Catherine Munschy

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.

Monitoring of trace-levels of herbicides and their degradation products in the river Rhône, France, by gas chromatography-mass spectrometry

Sampling of 5 liters of river Rhone water in each of seven stations located at the Camargue region took place in November 1990 during an oceanographic cruise (Dypole 7) organized within the French scientific programme GDR-ICO (Groupement De Recherche, Interface Continent Ocean, CNRS). After sampling was completed, water samples were filtered through fiberglass filters and two fractions corresponding to dissolved and particulate matter were obtained. Dichloromethane was used for the liquid-liquid extraction of chlorotriazines dissolved in water with further quantitation by selected ion monitoring (SIM) gas chromatography-mass spectrometry (GC-MS). Concentrations of atrazine in the range of 12–30 ng/l and 1 ng/l in the dissolved and suspended phase, respectively, were found. Such levels were compared with previously reported data from other rivers and have been related with the distribution coefficients Koc. An estimation of the loss of applied atrazine in the Rhone basin is also reported.

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 1. Bioaccumulation and elimination kinetics of individual congeners and their debrominated metabolites

The uptake and elimination of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, then depurated over a five-month period. The results show that all of the studied PBDEs accumulate in fish tissues, including the higher brominated congener BDE-209. Several additional PBDE congeners were identified in the tissues of exposed fish, revealing PBDE transformation, mainly via debromination. The identified congeners originating from PBDE debromination include BDE-49 and BDE-202 and a series of unidentified tetra-, penta-, and hepta- BDEs. Contaminant assimilation efficiencies (AEs) were related to their hydrophobicity (log Kow) and influenced by PBDE biotransformation. Metabolism via debromination appears to be a major degradation route of PBDEs in juvenile sole in comparison to biotransformation into hydroxylated metabolites.

Levels and trends of the emerging contaminants HBCDs (hexabromocyclododecanes) and PFCs (perfluorinated compounds) in marine shellfish along French coasts

The levels and congener patterns of HBCDs (hexabromocyclododecanes) and PFCs (perfluorinated compounds) were determined in filter-feeding molluscs collected in 2008 and 2010 along the coasts of mainland France. α-HBCD and PFOS (perfluorooctane sulfonate) were detected in all samples, revealing widespread contamination of the coastal environment by these emerging contaminants. The spatial distribution of Σ-HBCD concentrations showed higher median levels in samples from the Mediterranean Sea and English Channel respectively, i.e. 0.19 ng g(-1) wet weight (ww) and 0.08 ng g(-1) ww, related to high anthropogenic pressure from urban and industrial activities, while the median concentration was 0.05 ng g(-1) ww in samples from the Atlantic coast. Among PFCs, PFOS was the only compound detected in all samples and PFDA (perfluorodecanoic acid) was the second most frequently-detected compound. PFOS median concentrations were 0.18 ng g(-1) ww, 0.09 ng g(-1) ww and 0.04 ng g(-1) ww in samples from the English Channel, the Atlantic coast and the Mediterranean coast respectively. The highest PFOS concentration was found in the Loire estuary, possibly related to local industrial activities. The Mediterranean samples showed a different pattern, with predominant long-chain PFCAs (perfluorocarboxylic acids), suggesting the presence of alternative sources on the Mediterranean coast. The temporal trends studied in archived samples from the Seine estuary site showed a significant exponential increase in HBCD concentrations between 1981 and 2011, with a doubling time of 7 years, while PFOS levels underwent a significant linear decrease over time. These trends are coherent with current regulations on the use of these compounds. The results presented in this paper provide the first data on the contamination of the French coastal marine environment by the selected emerging compounds, and constitute a reference for the future monitoring of French coastal contamination by emerging contaminants.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in marine mussels from French coasts: Levels, patterns and temporal trends from 1981 to 2005

The levels and temporal trends of toxic polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in archived marine mussels collected between 1981 and 2005 from selected sites along French coasts. The geographical distribution and levels of PCDD/Fs generally reflect regional inputs of these contaminants: the highest concentrations were determined in samples from the Seine river estuary (English Channel) and Toulon area (Mediterranean coast); the lowest levels were determined in Corsica (Mediterranean Sea). PCDD/F isomeric composition showed a fairly homogeneous distribution pattern throughout the various sampling sites. This pattern, dominated by 2,3,7,8-TCDF and OCDD, can be considered as typical for the study species. However, on a more local scale, some differences in isomeric composition in mussels were identified in relation to local source characteristics. The time trend study showed a pronounced decrease in PCDD/F concentrations over the 24-year period at most sites, except Toulon on the Mediterranean Sea, where the decrease was not significant. This overall decrease probably reflects the general drop in PCDD/F emissions in Europe since 1980. However, high concentrations were determined in mussels collected in recent years (1999, 2001 and 2005) from the mouth of the Seine river. These concentrations are related to particular hydrological conditions, and intensive sediment dredging due to a new port construction at the mouth of the estuary. The results presented in this paper provide reference data on the contamination of shellfish by persistent organic pollutants in the marine environment.

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.

Persistent organic pollutants in albacore tuna (Thunnus alalunga) from Reunion Island (Southwest Indian Ocean) and South Africa in relation to biological and trophic characteristics

The contamination of albacore tuna (Thunnus alalunga) by Persistent Organic Pollutants (POPs), namely polychlorinated biphenyls (PCBs) and dichlorodiphenyl-trichloroethane (DDT), was investigated in individuals collected from Reunion Island (RI) and South Africas (SA) southern coastlines in 2013, in relation to biological parameters and feeding ecology. The results showed lower PCB and DDT concentrations than those previously reported in various tuna species worldwide. A predominance of DDTs over PCBs was revealed, reflecting continuing inputs of DDT. Tuna collected from SA exhibited higher contamination levels than those from RI, related to higher dietary inputs and higher total lipid content. Greater variability in contamination levels and profiles was identified in tuna from RI, explained by a higher diversity of prey and more individualistic foraging behaviour. PCB and DDT contamination levels and profiles varied significantly in tuna from the two investigated areas, probably reflecting exposure to different sources of contamination.

Fish life-history traits are affected after chronic dietary exposure to an environmentally realistic marine mixture of PCBs and PBDEs

Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are persistent organic pollutants that have been shown to affect fish life-history traits such as reproductive success, growth and survival. At the individual level, their toxicity and underlying mechanisms of action have been studied through experimental exposure. However, the number of experimental studies approaching marine environmental situations is scarce, i.e., in most cases, individuals are exposed to either single congeners, or single types of molecules, or high concentrations, so that results can hardly be transposed to natural populations. In the present study, we evaluated the effect of chronic dietary exposure to an environmentally realistic marine mixture of PCB and PBDE congeners on zebrafish life-history traits from larval to adult stage. Exposure was conducted through diet from the first meal and throughout the life cycle of the fish. The mixture was composed so as to approach environmentally relevant marine conditions in terms of both congener composition and concentrations. Life-history traits of exposed fish were compared to those of control individuals using several replicate populations in each treatment. We found evidence of slower body growth, but to a larger asymptotic length, and delayed spawning probability in exposed fish. In addition, offspring issued from early spawning events of exposed fish exhibited a lower larval survival under starvation condition. Given their strong dependency on life-history traits, marine fish population dynamics and associated fisheries productivity for commercial species could be affected by such individual-level effects of PCBs and PBDEs on somatic growth, spawning probability and larval survival.

Tissue-specific distribution and maternal transfer of polybrominated diphenyl ethers (PBDEs) and their metabolites in adult common sole (Solea solea L.) over an entire reproduction cycle

Tissue-specific accumulation and distribution of polybrominated diphenyl ethers (PBDEs) and their debrominated metabolites were studied in common sole (Solea solea) over an entire reproduction cycle. The fish were dietary-exposed to selected PBDEs in laboratory-controlled conditions for one year. Fish of both sexes were sampled throughout the reproduction cycle and their muscle, liver, viscera, carcass, skin and gonads (female) were analysed for total lipid content, PBDEs and their debrominated metabolites. On a wet weight basis, the concentrations of most spiked congeners showed an increase at the end of the exposure time in the whole body of fish of both sexes. Conversely, BDE-99 and BDE-209 - the two most highly metabolized congeners - did not show a similar increase, while their debrominated metabolites exhibited a linear increase over time. Biomagnification factors (BMFs) calculated in whole body were > 1 for all PBDEs except BDE-99 (0.89 ± 0.22) and BDE-209 (0.013 ± 0.006). BMFs were strongly correlated to apparent assimilation efficiencies, which ranged from 1.6% ± 0.7% (BDE-209) to 88% ± 11% (BDE-100). Fish carcass was the most predominant storage compartment for all PBDEs except BDE-209 in both male and female fish, followed by skin, muscle, female gonads, liver and visceral tissue. BDE-209 showed a different distribution and was stored more predominantly in the liver, viscera and female gonads than other congeners, probably due to its transport with lipoproteins. All PBDEs except BDE-209 showed equilibrium partitioning between the liver and other studied compartments, while BDE-209 showed a higher affinity with blood-enriched tissues, leading to higher liver / carcass, skin and muscle concentration ratios. Visceral tissue and liver exhibited the most pronounced differences in terms of concentration variations between sexes and over time. In females, both tissues showed a significant decrease in most PBDE concentrations (ww) and TLC in March during the spawning season, with low inter-individual variability, reflecting the striking utilisation of lipids by females for reproduction at this time. In males, no differences were found in concentrations in these compartments over time and a high inter-individual variability was observed. Maternal transfer of PBDEs from gonad to eggs was constant, regardless of spawn rank in the spawning season. Egg / gonad PBDE concentration ratios (in lw) were 1.3 ± 0.7 for all congeners and 2.6 ± 0.3 for BDE-209, suggesting a higher transfer of this congener from gonads to eggs.