were identified along the transects of the Elbe and Rhine rivers, and the mass flux of OPEs appeared to be driven by water discharge

Regional variations of organophosphorus flame retardants - Fingerprint of large river basin estuaries/deltas in Europe compared with China

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. (C) 2018 Elsevier Ltd. All rights reserved

Brominated flame retardants and dechloranes in North Sea sediments in 2012/2013

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<1 ng/g dw for most compounds. Exceptions were the comparably high concentrations of BDE-209 with up to 7 ng/g dw in selected samples and TBBPA in UK samples with 2.7±1.5 ng/g dw. Apart from BDE-209 and TBBPA, alternate BFRs and Dechloranes were predominant in all analysed samples, displaying the increasing relevance of these compounds as environmental contaminants

Organophosphorus flame retardants and plasticizer in air samples at the German coast in 2011/2012

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

Ultra-trace carbazoles in sediment samples of the Weser and Elbe Rivers and the North Sea in 2012 to 2014

Carbazole and some of its derivatives may possess dioxin-like toxicity and could be persistent in the environment, but information on their distribution and environmental fate is limited. This study developed and validated an ultra-trace targeted-analysis method for the determination of carbazole, 1,2-benzocarbazole, and 13 halogenated carbazoles in sediments from the river, coast, and North Sea. An 8-g sediment sample was extracted using accelerated solvent extraction combined with in-cell cleanup and analyzed using gas chromatography-tandem mass spectrometry. The method was sensitive and reliable with method detection limits ranging from 4.54 to 52.9 pg/g, and most of the quantification biases and relative standard deviations were 75%, while those of 3,6-dibromo-, 1-bromo-3,6-dichloro-, and 1,8-dibromo-3,6-dichlorocarbazole were approximately 50%. Brominated carbazoles occurred more frequently in marine than river-influenced sediments, which could indicate halogenation after discharge into the river. This is the first study regarding these substances in coastal environments without apparent contamination history. The ubiquity and bioaccumulative potential of these substances needs to be considered

Poly- and perfluoroalkyl substances measured in air and seawater of the North Sea in 2009

Concentrations of neutral poly- and perfluoroalkyl substances (PFASs), such as fluorotelomer alcohols (FTOHs), perfluoroalkane sulfonamides (FASAs), perfluoroalkane sufonamidoethanols (FASEs), and fluorotelomer acrylates (FTACs), have been simultaneously determined in surface seawater and the atmosphere of the North Sea. Seawater and air samples were taken aboard the German research vessel Heincke on the cruise 303 from 15 to 24 May 2009. The concentrations of FTOHs, FASAs, FASEs, and FTACs in the dissolved phase were 2.6-74, <0.1-19, <0.1-63, and <1.0-9.0 pg/L, respectively. The highest concentrations were determined in the estuary of the Weser and Elbe rivers and a decreasing concentration profile appeared with increasing distance from the coast toward the central part of the North Sea. Gaseous FTOHs, FASAs, FASEs, and FTACs were in the range of 36-126, 3.1-26, 3.7-19, and 0.8-5.6 pg/m**3, which were consistent with the concentrations determined in 2007 in the North Sea, and approximately five times lower than those reported for an urban area of Northern Germany. These results suggested continuous continental emissions of neutral PFASs followed by transport toward the marine environment. Air-seawater gas exchanges of neutral PFASs were estimated using fugacity ratios and the two-film resistance model based upon paired air-seawater concentrations and estimated Henry's law constant values. Volatilization dominated for all neutral PFASs in the North Sea. The air-seawater gas exchange fluxes were in the range of 2.5 × 103-3.6 × 105 pg/m**2 for FTOHs, 1.8 × 102-1.0 × 105 pg/m**2 for FASAs, 1.1 × 102-3.0 × 105 pg/m**2 for FASEs and 6.3 × 102-2.0 × 104 pg/m**2 for FTACs, respectively. These results suggest that the air-seawater gas exchange is an important process that intervenes in the transport and fate for neutral PFASs in the marine environment

Fingerprint analysis of brominated flame retardants and Dechloranes in North Sea sediments

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<1 ng g−1 dw for most compounds. Exceptions were the comparably high concentrations of BDE-209 with up to 7 ng g−1 dw in selected samples and TBBPA in UK samples with 2.7±1.5 ng g−1 dw. Apart from BDE-209 and TBBPA, alternate BFRs and Dechloranes were predominant in all analysed samples, displaying the increasing relevance of these compounds as environmental contaminants.</p