POPs in free-ranging pilot whales, sperm whales and fin whales from the Mediterranean Sea: Influence of biological and ecological factors.

The pilot whale Globicephala melas, the sperm whale Physeter macrocephalus, and the fin whale Balaenoptera physalus are large cetaceans permanently inhabiting the Mediterranean Sea. These species are subjected to numerous anthropogenic threats such as exposure to high levels of contaminants. Therefore, selected persistent organic pollutants POPs (29 PCBs, 15 organochlorine compounds, 9 PBDEs and 17 PCDD/Fs) were analysed in blubber biopsies of 49 long-finned pilot whales, 61 sperm whales and 70 fin whales sampled in the North Western Mediterranean Sea (NWMS) from 2006 to 2013. Contamination profile and species feeding ecology were then combined through the use of stable isotopes. δ(13)C, δ(15)N values and POPs levels were assessed through IR-MS and GC-MS respectively. To assess the toxic potency of the dioxin-like compounds, the TEQ approach was applied. δ(15)N values were 12.2±1.3‰ for sperm whales, 10.5±0.7‰ for pilot whales and 7.7±0.8‰ in fin whales, positioning sperm whales at higher trophic levels. δ(13)C of the two odontocetes was similar and amounted to -17.3±0.4‰ for sperm whales and -17.8±0.3‰ for pilot whales; whilst fin whales were more depleted (-18.7±0.4‰). This indicates a partial overlap in toothed-whales feeding habitats, while confirms the differences in feeding behaviour of the mysticete. Pilot whales presented higher concentrations than sperm whales for ΣPCBs (38,666±25,731 ng g(-1)lw and 22,849±15,566 ng g(-1) lw respectively), ΣPBDEs (712±412 ng g(-1) lw and 347±173 ng g(-1) lw respectively) and ΣDDTs (46,081±37,506 ng g(-1) lw and 37,647±38,518 ng g(-1) lw respectively). Fin whales presented the lowest values, in accordance with its trophic position (ΣPCBs: 5721±5180 ng g(-1) lw, ΣPBDEs: 177±208 ng g(-1) lw and ΣDDTs: 6643±5549 ng g(-1) lw). Each species was characterized by large inter-individual variations that are more related to sex than trophic level, with males presenting higher contaminant burden than females. The discriminant analysis (DA) confirmed how DDTs and highly chlorinated PCBs were influential in differentiating the three species. Pollutant concentrations of our species were significantly higher than both their Southern Hemisphere and North Atlantic counterparts, possibly due to the particular Mediterranean geomorphology, which influences pollutants distribution and recycle. Dioxin-like PCBs accounted for over 80% of the total TEQ. This study demonstrated (1) an important exposure to pollutants of Mediterranean cetaceans, often surpassing the estimated threshold toxicity value of 17,000 ng g(-1) lw for blubber in marine mammals; and (2) how the final pollutant burden in these animals is strongly influenced not only by the trophic position but also by numerous other factors such as sex, age, body size and geographical distribution.

Identification of synthetic steroids in river water downstream from pharmaceutical manufacture discharges based on a bioanalytical approach and passive sampling.

A bioanalytical approach was used to identify chemical contaminants at river sites located downstream from a pharmaceutical factory, where reproductive alterations in wild fish have been previously observed. By using polar organic compound integrative samplers (POCIS) at upstream and downstream sites, biological activity profiles based on in vitro bioassays revealed the occurrence of xenobiotic and steroid-like activities, including very high glucocorticoid, antimineralocorticoid, progestogenic and pregnane X receptor (PXR)-like activities (µg standard-EQ/g of sorbent range), and weak estrogenic activity (ng E2-EQ/g of sorbent range). Chemical analyses detected up to 60 out of 118 targeted steroid and pharmaceutical compounds in the extracts. In vitro profiling of occurring individual chemicals revealed the ability of several ones to act as agonist and/or antagonist of different steroids receptors. Mass balance calculation identified dexamethasone, spironolactone, and 6-alpha-methylprednisolone as major contributors to corticosteroid activities and levonorgestrel as the main contributor to progestogenic activities. Finally, RP-HPLC based fractionation of POCIS extracts and testing activity of fractions confirmed identified compounds and further revealed the presence of other unknown active chemicals. This study is one of the first to report environmental contamination by such chemicals; their possible contribution to in situ effects on fish at the same site is suggested.

Development of the performance reference compound approach for the calibration of "polar organic chemical integrative sampler" (POCIS).

The purpose of the Water Framework Directive is to ensure the quality of the natural water across Europe. In this context, passive samplers have shown interesting capacities for the monitoring of contaminants in aqueous ecosystems. They allow the measurement of time-weighted average concentrations, overcoming many drawbacks of the spot-sampling techniques known to be expensive and time consuming. However, application of passive samplers such as polar organic chemical integrative samplers (POCIS) for the monitoring of hydrophilic contaminants requires calibration to define compound sampling rates; key parameters to deduce the pollutant water concentrations from the amounts of pollutants accumulated by the device. Unfortunately, sampling rates are influenced by a range of environmental factors; in that respect, a question remains: is it not evident to know to what extent the sampling rates obtained in laboratory experiments can be used in field conditions? The problem can be solved for hydrophobic samplers by using performance reference compounds (PRCs), and an ongoing challenge for POCIS is focused on the improvement of the quantitative aspect of this family of samplers. In this study, potential PRCs have been selected during a specific experiment and their performance was tested in the laboratory under two hydrodynamic conditions. Results revealed a good proportionality between elimination rates of PRCs and sampling rates of chemicals. Afterwards, the application of the approach under environmental conditions was assessed by deploying POCIS in the Arcachon Bay (France) where POCIS-PRC-derived water concentrations appear to be close to the simultaneous grab-sampling results.

Evaluating pesticide mixture risks in French Mediterranean coastal lagoons waters.

To assess the risk of pesticide mixtures in lagoon waters, this study adopted a multi-step approach using integrative passive samplers (POCIS) and concentration addition (CA) toxicological models. Two French Mediterranean lagoons (Thau and Or) were monitored for a range of 68 pesticides continuously over a period of a year (2015-16). The findings revealed mixtures of dissolved pesticides with varying composition and levels over the year. The Or site contained more pesticides than Thau site (37 vs 28 different substances), at higher concentrations (0.1-58.6 ng.L-1 at Or vs <0.1-9.9 at Thau) and with overall higher detection frequencies. All samples showed a potential chronic toxicity risk, depending on the composition and concentrations of co-occurring pesticides. In 74 % of the samples, this pesticide risk was driven by a few single substances (ametryn, atrazine, azoxystrobin, carbendazim, chlorotoluron, irgarol, diuron and metolachlor) and certain transformation products (e.g. DPMU and metolachlor OA/ESA). Individually, these were a threat for the three taxa studied (phytoplankton, crustaceans and fish). Yet even a drastic reduction of these drivers alone (up to 5 % of their current concentration) would not eliminate the toxicity risks in 56 % of the Or Lagoon samples, due to pesticide mixtures. The two CA-based approaches used to assess the combined effect of these mixtures, determined chronic potential negative impacts for both lagoons, while no acute risk was highlighted. This risk was seasonal, indicating the importance of monitoring in key periods (summer, winter and spring) to get a more realistic picture of the pesticide threat in lagoon waters. These findings suggest that it is crucial to review the current EU Water Framework Directive's risk-assessment method, as it may incorrectly determine pesticide risk in lagoons.

Lab-scale investigation of the ability of Polar Organic Chemical Integrative Sampler to catch short pesticide contamination peaks.

In this lab-scale study, the POCIS capacity to integrate short contamination peaks of variable intensity and duration was evaluated. POCIS were immersed for 14 days in tanks filled with tap water and spiked at different concentrations with 12 pesticides of various polarities (log Kow = 1.1-4.7) and classes (herbicides, fungicides, and insecticides). Concentrations were kept relatively constant at 1 µg L-1 and 5 µg L-1, respectively, in two "background" exposure tanks. Three contamination peaks of increasing intensity and decreasing duration were simulated (10 µg L-1 for 24 h, 40 µg L-1 for 6 h, and 60 µg L-1 for 1 h). This lab-scale study demonstrated that ten moderately polar compounds (2 < log Kow < 4) showed a linear uptake, as observed in previous studies, while a non-linear model fits the data of the two most polar pesticides (log Kow < 2). Depending on chemical polarity, some compounds exhibited a "burst effect" or "lag effect" during the first 3 days of exposure. After 14 days of exposure, contamination peaks appeared integrated for seven compounds, showing the ability of POCIS to catch very short pollution events and to provide acceptable time-weighted average concentration estimates under laboratory-controlled conditions.

Environmental fate of chlordecone in coastal habitats: recent studies conducted in Guadeloupe and Martinique (Lesser Antilles).

The organochlorine pollution by chlordecone, an insecticide spread in the past in banana plantations, is now recognized as a major ecological, economic, and social crisis in Guadeloupe and Martinique Islands. Due to its physical and chemical properties, this molecule is particularly persistent in the natural environment. Volcanic soil of Guadeloupe and Martinique contain allophanes (amorphous clays), which favor chlordecone trapping due to their structure and physical properties. Thus, with this trapping ability, allophanes serve as a vector allowing chlordecone to contaminate runoff waters and, finally, the sea. In the present publication, several studies recently conducted in the Lesser Antilles have been compiled in order to evaluate the desorption of chlordecone from allophanes when arriving in the estuarine environment and to determine the transfer of chlordecone along marine trophic food webs. The experiments showed that 20% of the initial quantity of chlordecone was released from allophanes in estuarine conditions and 10% in the marine environment. These results could explain the high level of contamination found in the suspended organic matter and zooplankton in the coastal areas located downstream of the contaminated watersheds. The contamination of the marine food webs of mangroves, seagrass beds, and coral reefs is dominated by a contamination "by bath" in littoral waters containing chlordecone and by bioamplification seawards.

Chlordecone-contaminated epilithic biofilms show increased adsorption capacities.

The rivers of Guadeloupe and Martinique (French West Indies) show high levels of chlordecone (CLD) contamination. This persistent molecule has a dramatic impact on both aquatic ecosystems and human health. In these rivers, epilithic biofilms are the main endogenous primary producers and represent a central food source for fish and crustaceans. Recently, their viscoelastic properties have been shown to be effective in bio-assessing pollution in tropical environments. As these properties are closely related to the biochemical composition of the biofilms, biochemical (fatty acids, pigments, extracellular polymeric substances (EPS) monosaccharides) and molecular markers (T-RFLP fingerprints of bacteria, archaea and eukaryotes) were investigated. Strong links between CLD pollution and both biofilm biochemistry and microbial community composition were found. In particular, high levels of CLD were linked with modified exo-polysaccharides corresponding to carbohydrates with enhanced adsorption and adhesion properties. The observed change probably resulted from a preferential interaction between CLD and sugars and/or a differential microbial secretion of EPS in response to the pollutant. These changes were expected to impact viscoelastic properties of epilithic biofilms highlighting the effect of CLD pollution on biofilm EPS matrix. They also suggested that microorganisms implement a CLD scavenging strategy, providing new insights on the role of EPS in the adaptation of microorganisms to CLD-polluted environments.

Temporal variations in the level of chlordecone in seawater and marine organisms in Martinique Island (Lesser Antilles).

The present study, conducted in the Galion Bay in Martinique, aims to highlight the temporal and seasonal variations of chlordecone contamination (an organochlorine pollutant) in the ambient environment (seawater) and also in the marine organisms in three main coastal marine habitats (mangroves, seagrass beds and coral reefs). To this end, two methodologies were used to measure and compare the chemical contamination of seawater during 13 months (spot samplings and POCIS technique). In parallel, concentrations of chlordecone and isotopic ratios (C and N) were carried out on marine organisms, collected during two contrasting climatic periods (dry and rainy), to evidence seasonal variations. The results showed that the contamination of seawater displayed significant variations over time and depended on environmental factors such as water flows, which imply dilution and dispersion phenomena. Concerning the marine organisms, the level of contamination varied considerably between the two seasons in seagrass beds with higher levels of contamination during the rainy season. Reef organisms were more moderately affected by this pollution, while mangrove organisms showed a high level of chlordecone whatever the season. Finally, isotope analyses highlighted that bioamplification along marine food webs occurs at each season and each station.

Removal efficiency of emerging micropollutants in biofilter wastewater treatment plants in tropical areas.

We studied the removal of 61 emerging micropollutants, including illicit drugs, in a biofilter wastewater treatment plant located in the French Indies (Martinique). Raw wastewater concentrations were the highest for paracetamol followed by caffeine, naproxen, ibuprofen, its metabolite 2-hydroxyibuprofen, atenolol, ketoprofen, furosemide, methylparaben, cocaine, benzoylecgonine, and 11-nor-delta-9-carboxytetrahydrocannabinol (THC-COOH). The calculated removals were better than those reported in the literature, while the cumulative removal efficacy (i.e., removal of the total mass load) was estimated to be 92 ± 4%. However, this good performance may be partly explained by the removal of paracetamol (also named acetaminophen) and caffeine, which represented 86.4% of the total mass load. Our results point to the adsorption of some molecules on sludge, thus raising the question about local soil pollution from sludge spreading.

Evaluation of an hPXR reporter gene assay for the detection of aquatic emerging pollutants: screening of chemicals and application to water samples.

Many environmental endocrine-disrupting compounds act as ligands for nuclear receptors. Among these receptors, the human pregnane X receptor (hPXR) is well described as a xenobiotic sensor to various classes of chemicals, including pharmaceuticals, pesticides, and steroids. To assess the potential use of PXR as a sensor for aquatic emerging pollutants, we employed an in vitro reporter gene assay (HG5LN-hPXR cells) to screen a panel of environmental chemicals and to assess PXR-active chemicals in (waste) water samples. Of the 57 compounds tested, 37 were active in the bioassay and 10 were identified as new PXR agonists: triazin pesticides (promethryn, terbuthryn, terbutylazine), pharmaceuticals (fenofibrate, bezafibrate, clonazepam, medazepam) and non co-planar polychlorobiphenyls (PCBs; PCB101, 138, 180). Furthermore, we detected potent PXR activity in two types of water samples: passive polar organic compounds integrative sampler (POCIS) extracts from a river moderately impacted by agricultural and urban inputs and three effluents from sewage treatment works (STW). Fractionation of POCIS samples showed the highest PXR activity in the less polar fraction, while in the effluents, PXR activity was mainly associated with the dissolved water phase. Chemical analyses quantified several PXR-active substances (i.e., alkylphenols, hormones, pharmaceuticals, pesticides, PCBs, bisphenol A) in POCIS fractions and effluent extracts. However, mass-balance calculations showed that the analyzed compounds explained only 0.03% and 1.4% of biological activity measured in POCIS and STW samples, respectively. In effluents, bisphenol A and 4-tert-octylphenol were identified as main contributors of instrumentally derived PXR activities. Finally, the PXR bioassay provided complementary information as compared to estrogenic, androgenic, and dioxin-like activity measured in these samples. This study shows the usefulness of HG5LN-hPXR cells to detect PXR-active compounds in water samples, and further investigation will be necessary to identify the detected active compounds.

Physical properties of epilithic river biofilm as a new lead to perform pollution bioassessments in overseas territories.

Chlordecone (CLD) levels measured in the rivers of the French West Indies were among the highest values detected worldwide in freshwater ecosystems, and its contamination is recognised as a severe health, environmental, agricultural, economic, and social issue. In these tropical volcanic islands, rivers show strong originalities as simplified food webs, or numerous amphidromous migrating species, making the bioindication of contaminations a difficult issue. The objective of this study was to search for biological responses to CLD pollution in a spatially fixed and long-lasting component of the rivers in the West Indies: the epilithic biofilm. Physical properties were investigated through complementary analyses: friction, viscosity as well as surface adhesion were analyzed and coupled with measures of biofilm carbon content and exopolymeric substance (EPS) production. Our results have pointed out a mesoscale chemical and physical reactivity of the biofilm that can be correlated with CLD contamination. We were able to demonstrate that epilithic biofilm physical properties can effectively be used to infer freshwater environmental quality of French Antilles rivers. The friction coefficient is reactive to contamination and well correlated to carbon content and EPS production. Monitoring biofilm physical properties could offer many advantages to potential users in terms of effectiveness and ease of use, rather than more complex or time-consuming analyses.

Temporal variations of perfluoroalkyl substances partitioning between surface water, suspended sediment, and biota in a macrotidal estuary.

A one-year monitoring study was conducted in a macrotidal estuary to assess the temporal variations and partitioning behavior of perfluoroalkyl and polyfluoroalkyl substances (PFASs). Surface water, suspended particulate matter (SPM), and invertebrates including zooplankton (copepods, mysids) and shrimps were sampled on a monthly basis in the Gironde Estuary (SW France). Environmental parameters such as suspended solid loads, salinity, and river water flow rate were highly variable at the study site. However, moderate seasonal variations were observed in terms of PFAS levels and profiles. Summed PFAS (Σ22PFASs) concentrations averaged 6.5 ±â€¯2.7 ng L-1 in the dissolved phase and 3.0 ±â€¯1.2 ng g-1 dry weight in the SPM. The Σ22PFASs was in the range of 1.7-13 ng g-1 wet weight in invertebrates. C5-C8 perfluoroalkyl carboxylates (PFCAs) generally prevailed in the dissolved phase, while perfluorooctane sulfonate (PFOS) was dominant in the SPM and biota. Suspended sediment-water partitioning coefficients Log KD and Log KOC were correlated with the perfluoroalkyl chain length, as were the particle-bound fraction and bioaccumulation factors (Log BAF). Compound-specific Log BAFs varied within a limited range over the period surveyed. Biomagnification factors (mysids/copepods) were consistently >1 for PFOS, perfluorooctane sulfonamide, and long-chain PFCAs (perfluorodecanoate and perfluorododecanoate), suggesting biomagnification at the base of the estuarine food web.

Demonstrating the need for chemical exposure characterisation in a microplate test system: toxicity screening of sixteen pesticides on two marine microalgae.

Pesticides used in viticulture create a potential risk for the aquatic environment due to drift during application, runoff and soil leaching. The toxicity of sixteen pesticides and one metabolite were evaluated on the growth of two marine microalgae, Tisochrysis lutea and Skeletonema marinoi, in 96-h exposure assays conducted in microplates. For each substance, concentrations of stock solutions were analytically measured and abiotic assays were performed to evaluate the chemical stability of pesticides in microplates. For two chemicals, microalgae exposures were run simultaneously in microplates and culture flasks to compare EC50 calculated from the two exposure systems. Results from chemical analyses demonstrated the low stability of hydrophobic pesticides (log KOW > 3). For such chemicals, EC50 values calculated using measured pesticide concentrations were two-fold lower than those first estimated using nominal concentrations. Photosystem II inhibitors were the most toxic herbicides, with EC50 values below 10 µg L-1 for diuron and around double this for isoproturon. Chlorpyrifos-methyl was the only insecticide to significantly affect the growth of T. lutea, with an EC50 around 400 µg L-1. All fungicides tested were significantly toxic to both species: strobilurins showed low overall toxicity, with EC50 values around 400 µg L-1, whereas quinoxyfen, and spiroxamine, showed high toxicity to both species, especially to T. lutea, with an EC50 below 1 µg L-1 measured for spiroxamine in culture flasks. This study highlights the need to perform chemical analyses for reliable toxicity assessment and discusses the advantages and disadvantages of using microplates as a toxicity screening tool.

A model for estimating the potential biomagnification of chemicals in a generic food web: preliminary development.

GOAL, SCOPE AND BACKGROUND: Bioaccumulation and biomagnification of organic pollutants have been increasingly assessed and modeled during the last years. Due to the complexity of these processes and the large variability of food webs, setting generic assessments for these parameters is really difficult. Equilibrium models, based on a compound's lipophylicity, are the main tool in regulatory proposals, such as for identifying Persistent, Bioaccumulative and Toxic Substances (PBTs), although a refinement has been claimed by the scientific community. Toxicokinetic studies offer an alternative for these estimations, where biomagnification is modeled as a succession of bioaccumulation processes, each one regulated by toxicokinetic parameters. METHODS: A review of kinetic models covering species belonging to different trophic levels and with different ecological behavior has been conducted. The results were employed for setting a conceptual model for estimating the biomagnification potential in a generic food web, which was mathematically implemented through system dynamic models developed under data sheet software. Crystal Ball was then employed for allowing Monte Carlo based probabilistic calculations. Bioaccumulation laboratory assays have been performed to estimate toxicokinetic parameters in mussels (Mytilus edulis) with two PAHs (chrysene and benzo[a]pyrene). The contamination was delivered via food. The exposure period lasted more than one month followed then by a depuration phase. The contaminant content was determined on an individual basis on five replicates. RESULTS AND DISCUSSION: . The reviewed information suggested the development of a tiered conceptual biomagnification model, starting with a simplified food chain which can be refined to more realistic and complex models in successive levels. CONCLUSIONS: The mathematical implementation of the conceptual model offers tools for estimating the potential for bioaccumulation and biomagnification of chemicals under very different conditions. The versatility of the model can be used for both comparative estimations and for validating the model. RECOMMENDATIONS AND PERSPECTIVES: Since bioaccumulation and biomagnification processes are crucial elements for a proper risk assessment of chemicals, their estimation by mathematical models has been widely tested. However, inregulatory assessments, too simplistic models are still being used quite often. The biomagnification model presented in this study should be amore accurate alternative to these models. In comparison to other previously published biomagnification models, the present one covers the time variation of bioaccumulation using just a few toxicokinetic parameters.

Adaptive response under multiple stress exposure in fish: From the molecular to individual level.

Aquatic systems are subjected to various sources of stress due to global changes, such as increasing temperature and pollution. A major challenge for the next decade will be to evaluate the combined effects of these multiple stressors on organisms and ecosystems. For organisms submitted to chemical, biological or physical stressors, the capacity to set up an efficient adaptive response is a fundamental prerequisite for their long-term survival and performance. In this study, goldfish (Carassius auratus) were subjected to individual and combined pesticide mixtures and increased temperatures to evaluate their adaptive response in multistress conditions from the molecular to the individual level. Fish were exposed for 16 days to a mixture of pesticides at environmental relevant concentrations (S-metolachlor, isoproturon, linuron, atrazine-desethyl, aclonifen, pendimethalin and tebuconazole) and at two temperatures (22 °C and 32 °C). Three major physiological traits of the stress response were measured: the hormonal response (i.e. plasma cortisol), the metabolic balance from molecular to individuals' levels (metabolomics, cellular energy allocation, energy reserves and global condition indexes), and the cellular defense system induction (SOD, CAT and GST). Results show that (1) environmentally relevant concentrations of pesticides lead to significant responses in fish at all biological levels; (2) the metabolic response depends on the nature of stress (thermal vs. chemical); and (3) fish may be unable to set up an efficient adaptive response when chemical and thermal stresses were combined, with adverse outcomes at the individuals' level.

Combined effects of pollutants and salinity on embryo-larval development of the Pacific oyster, Crassostrea gigas.

For several years, low larval recruitment has been observed in Arcachon Bay, in southwest France. Exposure to pollutants could partly account for the reduction of early life stages of the Pacific oyster. This study evaluated the effects of copper and S-metolachlor in combination with salinity on the early life stages of Crassostrea gigas. Embryos were exposed to concentrations of copper (1, 10 and 50 µg L(-1)) or S-metolachlor (10, 100 and 1000 ng L(-1)) and six salinities (18, 21, 24, 27, 30 and 33 u.s.i). Embryotoxicity was measured by considering both the percentage of abnormalities and arrested development in D-shaped larvae. Embryo-larval development was only affected at salinities ≤24 u.s.i, which have never been observed during C. gigas reproduction period in Arcachon Bay. Both contaminants had an effect at environmental concentrations. Our results suggest that copper and metolachlor toxicity was enhanced with decreasing salinity.

Occurrence of pharmaceutical compounds and pesticides in aquatic systems.

This paper deals with the detection and quantification of APIs and other priority substances in the Arade River estuary (Portugal) providing the usefulness of Polar Organic Compound Integrative Samplers (POCIS). Thirteen APIs were detected whose variation was site and time dependent. Caffeine was at the highest concentration (804±209 ng/L) followed by theophylline (184±44 ng/L). Other APIs were analgesic, anticonvulsant, non-steroidal anti-inflammatory drugs, anti-lipidemic, anxiolytic and antidepressants. Twenty pesticides comprising atrazine, diuron, isoproturon, terbutryn and simazine included in the Water Framework Directive priority list were also site and time dependent. Carbendazim occurred at the highest concentration (45±18 ng/L at site 1) but atrazine, diuron, isoproturon and simazine levels were below the Environmental Quality Standards. Although the summer impact was unclear, the results highlighted POCIS suitability for profiling these contaminants. This is to our knowledge the first study concerning APIs and pesticides in this area.

Comparative responses of sperm cells and embryos of Pacific oyster (Crassostrea gigas) to exposure to metolachlor and its degradation products.

Metolachlor is one of the most intensively used chloroacetanilide herbicides in agriculture. Consequently, it has been frequently detected in coastal waters as well as its major degradation products, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOA) which are encountered at higher concentrations than metolachlor. Although a few studies of metolachlor toxicity have been conducted on marine organisms, little is known about the environmental toxicity of metolachlor degradation products. In this study, the deleterious effects of metolachlor and its degradation products on spermatozoa and embryos of Crassostrea gigas have been compared using biomarkers of developmental defects, DNA damage and gene transcription levels. After 24h exposure, significant increases in the percentage of abnormal D-larvae and DNA damage were observed from 0.01 µg L(-1) for S-metolachlor and 0.1 µg L(-1) for MESA and MOA. Results showed that S-metolachlor was more embryotoxic and genotoxic than its degradation products. Oyster sperm was also very sensitive to metolachlor exposure and followed the pattern: metolachlor (0.01 µg L(-1))>MOA (0.1 µg L(-1))>MESA (1 µg L(-1)). Metolachlor and MESA mainly triggered variations in the transcription level of genes encoding proteins involved in oxidative stress responses (mitochondrial superoxide dismutase and catalase). Overall, no significant variation in transcription levels could be detected in C. gigas embryos exposed to MOA. This study demonstrates that metolachlor and its main degradation products have the potential to impact several steps of oyster development and therefore recruitment in coastal areas exposed to chronic inputs of pesticides.

Distribution of steroid- and dioxin-like activities between sediments, POCIS and SPMD in a French river subject to mixed pressures.

The contamination of aquatic systems by endocrine disrupting chemicals (EDCs) is now a widely established fact. Nevertheless, there is still a scarcity of knowledge concerning the source, transport, fate and bioavailability of such active compounds. In the present study we assessed the distribution of estrogenic, (anti-)androgenic, pregnane X receptor-like (PXR) and dioxin-like activities between sediment and water compartments using a polar organic compound integrative sampler (POCIS) and a semi-permeable membrane device (SPMD) passive sampler in a river where sediment has been previously described as highly and multi-contaminated. We first confirmed the contamination pattern of this river sediment between 2004, 2009 and 2010 samples, suggesting that this river is subject to a constant high contamination level. However, we showed a different distribution pattern of these activities between compartments: estrogenic activity was mainly detected in POCIS extracts and to a lesser extent in sediment and SPMD extracts; anti-androgenic activities were mainly detected in SPMD and sediment extracts while no activity was detected in POCIS extracts; PXR-like activity was detected in all three investigated compartments, with POCIS > SPMD > sediment; dioxin-like activity was mainly found in the sediment and the SPMD extracts. Overall, partitioning of the biological activities was in accordance with physicochemical properties (e.g., log K ow) of typical known active chemicals in each bioassay. Furthermore, in order to establish whether the chemicals involved in these activities were similar between the compartments, we fractionated sediment, POCIS and SPMD extracts using a multi-step fractionation procedure. This highlighted differences in the nature of active chemicals between compartments. Altogether, our results support the need to consider different compartments in order to enhance exposure assessment.

PBDE and PCB contamination of eels from the Gironde estuary: from glass eels to silver eels.

Since the 1980s, the eel population has been decreasing dangerously. Persistent Organic Pollutants (POPs) such as Polychlorinated Biphenyls (PCBs) are one of the suspected causes of this decline. A preliminary study of PCB contamination carried out on different fish from the Gironde estuary (southwest of France, Europe) has shown a relatively high level of contamination of eel muscles. In order to characterize the contamination level of PCBs and PBDEs (PolyBrominated Diphenyl-Ethers) in eels from this estuary more than 240 eels were collected during the years 2004-2005 in the Gironde estuarine system, from glass eels to silver eels. Individual European eels were grouped according to length and localization sites. The results have shown a low contamination level of glass eels: respectively 28±11 ng g(-1)dw for PCBs and 5±3 ng g(-1)dw for PBDEs. The contamination level in eels (expressed in ng g(-1)dw) increases from glass eels to silver eels up to 3399 ng g(-1)dw of PCBs for the most contaminated silver eel. Such levels of PCBs similar to those observed in Northern Europe, could raise sanitary problems connected with the World Health Organization (WHO) recommendations. These results are worrying for the local people who regularly eat eels caught in the Gironde estuary.