Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant worldwide. A detailed examination of the degradation products emitted during thermal decomposition of TBBPA is presented in the study. Runs were performed in a laboratory furnace at different temperatures (650 and 800 °C) and in different atmospheres (nitrogen and air). More than one hundred semivolatile compounds have been identified by GC/MS, with special interest in brominated ones. Presence of HBr and brominated light hydrocarbons increased with temperature and in the presence of oxygen. Maximum formation of PAHs is observed at pyrolytic condition at the higher temperature. High levels of 2,4-, 2,6- and 2,4,6- bromophenols were found. The levels of polybrominated dibenzo-p-dioxins and furans have been detected in the ppm range. The most abundant isomers are 2,4,6,8-TeBDF in pyrolysis and 1,2,3,7,8-PeBDF in combustion. These results should be considered in the assessment of thermal treatment of materials containing brominated flame retardants.

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant worldwide. A detailed examination of the degradation products emitted during thermal decomposition of TBBPA is presented in the study. Runs were performed in a laboratory furnace at different temperatures (650 and 800 °C) and in different atmospheres (nitrogen and air). More than one hundred semivolatile compounds have been identified by GC/MS, with special interest in brominated ones. Presence of HBr and brominated light hydrocarbons increased with temperature and in the presence of oxygen. Maximum formation of PAHs is observed at pyrolytic condition at the higher temperature. High levels of 2,4-, 2,6- and 2,4,6- bromophenols were found. The levels of polybrominated dibenzo-p-dioxins and furans have been detected in the ppm range. The most abundant isomers are 2,4,6,8-TeBDF in pyrolysis and 1,2,3,7,8-PeBDF in combustion. These results should be considered in the assessment of thermal treatment of materials containing brominated flame retardants. | Support for this work was provided by the Generalitat Valenciana (Spain), research project Prometeo/2009/043/FEDER, and by the Spanish Ministry of Education and Science, research project CTQ2008-05520.

This study is intended to examine the quality and quantity of floating plastic debris in the River Seine through use of an extensive regional network of floating debris-retention booms; it is one of the first attempts to provide reliable information on such debris at a large regional scale. Plastic debris represented between 0.8% and 5.1% of total debris collected by weight. A significant proportion consisted of food wrappers/containers and plastic cutlery, probably originating from voluntary or involuntary dumping, urban discharges and surface runoff. Most plastic items are made of polypropylene, polyethylene and, to a lesser extent, polyethylene terephthalate. By extrapolation, some 27 tons of floating plastic debris are intercepted annually by this network; corresponding to 2.3 g per Parisian inhabitant per year. Such data could serve to provide a first evaluation of floating plastic inputs conveyed by rivers.

International audience | This study is intended to examine the quality and quantity of floating plastic debris in the River Seine through use of an extensive regional network of floating debris-retention booms; it is one of the first attempts to provide reliable information on such debris at a large regional scale. Plastic debris represented between 0.8% and 5.1% of total debris collected by weight. A significant proportion consisted of food wrappers/containers and plastic cutlery, probably originating from voluntary or involuntary dumping, urban discharges and surface runoff. Most plastic items are made of polypropylene, polyethylene and, to a lesser extent, polyethylene terephthalate. By extrapolation, some 27 tons of floating plastic debris are intercepted annually by this network; corresponding to 2.3 g per Parisian inhabitant per year. Such data could serve to provide a first evaluation of floating plastic inputs conveyed by rivers.

Polycyclic Aromatic Hydrocarbons (PAHs) molecular diagnostic ratios (MDRs) are unitless concentration ratios of pair-PAHs with the same molecular weight (MW); MDRs have long been used as a tool for PAHs source identification purposes. In the present paper, the efficiency of the MDR methodology is evaluated through the use of a multimedia fate model, the calculation of characteristic travel distances (CTD) and the estimation of air concentrations for individual PAHs as a function of distance from an initial point source. The results show that PAHs with the same MW are sometimes characterized by substantially different CTDs and therefore their air concentrations and hence MDRs are predicted to change as the distance from the original source increases. From the assessed pair-PAHs, the biggest CTD difference is seen for Fluoranthene (107 km) vs. Pyrene (26 km). This study provides a strong indication that MDRs are of limited use as a source identification tool.

Polycyclic Aromatic Hydrocarbons (PAHs) molecular diagnostic ratios (MDRs) are unitless concentration ratios of pair-PAHs with the same molecular weight (MW); MDRs have long been used as a tool for PAHs source identification purposes. In the present paper, the efficiency of the MDR methodology is evaluated through the use of a multimedia fate model, the calculation of characteristic travel distances (CTD) and the estimation of air concentrations for individual PAHs as a function of distance from an initial point source. The results show that PAHs with the same MW are sometimes characterized by substantially different CTDs and therefore their air concentrations and hence MDRs are predicted to change as the distance from the original source increases. From the assessed pair-PAHs, the biggest CTD difference is seen for Fluoranthene (107 km) vs. Pyrene (26 km). This study provides a strong indication that MDRs are of limited use as a source identification tool. | acceptedVersion

We examined copper (Cu) absorption, distribution and toxicity and the role of a silicon (Si) supplementation in the bamboo Phyllostachys fastuosa. Bamboos were maintained in hydroponics for 4 months and submitted to two different Cu (1.5 and 100 μm Cu2+) and Si (0 and 1.1 mM) concentrations. Cu and Si partitioning and Cu speciation were investigated by chemical analysis, microscopic and spectroscopic techniques. Copper was present as Cu(I) and Cu(II) depending on plant parts. Bamboo mainly coped with high Cu exposure by: (i) high Cu sequestration in the root (ii) Cu(II) binding to amino and carboxyl ligands in roots, and (iii) Cu(I) complexation with both organic and inorganic sulfur ligands in stems and leaves. Silicon supplementation decreased the visible damage induced by high Cu exposure and modified Cu speciation in the leaves where a higher proportion of Cu was present as inorganic Cu(I)S compounds, which may be less toxic.

We examined copper (Cu) absorption, distribution and toxicity and the role of a silicon (Si) supplementation in the bamboo Phyllostachys fastuosa. Bamboos were maintained in hydroponics for 4 months and submitted to two different Cu (1.5 and 100 mm Cu2þ) and Si (0 and 1.1 mM) concentrations. Cu and Si partitioning and Cu speciation were investigated by chemical analysis, microscopic and spectroscopic techniques. Copper was present as Cu(I) and Cu(II) depending on plant parts. Bamboo mainly coped with high Cu exposure by: (i) high Cu sequestration in the root (ii) Cu(II) binding to amino and carboxyl ligands in roots, and (iii) Cu(I) complexation with both organic and inorganic sulfur ligands in stems and leaves. Silicon supplementation decreased the visible damage induced by high Cu exposure and modified Cu speciation in the leaves where a higher proportion of Cu was present as inorganic Cu(I)S compounds, which may be less toxic. (Résumé d'auteur)

Intra-specific variability of root biomass production (RP) of six rooted macrophytes, i.e. Juncus effusus, Phragmites australis, Schoenoplectus lacustris, Typha latifolia, Phalaris arundinacea, and Iris pseudacorus grown from clones, in response to Cu exposure was investigated. Root biomass production varied widely for all these macrophytes in control conditions (0.08 μM) according to the sampling site. Root biomass production of T. latifolia and I. pseudacorus in the 2.5–25 μM Cu range depended on the sampling location but not on the Cu dose in the growth medium. For P. australis, J. effusus, S. lacustris, and P. arundinacea, an intra-specific variability of RP depending on both the sampling location and the Cu-dose was evidenced. This intra-specific variability of RP depending on the sampling location and of Cu-tolerance for these last four species suggests that Cu constitutive tolerance for all rooted macrophytes is not a species-wide trait but it exhibits variability for some species.

Intra-specific variability of root biomass production (RP) of six rooted macrophytes, i.e. Juncus effusus, Phragmites australis, Schoenoplectus lacustris, Typha latifolia, Phalaris arundinacea, and Iris pseudacorus grown from clones, in response to Cu exposure was investigated. Root biomass production varied widely for all these macrophytes in control conditions (0.08 μM) according to the sampling site. Root biomass production of T. latifolia and I. pseudacorus in the 2.5–25 μM Cu range depended on the sampling location but not on the Cu dose in the growth medium. For P. australis, J. effusus, S. lacustris, and P. arundinacea, an intra-specific variability of RP depending on both the sampling location and the Cu-dose was evidenced. This intra-specific variability of RP depending on the sampling location and of Cu-tolerance for these last four species suggests that Cu constitutive tolerance for all rooted macrophytes is not a species-wide trait but it exhibits variability for some species.

International audience | Intra-specific variability of root biomass production (RP) of six rooted macrophytes, i.e. Juncus effusus, Phragmites australis, Schoenoplectus lacustris, Typha latifolia, Phalaris arundinacea, and Iris pseudacorus grown from clones, in response to Cu exposure was investigated. Root biomass production varied widely for all these macrophytes in control conditions (0.08 μM) according to the sampling site. Root biomass production of T. latifolia and I. pseudacorus in the 2.5–25 μM Cu range depended on the sampling location but not on the Cu dose in the growth medium. For P. australis, J. effusus, S. lacustris, and P. arundinacea, an intra-specific variability of RP depending on both the sampling location and the Cu-dose was evidenced. This intra-specific variability of RP depending on the sampling location and of Cu-tolerance for these last four species suggests that Cu constitutive tolerance for all rooted macrophytes is not a species-wide trait but it exhibits variability for some species.

The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the 110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectroscopy. After two weeks of ageing the E-values for Ag decreased by 20–90% with a further decrease of 10–40% after six months. The overall decrease in labile Ag for all soils after the 6 month ageing period was 50–100%. The ageing was more rapid and pronounced in the alkaline soils. XANES results for Ag in soils indicated that for the majority of soils the added Ag+ was reduced to metallic Ag over time, and associations with Fe-oxohydroxides and reduced S groups in organic matter also decreased Ag lability. Strong positive correlations were found between metallic Ag and non-labile Ag and between organic carbon and Ag bonded with S species.

Abstract not available | Lara Settimio, Mike J. McLaughlin, Jason K. Kirby, Kate A. Langdon, Enzo Lombi, Erica Donner, Kirk G. Scheckel

The influence of earthworm activity on soil-to-plant metal transfer was studied by carrying out six weeks mesocosms experiments with or without lettuce and/or earthworms in soil with a gradient of metal concentrations due to particles fallouts. Soil characteristics, metal concentrations in lettuce and earthworms were measured and soil porosity in the mesocosms was determined. Earthworms increased the soil pH, macroporosity and soil organic matter content due to the burying of wheat straw provided as food. Earthworm activities increased the metals concentrations in lettuce leaves. Pb and Cd concentrations in lettuce leaves can increase up to 46% with earthworm activities … These results and the low correlation between estimated by CaCl2 and EDTA and measured pollutant phytoavailability suggest that earthworm bioturbation was the main cause of the increase. Bioturbation could affect the proximity of pollutants to the roots and soil organic matter.

International audience | The influence of earthworm activity on soil-to-plant metal transfer was studied by carrying out six weeks mesocosms experiments with or without lettuce and/or earthworms in soil with a gradient of metal concentrations due to particles fallouts. Soil characteristics, metal concentrations in lettuce and earthworms were measured and soil porosity in the mesocosms was determined. Earthworms increased the soil pH, macroporosity and soil organic matter content due to the burying of wheat straw provided as food. Earthworm activities increased the metals concentrations in lettuce leaves. Pb and Cd concentrations in lettuce leaves can increase up to 46% with earthworm activities ... These results and the low correlation between estimated by CaCl2 and EDTA and measured pollutant phytoavailability suggest that earthworm bioturbation was the main cause of the increase. Bioturbation could affect the proximity of pollutants to the roots and soil organic matter.

Excessive nitrogen input in natural ecosystems is a major threat to biodiversity. A coastal dune area near Amsterdam in the Netherlands suffers from high atmospheric nitrogen deposition affecting sensitive habitats such as fixed coastal dunes with herbaceous vegetation (‘grey dunes’). To mitigate its effect year round grazing was applied from 2007 until 2012. In winter, when natural food supply is low, the cattle received supplementary hay that caused additional inputs of nitrogen. Estimates based on nitrogen contents of hay, as well as of manure, showed the input through winter feeding (c. 3–14 kg N ha-1.y-1) is in the same order of magnitude as both the actual deposition (c. 17 kg N ha-1.y-1) and the critical load for a number of herbaceous habitat types (10–15 kg N ha-1.y-1). Locally, the effect of winter feeding adds to the effect of nitrogen redistribution within the area caused by the cattle's terrain usage. We conclude that winter feeding may aggravate effects of atmospheric nitrogen deposition. Keywords: Vegetation management; Manure; Nitrogen; Eutrophication; Natura 2000; Grey dune

Excessive nitrogen input in natural ecosystems is a major threat to biodiversity. A coastal dune area near Amsterdam in the Netherlands suffers from high atmospheric nitrogen deposition affecting sensitive habitats such as fixed coastal dunes with herbaceous vegetation (‘grey dunes’). To mitigate its effect year round grazing was applied from 2007 until 2012. In winter, when natural food supply is low, the cattle received supplementary hay that caused additional inputs of nitrogen. Estimates based on nitrogen contents of hay, as well as of manure, showed the input through winter feeding (c. 3–14 kg N ha−1.y−1) is in the same order of magnitude as both the actual deposition (c. 17 kg N ha−1.y−1) and the critical load for a number of herbaceous habitat types (10–15 kg N ha−1.y−1). Locally, the effect of winter feeding adds to the effect of nitrogen redistribution within the area caused by the cattle's terrain usage. We conclude that winter feeding may aggravate effects of atmospheric nitrogen deposition.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants that can be present at high levels as mixtures in polluted aquatic environments. Many PAHs are potent mutagens and several are well-known carcinogens. Despite numerous studies on individual compounds, little is known about the toxicity of PAHs mixtures that are encountered in environmental situations. In the presentwork, zebrafish were continuously fed from 5 days post-fertilisation to 14 months post-fertilisation (mpf) with a diet spiked with fractions of either pyrolytic (PY), petrogenic light oil (LO), or petrogenic heavy oil (HO) origin at three concentrations. A decrease in survival was identified after 3 mpf in fish fed with the highest concentration of HO or LO, but not for PY. All PAH fractions caused preneoplastic and neoplastic disorders in longterm-exposed animals. Target tissues were almost exclusively of epithelial origin, with the bile duct epithelium being themost susceptible to chronic exposure to all PAH fractions, and with germ cells being the second most responsive cells. Significantly higher incidences of neoplasms were observed with increasing PAH concentration and exposure duration. Themost severe carcinogenic effects were induced by dietary exposure to HO compared to exposure to LO or PY (45, 30 and 7 %, respectively, after 9 to 10 months of exposure to an intermediate concentration of PAHs). In contrast, earliest carcinogenic effects were detected as soon as 3 mpf after exposure to LO, including the lowest concentration, or to PY. PAHbioactivation and genotoxicity in blood was assessed by ethoxyresorufin-Odeethylase activity quantification and comet and micronuclei assays, respectively, but none of these were positive. Chronic dietary exposure of zebrafish to PAH mixtures results in carcinogenotoxic events that impair survival and physiology of exposed fish.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants that can be present at high levels as mixtures in polluted aquatic environments. Many PAHs are potent mutagens and several are well-known carcinogens. Despite numerous studies on individual compounds, little is known about the toxicity of PAHs mixtures that are encountered in environmental situations. In the present work, zebrafish were continuously fed from 5 days post-fertilisation to 14 months post-fertilisation (mpf) with a diet spiked with fractions of either pyrolytic (PY), petrogenic light oil (LO), or petrogenic heavy oil (HO) origin at three concentrations. A decrease in survival was identified after 3 mpf in fish fed with the highest concentration of HO or LO, but not for PY. All PAH fractions caused preneoplastic and neoplastic disorders in long-term-exposed animals. Target tissues were almost exclusively of epithelial origin, with the bile duct epithelium being the most susceptible to chronic exposure to all PAH fractions, and with germ cells being the second most responsive cells. Significantly higher incidences of neoplasms were observed with increasing PAH concentration and exposure duration. The most severe carcinogenic effects were induced by dietary exposure to HO compared to exposure to LO or PY (45, 30 and 7 %, respectively, after 9 to 10 months of exposure to an intermediate concentration of PAHs). In contrast, earliest carcinogenic effects were detected as soon as 3 mpf after exposure to LO, including the lowest concentration, or to PY. PAH bioactivation and genotoxicity in blood was assessed by ethoxyresorufin-O-deethylase activity quantification and comet and micronuclei assays, respectively, but none of these were positive. Chronic dietary exposure of zebrafish to PAH mixtures results in carcinogenotoxic events that impair survival and physiology of exposed fish.