Fourteen organophosphate esters (OPEs) were measured in the filter fraction of 117 active air samples from yearly ship-based sampling campaigns (2007-2013) and two land-based stations in the Canadian Arctic, to assess trends and long-range transport potential of OPEs. Four OPEs were detected in up to 97% of the samples, seven in 50% or less of the samples, and three were not detected. Median concentrations of ∑OPEs were 237 and 50 pg m(-3) for ship- and land-based samples, respectively. Individual median concentrations ranged from below detection to 119 pg m(-3) for ethanol, 2-chloro-, phosphate (3:1) (TCEP). High concentrations of up to 2340 pg m(-3) were observed for Tri-n-butyl phosphate (TnBP) at a land-based sampling location in Resolute Bay from 2012, whereas it was only detected in one ship-based sample at a concentration below 100 pg m(-3). Concentrations of halogenated OPEs seemed to be driven by river discharge from the Nelson and Churchill Rivers (Manitoba) and Churchill River and Lake Melville (Newfoundland and Labrador). In contrast, nonhalogenated OPE concentrations appeared to have diffuse sources or local sources close to the land-based sampling stations. Triphenyl phosphate (TPhP) showed an apparent temporal trend with a doubling-time of 11 months (p = 0.044). The results emphasize the increasing relevance of halogenated and nonhalogenated OPEs as contaminants in the Arctic.
Gas-particle partitioning is one of the key factors that affect the environmental fate of semivolatile organic chemicals. Many organophosphate esters (OPEs) have been reported to primarily partition to particles in the atmosphere. However, because of the wide range of their physicochemical properties, it is unlikely that OPEs are mainly in the particle phase "as a class". We compared gas-particle partitioning predictions for 32 OPEs made by the commonly used OECD POV and LRTP Screening Tool ("the Tool") with the partitioning models of Junge-Pankow (J-P) and Harner-Bidleman (H-B), as well as recently measured data on OPE gas-particle partitioning. The results indicate that half of the tested OPEs partition into the gas phase. Partitioning into the gas phase seems to be determined by an octanol-air partition coefficient (log KOA) < 10 and a subcooled liquid vapor pressure (log PL) > -5 (PL in Pa), as well as the total suspended particle concentration (TSP) in the sampling area. The uncertainty of the physicochemical property data of the OPEs did not change this estimate. Furthermore, the predictions by the Tool, J-P- and H-B-models agreed with recently measured OPE gas-particle partitioning.
Eleven organophosphate esters (OPEs) were detected in surface water and sediment samples from yearly sampling (2013−2018) in the Canadian Arctic. In water samples, ∑chlorinated-OPEs (Cl-OPEs) concentrations exceeded ∑non-chlorinated-OPEs (non-Cl-OPEs) with median concentrations of 10 ng L −1 and 1.3 ng L −1 , respectively. In sediment samples, ∑Cl-OPEs and ∑nonchlorinated-OPEs had median concentrations of 4.5 and 2.5 ng g −1 , respectively. High concentrations of OPEs in samples from the Mackenzie River plume suggest riverine discharge as an OPE source to the Canadian Arctic. The prevalence of OPEs at other sites is consistent with long-range transport. The OPE inventory of the Canadian Arctic Ocean representative of years 2013−2018 was estimated at 450−16,000 tonnes with a median ∑ 11 OPE mass of 4100 tonnes with >99% of the OPE inventory estimated to be in the water column. These results highlight the importance of OPEs as water-based Arctic contaminants subject to long-range transport and local sources. The high OPE inventory in the water column of the Canadian Arctic Ocean points to the need for international regulatory mechanisms for persistent and mobile organic contaminants (PMOCs) that are not covered by the risk assessment criteria of the Stockholm Convention.
The levels of PBDEs, alternate BFRs and dechloranes in European Eel (Anguilla anguilla) samples (elvers, yellow and silver eels) were investigated to compare the contamination of eels from the rivers Elbe and Rhine and to estimate the BFR contamination throughout the eel's life cycle. PBDEs were the dominating flame retardants (FRs) in muscle tissues of yellow and silver eels, while the alternate BFR 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and the Dechlorane 602 were the dominating FRs in elvers (juvenile eels). Concentrations of FRs in silver eels from river Rhine were generally higher than concentrations in other eels analysed with up to 46 ng g(-1) wet weight (ww) ∑PBDEs. The concentrations in yellow and silver eels from river Elbe were similar with an average of 9.0±5.1 ng g(-1)ww and 8.1±3.7 ng g(-1)ww respectively. PBDE concentrations in elvers were comparably low (0.02 (BDE-100) to 0.1 (BDE-183) ng g(-1)ww), which lead to the conclusion that these contaminants were mostly ingested within the rivers. Among the alternate BFRs and dechloranes, DPTE as well as the Dechlorane 602 and Dechlorane Plus (DP) were found in all life cycle stages and rivers with concentrations between 0.01 ng g(-1)ww and 0.7 ng g(-1)ww. Dechlorane 603 could only be detected in silver eels from river Rhine. Pentabromoethylbenzene (PBEB) was only found in yellow and silver eels and bis(2-ethylhexyl)tetrabromophthalate (BEHTBP) could only be detected in elvers. These are the first reports of Dec-602 and 603 in aquatic organisms from Europe. The results of this study show the lasting relevance of PBDEs as contaminants in rivers and river-dwelling species but also the growing relevance of emerging contaminants such as alternate BFRs and dechloranes.
Maternal transfer of emerging brominated and chlorinated flame retardants in European eels AbstractThe European eel (Anguilla anguilla) is regarded as a critically endangered species. Scientists are in agreement that the "quality of spawners" is a vital factor for the survival of the species. This quality can be impaired by parasites, disease and pollution. Especially endocrine disrupting organic chemicals pose a potential threat to reproduction and development of offspring.To our knowledge, the findings in this publication for the first time describe maternal transfer of contaminants in eels. We analysed the concentrations of in total 53 polybrominated diphenyl ethers (PBDEs) and their halogenated substitutes in muscle, gonads and eggs of artificially matured European eels and in muscle and gonads of untreated European eels that were used for comparison. We found evidence that persistent organic pollutants such as PBDEs, as well as their brominated and chlorinated substitutes are redistributed from muscle tissue to gonads and eggs. Concentrations ranged from 0.001 ng g -1 ww for sum Dechlorane metabolites (DPMA, aCL 10 DP, aCl 11 DP) to 2.1 ng g -1 ww for TBA in eggs, 0.001 ng g -1 ww for Dechlorane metabolites to 9.4 ng g -1 ww for TBA in gonads and 0.002 ng g -1 ww for Dechlorane metabolites to 54 ng g -1 ww for TBA in muscle tissue.Average egg muscle ratios (EMRs) for compounds detectable in artificially matured eels from both Schlei Fjord and Ems River ranged from 0.01 for Dechlorane 602 (DDC-DBF) to 10.4 for PBEB. Strong correlations were found between flame retardant concentrations and lipid content in the analysed tissue types, as well as transfer rates and octanol-water partitioning
Cedarwood oil is an essential oil used as a fragrance material and insect repellent. Its main constituents are sesquiterpenes which are potentially bioaccumulative according to the REACH screening criteria. Cedarwood...
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