Organophosphate esters (OPEs) in the marine environment: Spatial distribution and profiles in French coastal bivalves.

Organophosphate esters (OPEs), chemicals widely used in industrial production, electronics and domestic products, have become ubiquitous environmental contaminants. In this study, the levels and spatial distribution of 11 OPEs (aryl, alkyl and halogenated) were investigated in over 100 samples of filter-feeding bivalves collected yearly between 2014 and 2021 at sites of contrasted pressure along the French coasts. OPEs were found in virtually all samples, indicating their widespread spatial and temporal occurrence in coastal bivalves and the relevance of their biomonitoring. The median concentrations were between 0.4 (TMPP) and 4.9 ng g-1 dry weight (TCIPP), with TCIPP, TNBP and EHDPP found at the highest median values. TCEP and TBOEP were not frequently detected overall, but each year, the same sites showed repeatedly high concentrations. Structurally-related OPEs generally correlated, but the geographical distributions were not predictable from known anthropogenic pressures (population in the catchment area, industry), with little comparability with other hydrophobic contaminants. If the relation between sources of OPEs and bioaccumulated levels remains uncertain, local hotspots, rather than riverine/atmospheric transportation, could account for their geographical distribution. A systematic review of the levels of OPEs found in filter-feeding bivalves worldwide revealed comparable levels in our study with those reported elsewhere; however, the levels across and within (when available) studies generally spanned several orders of magnitude, indicating high spatial and temporal heterogeneity. In view of the growing concerns regarding OPEs, this study provides essential reference data for future studies of their occurrence on European coasts and supports the need for a more systematic (bio)monitoring of this class of contaminant.

Cracked and shucked: GC-APCI-IMS-HRMS facilitates identification of unknown halogenated organic chemicals in French marine bivalves.

High resolution mass spectrometry (HRMS)-based non-target analysis coupled with ion mobility spectrometry (IMS) is gaining momentum due to its ability to provide complementary information which can be useful in the identification of unknown organic chemicals in support of efforts in unraveling the complexity of the chemical exposome. The chemical exposome in the marine environment, though not as well studied as its freshwater counterparts, is not foreign to chemical diversity specially when it comes to potentially bioaccumulative and bioactive polyhalogenated organic contaminants and natural products. In this work we present in detail how we utilized IMS-HRMS coupled with gas chromatographic separation and atmospheric pressure chemical ionization (APCI) to annotate polyhalogenated organic chemicals in French bivalves collected from 25 sites along the French coasts. We describe how we used open cheminformatic tools to exploit isotopologue patterns, isotope ratios, Kendrick mass defect (Cl scale), and collisional cross section (CCS), in order to annotate 157 halogenated features (level 1: 54, level 2: 47, level 3: 50, and level 4: 6). Grouping the features into 11 compound classes was facilitated by a KMD vs CCS plot which showed co-clustering of potentially structurally-related compounds. The features were semi-quantified to gain insight into the distribution of these halogenated features along the French coast, ultimately allowing us to differentiate between sites that are more anthropologically impacted versus sites that are potentially biodiverse.

Mutagenicity and genotoxicity of suspended particulate matter in the Seine river estuary.

Highly mutagenic compounds such as some PAHs have been identified in surface waters and sediments of the Seine river estuary. Suspended particulate matter (SPM) represents a dynamic medium that may contribute to the exposure of aquatic organisms to toxic compounds in the water column of the estuary. In order to investigate major sources of mutagenic contaminants along the estuary, water samples were taken at 25 m downstream of the outlet of an industrial wastewater-treatment plant (WWTP). SPM samples were analyzed for their genotoxicity with two short-term tests, the Salmonella typhimurium mutagenicity assay (TA98+S9 mix) and the comet assay in the human HepG2 cell line. Sampling sites receiving effluents from a chemical dye industry and WWTP showed the highest mutagenic potencies, followed by petrochemical industries, petroleum refinery and pulp and paper mills. These data indicate that frame-shift mutagens are present in the Seine river estuary. Furthermore, the comet assay revealed the presence of compounds that were genotoxic for human hepatocytes (HepG2 cells). We also observed a high level of mutagenic potency in the sediment of the lower estuary (3 × 104 revertants/g). The source of mutagenic and genotoxic compounds seems to be associated with various types of effluents discharged in the Seine river estuary. Both test systems resulted in the same assessment of the genotoxicity of particulate matter, except for three of the 14 samples, underlying the complementarity of bioassays.

Levels and trends of synthetic musks in marine bivalves from French coastal areas.

The levels and trends of four bioaccumulative synthetic musks (galaxolide - HHCB, tonalide - AHTN, musk xylene - MX and musk ketone - MK) were investigated in filter-feeding bivalves collected yearly since 2010 at sites of contrasted pressure along the French coasts. Quantification rates were high for all 4 compounds (85-99%), indicating their geographical and temporal extensive occurrence in the French coastal environment. The polycyclic musks HHCB and AHTN prevailed, with median concentrations of 2.27 ng g-1 dw and of 0.724 ng g-1 dw, whilst nitromusks were found 1 to 2 orders of magnitude lower. These levels were in the high range of those encountered for various other CEC families at the same sites and comparable to those from other locations on European coasts. Unlike for the other musks, the accumulation of HHCB was evidenced to be species-specific, with significantly lower levels found in oysters in comparison with mussels, possibly suggesting a higher metabolization in oysters. Geographical differences in musk distribution highlighted the sites under strong anthropogenic pressures and these differences were found to be consistent between years. The HHCB/AHTN ratio proved to be discriminant to explain the relative occurrence of polycyclic musks. The 8-year time series showed that only the now-banned compound MX displayed a significant decrease in most sites, whilst stable concentrations of the other musks suggested consistency in their usage over the last decade. These results provide reference data for future studies of the occurrence of personal care products on European coasts.

Polybrominated diphenyl ethers (PBDEs) in mussels from selected French coastal sites: 1981-2003.

The present study focused on the retrospective analysis of PBDEs in archived blue mussel (Mytilus edulis or Mytilus galloprovincialis) samples collected over the past 22 years (1981-2003) from coastal areas of France. We have found that PBDE levels in mussels from the English Channel increased markedly from 1981 to 1991-1995, doubling approximately every 5-6 years followed by a levelling off and a possible beginning of a decrease. The rate of the decline of hexa- and hepta-BDE congeners was more rapid than the decline of tetra- and penta-BDEs in these mussel samples. The difference in the course of time of lower and higher brominated PBDE concentrations suggests that the congener profile in the mussel samples changes over time. The increase in PBDE concentrations in the mussel samples contrasts with a concomitant constant decrease of chlorobiphenyls (CBs) in the same set of samples. However, pulse inputs of both groups of organohalogen compounds were determined for the mussel samples collected at the mouth of the Seine estuary and were probably related to riverine inundations and a flushing out of the deposited sediments from the internal estuary into the bay of the River Seine, as well as considerable dredging activities taking place during same years. In France, the highest PBDE concentrations were determined in the mussels from the English Channel, more precisely in the bay of the Seine, and the regional differences in PBDE levels were mainly connected to the difference in anthropogenic urban and industrial environmental pressures. Published data comparing PBDE levels in mussels have shown significant differences in concentrations between North/South America and Europe. This observation further confirms that the PBDE levels in the North American environment are higher than in Europe. However, the data used for this comparison of mussel contamination by PBDEs is still relatively sparse.

PCDD/F, PBDE, and nonylphenol contamination in a semi-enclosed bay (Masan Bay, South Korea) and a Mediterranean lagoon (Thau, France).

Chemical contamination of the coastal marine environment by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was assessed along with emerging contaminants such as polybrominated diphenyl ethers (PBDEs) in an industrially well-developed country (France) and a fast-developing country (Korea). Other chemicals, i.e. nonylphenol (NP) and 5 beta(H)-cholestan-3beta-ol (coprostanol) were determined to trace industrial waste and/or domestic inputs. These compounds were analyzed in coastal sediments and mussels in two enclosed coastal water bodies: Masan Bay (South Korea) and Thau lagoon (France). The overall levels of target organic contaminants were higher in Masan Bay than in Thau lagoon. The mean concentrations of 17 PCDD/Fs, 13 PBDEs, NP and coprostanol in Masan Bay sediments were, respectively, 1.3, 11, 248 and 291 ng g(-1) dry weight (d.w.); in Thau lagoon sediments they were, respectively, 0.39, not detectable (nd), 23 and 395 ng g(-1)d.w. Mean concentrations in mussels (coprostanol and cholestanol were not measured) were 0.0093, 13, 140 ng g(-1)d.w. in Masan Bay and 0.016, 0.94, 38 ng g(-1)d.w. in Thau lagoon. Principal component analysis of the contaminants and chemical tracers indicates possible point sources of pollution for Masan Bay and Thau lagoon. This study highlights a growing pollution problem in Asia and in particular a tremendous uptrend in Korea, in comparison to more controlled discharges and releases in Western Europe.