[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | International audience | Estuarine areas represent complex and highly changing environments at the interface between freshwater and marine aquatic ecosystems. Therefore, the aquatic organisms living in estuaries have to face highly variable environmental conditions. The aimof this work was to study the influence of environmental changes from either natural or anthropogenic origins on the physiological responses of Mytilus edulis. Mussels were collected in theVilaine estuary during early summer because this season represents a critical period of active reproduction in mussels and of increased anthropogenic inputs from agricultural and boating activities into the estuary. The physiological status of the mussel M. edulis was evaluated through measurements of a suite of biomarkers related to: oxidative stress (catalase, malondialdehyde), detoxication (benzopyrene hydroxylase, carboxylesterase), neurotoxicity (acetylcholinesterase), reproductive cycle (vitelline, condition index, maturation stages), immunotoxicity (hemocyte concentration, granulocyte percentage, phagocytosis, reactive oxygen species production, oxidative burst), and general physiological stress (lysosomal stability). A selection of relevant organic contaminant (pesticides, (polycyclic aromatic hydrocarbons, polychlorobiphenyls) was measured as well as environmental parameters (water temperature, salinity, total suspended solids, turbidity, chlorophyll a, pheopigments) and mussel phycotoxin contamination. Two locations differently exposed to the plume of the Vilaine River were compared. Both temporal and inter-site variations of these biomarkers were studied. Our results show that reproduction cycle and environmental parameters such as temperature, organic ontaminants, and algal blooms could strongly influence the biomarker responses. These observations highlight the necessity to conduct integrated environmental approaches in order to better understand the causes of biomarker variations.

[Departement_IRSTEA]Ecotechnologies [TR1_IRSTEA]TED [Axe_IRSTEA]TED-SOWASTE [Axe_IRSTEA]TED-EPURE | Many xenobiotics, including several pharmaceuticals and pesticides, are poorly treated in domestic wastewater treatment plants. Adsorption processes, such as with activated carbons, could be a solution to curb their discharge into the aquatic environment. As adsorbent-like activated carbon is known to be expensive, identifying promising alternative adsorbent materials is a key challenge for efficient yet affordable xenobiotic removal from wastewaters. As part of the effort to address this challenge, we surveyed the literature on pharmaceutical and pesticide xenobiotics and built a database compiling data from 38 scientific publications covering 65 xenobiotics and 58 materials. Special focus was given to the relevance and comparability of the data to the characteristics of the adsorbent materials used and to the operating conditions of the batch tests inventoried. This paper gives an in-depth overview of the adsorption capacities of various adsorbents. The little data on alternative adsorbent materials, especially for the adsorption of pharmaceuticals, makes it difficult to single out any one activated carbon alternative capable of adsorbing pesticides and pharmaceuticals at the tertiary stage of treatment. There is a pressing need for further lab-scale experiments to investigate the tertiary treatment of discharged effluents. We conclude with recommendations on how future data should best be used and interpreted.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | International audience | Estuarine areas represent complex and highly changing environments at the interface between freshwater and marine aquatic ecosystems. Therefore, the aquatic organisms living in estuaries have to face highly variable environmental conditions. The aimof this work was to study the influence of environmental changes from either natural or anthropogenic origins on the physiological responses of Mytilus edulis. Mussels were collected in theVilaine estuary during early summer because this season represents a critical period of active reproduction in mussels and of increased anthropogenic inputs from agricultural and boating activities into the estuary. The physiological status of the mussel M. edulis was evaluated through measurements of a suite of biomarkers related to: oxidative stress (catalase, malondialdehyde), detoxication (benzopyrene hydroxylase, carboxylesterase), neurotoxicity (acetylcholinesterase), reproductive cycle (vitelline, condition index, maturation stages), immunotoxicity (hemocyte concentration, granulocyte percentage, phagocytosis, reactive oxygen species production, oxidative burst), and general physiological stress (lysosomal stability). A selection of relevant organic contaminant (pesticides, (polycyclic aromatic hydrocarbons, polychlorobiphenyls) was measured as well as environmental parameters (water temperature, salinity, total suspended solids, turbidity, chlorophyll a, pheopigments) and mussel phycotoxin contamination. Two locations differently exposed to the plume of the Vilaine River were compared. Both temporal and inter-site variations of these biomarkers were studied. Our results show that reproduction cycle and environmental parameters such as temperature, organic ontaminants, and algal blooms could strongly influence the biomarker responses. These observations highlight the necessity to conduct integrated environmental approaches in order to better understand the causes of biomarker variations.

International audience | The potential leaching of pollutants present in harbor sediments has to be evaluated in order to choose the best practices for managing them. Little is known about the speciation and mobility of heavy metals in these specific solid materials. The objective of this paper is to determine and model the leachability of copper, lead, and zinc present in harbor sediments in order to obtain essential new data. The mobility of inorganic contaminants in a polluted harbor sediment collected in France was investigated as a function of physicochemical conditions. The investigation relied mainly on the use of leaching tests performed in combina- tion with mineralogical analysis and thermodynamic mod- eling using PHREEQC. The modeling phase was dedicated to both confirm the hypothesis formulated to explain the experimental results and improve the determination of the main physico-chemical parameters governing mobility. The experimental results and modeling showed that the release of copper, lead, and zinc is very low with deionized water which is due to the stability of the associated solid phases (organic matter, carbonate minerals, and/or iron sulfides) at natural slightly basic conditions. However, increased mobilization is observed under pH values below 6.0 and above 10.0. This methodology helped to consistently obtain the geochemical parameters governing the mobility of the contaminants studied.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | International audience | The feeding activity and subsequent assimilation of the products resulting from food digestion allow organisms to obtain energy for growth, maintenance and reproduction. Among these biological parameters, we studied digestive enzymes (amylase, cellulase and trypsin) in Gammarus fossarum to assess the impact of contaminants on their access to energy resources. However, to enable objective assessment of a toxic effect of decreased water quality on an organisms’ digestive capacity, it is necessary to establish reference values based on its natural variability as a function of changing biotic and abiotic factors. To limit the confounding influence of biotic factors, a caging approach with calibrated male organisms from the same population was used. This study applied an in situ deployment at 23 sites of the Rhone basin rivers, complemented by a laboratory experiment assessing the influence of two abiotic factors (temperature and conductivity). The results showed a small effect of conductivity on cellulase activity and a significant effect of temperature on digestive enzyme activity but only at the lowest temperature (7 °C). The experimental conditions allowed us to define an environmental reference value for digestive enzyme activities to select sites where the quality of the water impacted the digestive capacity of the organisms. In addition to the feeding rate, this study showed the relevance of digestive enzymes as biomarkers to be used as an early warning tool to reflect organisms’ health and the chemical quality of aquatic ecosystems.

A 2-year study was implemented to characterize the contamination of estuarine continuums in the Bay of Vilaine area (NW Atlantic Coast, Southern Brittany, France) by 30 pesticide and biocide active substances and metabolites. Among these, 11 triazines (ametryn, atrazine, desethylatrazine, desethylterbuthylazine, desisopropyl atrazine, Irgarol 1051, prometryn, propazine, simazine, terbuthylazine, and terbutryn), 10 phenylureas (chlortoluron, diuron, 1-(3,4-dichlorophenyl)-3-methylurea, fenuron, isoproturon, 1-(4-isopropylphenyl)-3-methylurea, 1-(4-isopropylphenyl)-urea, linuron, metoxuron, and monuron), and 4 chloroacetanilides (acetochlor, alachlor, metolachlor, and metazachlor) were detected at least once. The objectives were to assess the corresponding risk for aquatic primary producers and to provide exposure information for connected studies on the responses of biological parameters in invertebrate sentinel species. The risk associated with contaminants was assessed using risk quotients based on the comparison of measured concentrations with original species sensitivity distribution-derived hazardous concentration values. For EU Water Framework Directive priority substances, results of monitoring were also compared with regulatory Environmental Quality Standards. The highest residue concentrations and risks for primary producers were recorded for diuron and Irgarol 1051 in Arzal reservoir, close to a marina. Diuron was present during almost the all survey periods, whereas Irgarol 1051 exhibited a clear seasonal pattern, with highest concentrations recorded in June and July. These results suggest that the use of antifouling biocides is responsible for a major part of the contamination of the lower part of the Vilaine River course for Irgarol 1051. For diuron, agricultural sources may also be involved. The presence of isoproturon and chloroacetanilide herbicides on some dates indicated a significant contribution of the use of plant protection products in agriculture to the contamination of Vilaine River. Concentration levels and associated risk were always lower in estuarine sites than in the reservoir, suggesting that Arzal dam reduces downstream transfer of contaminants and favors their degradation in the freshwater part of the estuary. Results of the additional monitoring of two tidal streams located downstream of Arzal dam suggested that, although some compounds may be transferred to the estuary, their impact was probably very low. Dilution by marine water associated with tidal current was also a major factor of concentration reduction. It is concluded that the highest risks associated to herbicides and booster biocides concerned the freshwater part of the estuary and that its brackish/saltwater part was exposed to a moderate risk, although some substances may sometimes exhibit high concentration but mainly at low tide and on an irregular basis.

International audience | Complex mixtures of contaminants with potential adverse effects on human health and wildlife are found in the environment and in the food chain. These mixtures include numerous anthropogenic compounds of various origins and structures, which may behave as endocrine disruptors. Mixture's complexity is further enhanced by biotic and abiotic transformations. It is therefore necessary to develop new strategies allowing the identification of the structure of known, as well as unknown, nuclear receptor (NR) ligands present in complex matrices. We explored the possibility to use NR-based affinity columns to characterize the presence of bioactive molecules in environmental complex mixtures. Estrogen receptor alpha (ERalpha)-based affinity columns were used to trap and purify estrogenic substances present in surface sediment samples collected in a French river under mixed anthropogenic pressure. We combined biological, biochemical and analytical approaches to characterize the structure of ligands retained on columns and demonstrate the presence of known active molecules such as bisphenol A and octylphenol, but also of unexpected ERalpha ligands (n-butylparaben, hydroxyl-methyl-benzofuranone). High resolution mass spectrometry results demonstrate that ERalpha affinity columns can be used for the isolation, purification and identification of known as well as unknown estrogenic contaminants present in complex matrices.

International audience | The quality of fish produced in ponds needs to be ensured. Indeed, pond is often strongly connected to an agricultural watershed, and pesticides are a main health and environmental issue of concern. In this context, the purpose of this study is to highlight the management practices which could impact the pesticide contamination profiles in edible fish and to give recommendations for better practices. A principal component analysis, coupled to a hierarchical cluster analysis, was performed to evaluate temporal evolution of contamination profiles and to assess variability among fish species and among sites according to watershed characteristics. The explicative variables correspond to muscular concentrations of pesticides (azoxystrobin, clomazone, diflufenican, carbendazim, isoproturon, metazachlor, napropamid) in three species of fish (Perca fluviatilis, Cyprinus carpio and Rutilus rutilus), caught in five ponds during two sampling campaigns. Management data are added variables in order to discuss about parameters suspected to be implicated in the contamination profiles recorded. This work shows that high amounts of pesticides applied, short crop rotation durations and bare soil practices led to contamination of sediments and fish and were associated to a ``bad'' management of watershed. Breeding fish that had low masses and establishing the fishing period at the end of winter seemed to be ``bad'' management of pond. Aggravating topological parameters were big watershed coupled to small pond and high proportions of sand soils in the watershed. Reducing amounts of pesticide used (e.g. policy agency plans, farmer acceptance), favouring long-term rotations and inter-cultures, adapting pond creation and fish farming practices to watershed management and topography all could reduce pesticide levels in edible fish and contribute to a better sustainability of the extensive fish farming in pond.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA [Axe_IRSTEA]DTAM-QT2-ADAPTATION [TR2_IRSTEA]ARCEAU [TR2_IRSTEA]DTAM | Global climate change will affect worldwide agriculture in many ways. The anticipated or already occurring changes raise concerns about the sustainability of production and the ability of agriculture to feed human populations. This appeals to sustainable agriculture providing ecosystem services more efficiently than today, and accordingly to substantial evolutions of pesticide risk assessment (RA) and risk management (RM). The RA/RM issues were discussed by two European research networks in a 2011 workshop. The RA-RM-monitoring conceptual cycle tends to be virtual, with poor connections between certain steps. The design of more comprehensive emissions scenarios could improve the accuracy of predicted runoff transport, while the microcosm/mesocosm approach could help establish causal relationships between fate / exposure and populations / communities. Combined with ecological modelling, effects can be extrapolated to higher spatial and temporal scales. Risk management of diffuse sources should be designed simultaneously at the watershed and individual plot scales. Monitoring is key to assessing the effectiveness of risk reduction measures reduce and evaluate the overall quality of the aquatic compartment. More flexible monitoring strategies clearly linked to RM decisions are therefore needed. Although some technical questions remain, it is time to apply passive samplers more routinely. A set of research and development needs covering the whole RA/RM cycle is listed in conclusion.

International audience | The former use of chlordecone (CLD) in the French West Indies has resulted in long-term pollution of soils and of food chains. CLD may be transferred into eggs of hens reared outdoors, through polluted soil ingestion. Tropical volcanic soils display variable capacities of pollutant retention: CLD is less available and more persistent in andosol than in nitisol. The impact of soil type on CLD bioavailability to hens was tested through a relative bioavailability study. The deposition of CLD in egg yolk and in abdominal fat was measured in 42 individually housed laying hens fed with diets containing graded levels of CLD from polluted andosol, nitisol, or spiked oil during 23 days. Within each ingested matrix, the concentration of CLD in yolk and in abdominal fat linearly increased with the amount of ingested CLD (P < 0.001). However, the response to andosol diets and to nitisol diets was not different from the response to oil diets (P > 0.1), indicating that CLD was equally bioavailable to laying hens, irrespective of the matrix. This suggests that the hen's gastrointestinal tract efficiently extracts CLD from the two tropical volcanic soils, regardless of their retention capacity. Thus, hens reared on polluted soils with CLD may lay contaminated eggs.