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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., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Perfluoroalkyl acids (PFAAs) have been determined in the environment globally. However, studies on the occurrence of PFAAs in marine sediment remain limited. In this study, 16 PFAAs are investigated in surface sediments from the German Bight, which provided a good overview of the spatial distribution. The concentrations of ΣPFAAs ranged from 0.056 to 7.4 ng/g dry weight. The highest concentration was found at the estuary of the River Ems, which might be the result of local discharge source. Perfluorooctane sulfonic acid (PFOS) was the dominant compound, and the enrichment of PFOS in sediment might be strongly related to the compound structure itself. The geographical condition of the German Bight influenced the movement of water and sediment, resulting in complex distribution. Following normalization according to total organic carbon (TOC) content, PFAA distributions showed a different picture. Significant linear relationships were found between total PFAA concentrations and TOC (R2=0.50, p<0.01). Compared with a previous study conducted in the same area, a declining trend was presented for the concentrations of PFOS and perfluorooctanoic acid (PFOA). Compound structure, geographical condition, and organic carbon in the sediment influence the distribution of PFAAs in the German Bight. Environmental risk assessment indicated that the risk from PFOA is negligible, whereas PFOS in marine sediment may present a risk for benthic organisms in the German Bight., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Long-term temporal trends (1991-2008) and spatial differences of perfluoroalkylated substances (PFASs) were investigated in harbor porpoise (Phocoena phocoena) liver samples of juvenile females from the Baltic and North Sea. Additionally, spatial differences between the populations in the Baltic Sea and Atlantic Ocean (i.e. Iceland and Norway) and the influence of the body mass, age and sex on the PFAS concentrations were examined. Perfluorooctane sulfonate (PFOS) was the predominant compound with a concentration range of 160-2425 ng/g wet weight (ww), followed by perfluorooctane sulfonamide (PFOSA, 1-237 ng/g ww) and perfluoroundecanoate (PFUnA, 3-124 ng/g ww). In terms of temporal trends, perfluoroalkyl sulfonates (PFSAs) and PFOSA concentrations decreased over time, while, conversely, the C(9)-C(13) perfluoroalkyl carboxylate (PFCA) concentrations increased. Spatial distribution of the contaminant concentrations showed consistently higher concentrations in the Baltic Sea and lowest concentrations in the Icelandic population of the Atlantic Ocean., (Copyright © 2012 Elsevier B.V. All rights reserved.)

This comprehensive study focused on the spatial and seasonal variations of organophosphorus flame retardants and plasticizers (OPs) in surface water from the estuary of the River Elbe and the German Bight (North Sea). 100 surface water samples were extracted by solid phase extraction (SPE) and analyzed by gas chromatography-mass spectrometry (GC-MS) with regard to 16 different OPs. The dominating substance was found to be tris(1-chloro-2-propyl) phosphate (TCPP) (Elbe: 40-250 ng L(-1), German Bight: 3-28 ng L(-1)). Furthermore, triethyl phosphate (TEP), tri-iso-butyl phosphate (TiBP), tris(2-butoxyethyl) phosphate (TBEP), and triphenylphosphine oxide (TPPO) were detected in concentrations up to 180 ng L(-1). Seasonal trends were detected for the longitudinal profile of the Elbe estuary. Besides the dilution of river water with North Sea water toward the mouth, leading to decreasing concentrations at the four sampling cruises (March, May, August, and October, 2010), an additional depletion of non-halogenated OPs was observed in summer which is supposed to be due to biodegradation or photodegradation. In addition, a comparison of all important tributaries of the German Bight (Elbe, Ems, and Weser) as well as the indirect tributaries Meuse, Rhine, and Scheldt was done by multivariate statistical methods. It could be shown that the contribution of non-halogenated alkylated OPs in the Rhine was higher than in all other tributaries. The riverine input of OPs into the North Sea via the investigated tributaries was estimated to be about 50 tyr(-1)., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Air samples collected in the German part of the North Sea from March to July 2010 were investigated for organophosphorus compounds (OPs) being applied as flame retardants and plasticizers. The ∑(8)OPs concentration ranged from 110 to 1400 pg m(-3) while tris(2-chloroisopropyl) phosphate (TCPP) dominated all samples with individual concentrations up to 1200 pg m(-3). The highest concentrations were observed in continental air masses showing the high influence of industrialized regions including production sites on atmospheric emissions and concentrations. The occurrence of OPs even in oceanic/Arctic air masses shows that OPs can undergo long-range atmospheric transport. Dry particle-bound deposition fluxes from 9 to 240 ng m(-2) d(-1) for ∑(8)OPs were estimated leading to a minimum annual flux of 710 ± 580 kg y(-1) OPs into the German North Sea. This study presents the first occurrence of OPs in the marine atmosphere together with important information on their long-range transport potential., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Benzotriazole (BT) and tolyltriazole (TT) are high production volume chemicals which are used in various industrial and household applications. In this study, the distribution of benzotriazoles in the estuaries of different rivers of central Europe and in the North Sea was analyzed by solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (HPLC-MS/MS). BT as well as TT was detected in all water samples. The concentrations for total benzotriazoles (BTs) ranged from 1.7 to 40 ng/L in the North Sea in costal areas. Concentrations in rivers are from 200 to 1250 ng/L, respectively. The mass flux of total benzotriazoles from the major rivers of central Europe into the North Sea was calculated to 78 t/a, dominated by the Rhine with an individual flux of 57 t/a of BTs. The analysis of the distribution profile in the North Sea showed that the decrease of the concentration was mostly caused by dilution and that the benzotriazoles are poorly degradable in the North Sea. This paper presents the first report of benzotriazoles in the marine environment., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The spatial distribution of polyfluoroalkyl compounds (PFCs) was investigated in dab (Limanda limanda) bile fluids collected from Iceland and the North Sea. Concentrations of various PFCs, including perfluorinated sulfonates (C(4)-C(6), C(8) PFSAs), perfluorinated carboxylic acids (C(9)-C(14) PFCAs) and n-methyl perfluorooctane sulfonamidoethanol (MeFOSE), were quantified. Perfluorooctane sulfonate (PFOS) was the predominant compound with highest concentrations along the Danish and German coast (mean 9.36ng/g wet weight (ww)). Significantly lower PFOS concentrations were found at the other sampling stations in the North Sea and Iceland (p<0.01, t-test). Conversely, the spatial distribution of the PFCAs in Iceland and the North Sea was more uniform. The most abundant PFCA was perfluorononanoic acid (PFNA), while the mean concentration decreased with increasing chain length from 4.7 ng/g ww for PFNA to 0.04 ng/g ww for perfluorotetradecanoic acid (PFTeDA). Overall, the different spatial distribution of PFCs indicates different origin of sources and different transportation mechanism., (Copyright 2009 Elsevier Ltd. All rights reserved.)

Total body burden and tissue distribution of polyfluorinated compounds (PFCs) were investigated in harbor seals (Phoca vitulina) from the German Bight in 2007. A total number of 18 individual PFCs from the following groups could be quantified in the different tissues: perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonates (PFSAs) and their precursors perfluorinated sulfinates (PFSiAs), perfluorinated sulfonamides, and sulfonamido ethanols. Perfluorooctanesulfonate (PFOS) was the predominant compound in all measured seal tissues (up to 1665 ng g(-1) wet weight in liver tissue). The dominant PFCAs were perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA), but their concentrations were much lower compared to PFOS. The mean whole body burden in harbor seals of all detected PFCs was estimated to be 2665+/-1207 microg absolute. The major amount of the total PFCs burden in the bodies was in blood (38%) and liver (36%), followed by muscle (13%), lung (8%), kidney (2%), blubber (2%), heart (1%), brain (1%), thymus (<0.01%) and thyroid (<0.01%). These data suggest large differences in body burden and accumulation pattern of PFCs in marine mammals.

The potential of triclosan (TCS) acting as an endocrine disruptor has led to growing concern about the presence of TCS in the environment. In this study, seawater samples were collected from the German Bight during sampling campaigns conducted with the German research ships Gauss and Ludwig Prandtl. TCS was determined both in the dissolved phase and in the suspended particulate matters with concentrations ranging 0.8-6870 pg L(-1) and <1-95 pg L(-1), respectively. High concentrations of TCS were present in the estuaries of the Elbe and the Weser, indicating significant input of TCS by the river discharge. The correlation coefficient (R(2)) between the dissolved concentration and salinity was 0.79 for the data obtained from the Gauss cruise, showing an obvious declining trend from the coast to the open sea.

Synthetic polycyclic musk fragrances Galaxolide (HHCB) and Tonalide (AHTN) were measured simultaneously in air and seawater in the Arctic and the North Sea and in the rural air of northern Germany. Median concentrations of gas-phase HHCB and AHTN were 4 and 18 pg m(-3) in the Arctic, 28 and 18 pg m(-3) in the North Sea, and 71 and 21 pg m(-3) in northern Germany, respectively. Various ratios of HHCB/AHTN implied that HHCB is quickly removed by atmospheric degradation, while AHTN is relatively persistent in the atmosphere. Dissolved concentrations ranged from 12 to 2030 pg L(-1) for HHCB and from below the method detection limit (3 pg L(-1)) to 965 pg L(-1) for AHTN with median values of 59 and 23 pg L(-1), respectively. The medians of volatilization fluxes for HHCB and AHTN were 27.2 and 14.2 ng m(-2) day(-1) and the depositional fluxes were 5.9 and 3.3 ng m(-2) day(-1), respectively, indicating water-to-air volatilization is a significant process to eliminate HHCB and AHTN from the North Sea. In the Arctic, deposition fluxes dominated the air-sea gas exchange of HHCB and AHTN, suggesting atmospheric input controls the levels of HHCB and AHTN in the polar region.