Ten antibiotics belonging to three groups (macrolides, fluoroquinolones and sulfonamides) were investigated in riverine runoff of the Pearl River Delta (PRD) and Pearl River Estuary (PRE), South China for assessing the importance of riverine runoff in the transportation of contaminants from terrestrial sources to the open ocean. All antibiotics were detected in the eight outlets with concentrations ranging from 0.7 to 127 ng L−1. The annual mass loadings of antibiotics from the PRD to the PRE and coast were 193 tons with 102 tons from the fluoroquinolone group. It showed that antibiotics decreased from the riverine outlets to the PRE and open ocean. Risk assessment showed that most of these antibiotics showed various ecological risks to the relevant aquatic organisms, in which ofloxacin (OFL), erythromycin (ETM) and ciprofloxacin (CIP) posed high ecological risks to the studied aquatic environments.

International audience | : This paper compares the removal performances of two complete wastewater treatment plants (WWTPs) for all priority substances listed in the Water Framework Directive and additional compounds of interest including flame retardants, surfactants, pesticides, and personal care products (PCPs) (n = 104). First, primary treatments such as physicochemical lamellar settling (PCLS) and primary settling (PS) are compared. Similarly, biofiltration (BF) and conventional activated sludge (CAS) are then examined. Finally, the removal efficiency per unit of nitrogen removed of both WWTPs for micropollutants is discussed, as nitrogenous pollution treatment results in a special design of processes and operational conditions. For primary treatments, hydrophobic pollutants (log K ow > 4) are well removed (>70 %) for both systems despite high variations of removal. PCLS allows an obvious gain of about 20 % regarding pollutant removals, as a result of better suspended solids elimination and possible coagulant impact on soluble compounds. For biological treatments, variations of removal are much weaker, and the majority of pollutants are comparably removed within both systems. Hydrophobic and volatile compounds are well (>60 %) or very well removed (>80 %) by sorption and volatilization. Some readily biodegradable molecules are better removed by CAS, indicating a better biodegradation. A better sorption of pollutants on activated sludge could be also expected considering the differences of characteristics between a biofilm and flocs. Finally, comparison of global processes efficiency using removals of micropollutants load normalized to nitrogen shows that PCLS + BF is as efficient as PS + CAS despite a higher compactness and a shorter hydraulic retention time (HRT). Only some groups of pollutants seem better removed by PS + CAS like alkylphenols, flame retardants, or di-2-ethylhexyl phthalate (DEHP), thanks to better biodegradation and sorption resulting from HRT and biomass characteristics. For both processes, and out of the 68 molecules found in raw water, only half of them are still detected in the water discharged, most of the time close to their detection limit. However, some of them are detected at higher concentrations (>1 μg/L and/or lower than environmental quality standards), which is problematic as they represent a threat for aquatic environment.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | International audience | The toxicity of dietary exposure to artificially aged TiO2 nanomaterial (T-Lite (TM)) used in sunscreen cream was studied on Danio rerio. Embryolarval assays were conducted to assess the effects of TiO2 residues of nanomaterial (RNM) on fish early life stages. Juvenile fishes were exposed by the trophic route in two experiments. During the first experiment, juvenile fishes were exposed to TiO2 RNM for 14 days by adding RNM to commercial fish food. The second one consisted in producing a trophic food chain. Pseudokirchneriella subcapitata algae, previously contaminated with TiO2 RNM in growth medium, was used to feed Daphnia magna neonates over a 48-h period. Daphnia were used next to feed juvenile fishes for 7 days. Accumulation of Ti, life traits (survival and growth) and biochemical parameters such as energy reserves, digestive (trypsin, esterase, cellulose and amylase) and antioxidant (superoxide dismutase and catalase) enzyme activity were measured at the end of exposures. As expected in the receiving aquatic system, TiO2 RNM at low concentrations caused a low impact on juvenile zebrafish. A slight impact on the early life stage of zebrafish with premature hatching was observed, and this effect appeared mainly indirect, due to possible embryo hypoxia. When juvenile fish are exposed to contaminated food, digestive enzyme activity indicated a negative effect of TiO2 RNM. Digestive physiology was altered after 14 days of exposure and seemed to be an indirect target of TiO2 RNM when provided by food.

International audience | This study evaluates the influence of a heavily urbanized area (Paris Metropolitan area), on receiving water contamination by both bisphenol A (BPA) and alkylphenol ethoxylate (APE) biodegradation product. The study began by investigating concentrations within urban sources. In addition to the more commonly studied wastewater treatment plant effluent, wet weather urban sources (including combined sewer overflows, urban runoff, and total atmospheric fallout) were considered. The initial results highlight a significant contamination of all urban sources (from a few nanograms per liter in atmospheric fallout to several micrograms per liter in the other sources) with clearly distinguishable distribution patterns. Secondly, concentration changes along the Seine River from upstream of the Paris Metropolitan area to downstream were investigated. While the concentrations of BPA and nonylphenoxy acetic acid (NP(1)EC) increase substantially due to urban sources, the 4-nonylphenol concentrations remain homogeneous along the Seine. These results suggest a broad dissemination of 4-nonylphenol at the scale of the Seine River basin. Moreover, the relationship between pollutant concentrations and Seine River flow was assessed both upstream and downstream of the Paris conurbation. Consequently, a sharp decrease in dissolved NP(1)EC concentrations relative to Seine River flow underscores the influence of single-point urban pollution on Seine River contamination. Conversely, dissolved 4-nonylphenol concentrations serve to reinforce the hypothesis of its widespread presence at the Seine River basin scale.

[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

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.

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 | The objective was to describe and model varia- tion patterns in individual fish responses to contaminants among estuaries, season and gender. Two hundred twenty- seven adult European flounders were collected in two sea- sons (winter and summer) in four estuaries along the Bay of Biscay (South West France), focusing on a pristine system (the Ster), vs. three estuaries displaying contrasted levels of contaminants (the Vilaine, Loire and Gironde). Twenty-three variables were measured by fish, considering the load of contaminants (liver metals, liver and muscle persistent organic pollutants, muscle polycyclic aromatic hydrocar- bons); the gene expression (Cyt C oxydase, ATPase, BHMT, Cyt P450 1A1, ferritin); the blood genotoxicity (Comet test); and liver histology (foci of cellular alteration-tumour, steatosis, inflammation, abnormal glycogen storage). Ca- nonical redundancy analysis (RDA) was used to model these variables using gender, season and estuary of origin as explanatory variables. The results underlined the homo- geneity of fish responses within the pristine site (Ster) and more important seasonal variability within the three contam- inated systems. The complete model RDA was significant and explained 35 % of total variance. Estuary and season respectively explained 30 and 5 % of the total independent variation components, whilst gender was not a significant factor. The first axis of the RDA explains nearly 27 % of the total variance and mostly represents a gradient of contami- nation. The links between the load of contaminants, the expression of several genes and the biomarkers were ana- lysed considering different levels of chemical stress and a possible multi-stress, particularly in the Vilaine estuary.

[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.