[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | Little information is available on the environmental occurrence and ecotoxicological effects of pharmaceutical gestagens released in the aquatic environment. Since eighteen different gestagens were found to be used in France, preliminary exposure and hazard assessment were done. Predicted environmental concentrations (PECs) suggest that if parent gestagens are expected to be found in the ng l−1 range, some active metabolites could be present at higher concentrations, although limited data on metabolism and environmental fate limit the relevance of PECs. The biological effects are not expected to be restricted to progestagenic activity. Both anti-androgenic activity (mainly for cyproterone acetate, chlormadinone acetate and their metabolites) and estrogenic activity (mainly for reduced metabolites of levonorgestrel and norethisterone) should also occur. All these molecules are likely to have a cumulative effect among themselves or with other xenoestrogens. Studies on occurrence, toxicity and degradation time are therefore needed for several of these compounds.

National audience | Nowadays, promoted as a renewable energy, biomass burning becomes more and more widespread all over the world. In urban and rural areas biomass, mainly wood, is burned for heating, cooking, and waste disposal purposes. This biofuel seems to be an alternative to the rarefaction of the fossil fuel and, moreover it decreases the emission of carbon dioxide causing global warming. However, wood smoke contains various air pollutants such as fine particulate matter (PM10, PM2.5), polycyclic aromatic hydrocarbons (PAHs), benzene, dioxins... and in consequence has an impact on the air quality. In order to estimate the contribution of wood burning on the atmospheric organic aerosol of urban areas, the French ministry of environment (MEEDDAT), called upon this study during the winter 2006/2007, in the French cities of Grenoble, Lille, Strasbourg and Gennevilliers. For this work, different species have been looked after. The global characterization of the atmospheric aerosols has been made taking in account the PM10, the organic carbon (OC), and the elementary carbon (EC). Measurement of biomass burning tracers (levoglucosan, mannosan, and galactosan) has been undertaken, as well as methoxyphenols, which are more specific wood smoke tracers. The analyses of organic tracers by gas chromatography coupled with a mass spectrometer detector (GC/MS) show average concentrations of levoglucosan in the range of 272 ng.m-3 for Gennevilliers to 1 148 ng.m-3 for Grenoble. Mannosan and galactosan have also been measured in all cities but in lower quantities. The methoxyphenols have been detected only in rare occasions and at the limit of detection of the analytical method. PM10 measurements range from 20.6 micro g.m-3 for Gennevilliers to 35.8 micro g.m-3 for Grenoble. At the same time, OC values range from 3.61 micro g.m-3 to 11.15 micro g.m-3. Moreover high correlations have been observed between levoglucosan and OC, respectively 0.80 and 0.86 for Grenoble and Strasbourg. In addition, with respectively 10.98 ng.m-3 and 8.20 ng.m-3, Grenoble and Strasbourg present the highest particulate PAHs average concentrations of the four cities. All these results seem to indicate that Grenoble and Strasbourg are more impacted by the biomass burning than the two other cities. And more particularly in Grenoble where the organic aerosol fraction is very huge, this last phenomenon is typically characteristic of the biomass burning. To conclude, this study shows and confirms the usefulness of levoglucosan as biomass burning tracer and the difficulty to use methoxyphenols as woodsmoke tracers in ambient areas. | De nos jours, l'utilisation du bois en tant que combustible est relativement répandue en France et dans le monde entier. L'augmentation du prix du pétrole et des autres sources d'énergie épuisables va certainement engendrer dans les années à venir une contribution accrue du chauffage domestique au bois. L'utilisation de cette source d'énergie renouvelable pose cependant de nombreux problèmes sur la santé humaine. En effet, la fumée émise lors de la combustion du bois contient un certain nombre de composés polluants, tels que les hydrocarbures aromatiques polycycliques (HAP), le benzène, les fines particules (PM10, PM2,5)... Les émissions de la combustion du bois ont donc un impact sur la qualité de l'air. Cet impact peut être évalué par l'étude de traceurs organiques spécifiques de la combustion du bois identifiables au sein de la composante organique des aérosols. Ces traceurs sont des produits provenant de la combustion de la cellulose et de l'hémicellulose tels que le lévoglucosan, mannosan, galactosan et des composés issus de la thermodégradation de la lignine tels que les méthoxyphénols. Cette méthode a été appliquée à une étude commanditée à l'INERIS par le ministère de l'Écologie, de l'Énergie, du Développement Durable et de l'Aménagement du Territoire (MEEDDAT), en partenariat avec des Associations agréées de la surveillance de la qualité de l'air (AASQA). L'objectif était de caractériser l'influence de la combustion du bois sur la composante organique de l'aérosol atmosphérique en site urbain. Des prélèvements d'aérosols ont été effectués sur une période allant de novembre 2006 à avril 2007, dans quatre grandes villes de France : Grenoble, Lille, Strasbourg, et Gennevilliers. L'analyse par chromatographie gazeuse couplée à un spectromètre de masse (GC/MS) des traceurs organiques les plus stables, lévoglucosan, mannosan et galactosan, confirme l'influence de cette source sur la qualité de l'air des quatre villes. Sur la période d'étude, la concentration moyenne en lévoglucosan varie de 272 ng.m-3 pour la ville de Gennevilliers à 1 148 ng.m-3 pour la ville de Grenoble. La confrontation des résultats de ces traceurs avec les données usuelles de caractérisation de l'aérosol, telles que le carbone organique (OC) et le carbone élémentaire (EC), montre une participation du chauffage au bois plus importante dans les villes de Grenoble et de Strasbourg. Les résultats d'analyse du lévoglucosan obtenus sur la ville de Gennevilliers indiquent une très bonne corrélation avec les HAP particulaires et les PM10. Ces résultats prouvent que la combustion du bois joue un rôle important sur la composition de la matière organique de l'aérosol atmosphérique et sur la pollution particulaire en milieu urbain. En revanche, les méthoxyphénols ont été peu détectés sur les divers échantillons analysés.

International audience | During a decade (1996–2006), ecotoxicological studies were carried out in biota of the Vaccarès Lagoon (Biosphere Reserve in Rhone Delta, France). A multicontamination was shown at all levels of the trophic web due to a direct bioconcentration of chemical from the medium combined with a food transfer. Here, the pollutants investigated were organochlorines, among which many compounds banned or in the course of prohibition (or restriction) (PCB, lindane, pp′-DDE, dieldrin, aldrin, heptachlor, endosulfan…) and some substances likely still used in the Rhone River basin (diuron, fipronil). The results confirmed the ubiquity of contamination. It proves to be chronic, variable and tends to regress; however contamination levels depend on the trophic compartment. A biomagnification process was showed. A comparison of investigation methods used in other Mediterranean wetlands provides basis of discussion, and demonstrates the urgent need of modelling to assess the ecotoxicological risk in order to improve the management of such protected areas. The Vaccarès Lagoon trophic web biomagnifies organochlorine pollutants.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | Among the numerous PCB congeners, most of the dioxin-like PCBs (DL-PCBs) need to be characterized by hyphenated techniques. It has been shown in several instances that these congeners are well related to the total PCB content in fish.We examined datasets collected mainly in France, on freshwater and marine fish and sediments. A statistical model linking DL- and indicator PCBs was developed for a dataset composed of freshwater fishes, and proved to predict well DL-PCBs from indicator PCBs in all other fish sets, including marine ones. Type II error rates remained low in almost all fish sets. A similar correlation was observed in sediments. Non-dioxin-like PCBs elicit various adverse effects and represent 95% of the total PCBs. A European guideline for them is needed; the correlation between DL- and indicator PCBs could help develop this standard in the future.

Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC50) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC50 for ZnO NPs (2.3 mg L-1) and bulk ZnO was not significantly different, but significantly different between Al2O3 NPs (82 mg L-1) and bulk Al2O3 (153 mg L-1), and between TiO2 NPs (80 mg L-1) and bulk TiO2 (136 mg L-1). Oxide solubility influenced the toxicity of ZnO and Al2O3 NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs. ZnO, Al2O3 and TiO2 nanoparticles are more toxic than their bulk counterparts to the nematode, Caenorhabditis elegans.

In this study, the influence of the co-existence of TiO2 nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO2 nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO2 nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO2 nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO2 nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO2 nanoparticles than in the absence of TiO2 nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO2 nanoparticles. The co-existence of TiO2 nanoparticles could change the speciation of arsenite by adsorption and photo-oxidation, and enhance its bioaccumulation to carp.

Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650 ± 20 mg Pb kg-1) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO4, PbSO4·PbO, α-PbO and Pb0. Morphology investigations revealed that PM2.5 (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 μm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01 M CaCl2 extraction. The soil-lettuce lead transfer from atmospheric industrial sub-micronic and micronic particles depends on particle size.

This study provides the first evidence on the influence of the semiconductor and electronics industries on perfluorinated chemicals (PFCs) contamination in receiving rivers. We have quantified ten PFCs, including perfluoroalkyl sulfonates (PFASs: PFBS, PFHxS, PFOS) and perfluoroalkyl carboxylates (PFCAs: PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA) in semiconductor, electronic, and optoelectronic industrial wastewaters and their receiving water bodies (Taiwan's Keya, Touchien, and Xiaoli rivers). PFOS was found to be the major constituent in semiconductor wastewaters (up to 0.13 mg/L). However, different PFC distributions were found in electronics plant wastewaters; PFOA was the most significant PFC, contributing on average 72% to the effluent water samples, followed by PFOS (16%) and PFDA (9%). The distribution of PFCs in the receiving rivers was greatly impacted by industrial sources. PFOS, PFOA and PFDA were predominant and prevalent in all the river samples, with PFOS detected at the highest concentrations (up to 5.4 μg/L). The semiconductor, electronics and optoelectronic industries are the primary source of PFC contamination in downstream aqueous environments.

In this study, a biomonitoring project using the moss Scorpiurum circinatum was carried out to evaluate the deposition and biological effects of heavy metals in the area of Acerra (Naples, S Italy), one of the vertices of the sadly called "Italian triangle of death" owing to the dramatic increase in tumours. The results clearly indicated that the study area is heavily polluted by heavy metals, a large proportion of which is likely present in the atmosphere in particulate form. The ultrastructural organization of exposed samples was essentially preserved, but cell membrane pits, cytoplasm vesicles and concentric multilamellar/multivesicular bodies, probably induced by pollution, were found, which may be involved in the tolerance mechanisms to metal pollution in this moss species. Although severe biological effects were not found at the ultrastructural level in the exposed moss, effects on humans, especially after long-term exposure, are to be expected. The moss Scorpiurum circinatum indicates that the "Italian triangle of death" is heavily polluted by heavy metals.

This study reports sorption isotherms of the endocrine disruptors nonylphenol (NP) and octylphenol (OP) in three sediment samples from the Ebro River basin (NE Spain), with organic carbon fractions (fOC) ranging from 0.0035 to 0.082 gOC g-1. All isotherms were fitted to the Freundlich model with slightly nonlinear exponents ranging from 0.80 to 0.94. The solubility of the compounds as well as the organic carbon (OC) content had the strongest influences on the sorption behavior of these compounds. Comparison of the laboratory-spiked samples with the native contamination of NP of 45 water and concurrent sediment samples resulted in reasonable matches between both data sets, even though the lowest concentrations in the field were not completely reached in laboratory tests. This good agreement indicates that sorption laboratory data can be extrapolated to environmental levels and therefore the distribution of nonylphenol between sediments and water can be predicted with a precision of one order of magnitude. Furthermore, laboratory experiments with simultaneous loading of NP and OP revealed negligible competition for sorption sites at low concentrations.