An original combined organic geochemistry and soil science approach was used to elucidate PAH availability controlling factors in a multi-contaminated industrial soil. Water granulodensimetric fractionation was applied to obtain five water-stable material fractions. These were characterized by elemental, molecular and mineral analysis, and microscopic observations. Among the different fractions, fine silts distinguished themselves by higher carbon and nitrogen contents, lower C/N ratio, an enrichment in total PAH and especially high molecular weight compounds, a coal tar signature and the lowest PAH availability. This fine silt fraction seemed to play a protective role for PAH that might be explained by its size and/or its specific reactivity. The mineral phases present in this fraction were proposed to explain the protection of organic matter. This led to a specific molecular signature of OM, having higher sorption properties both processes (sorption and mineral-bound protection) resulting in a lower PAH availability.

International audience | An original combined organic geochemistry and soil science approach was used to elucidate PAH availability controlling factors in a multi-contaminated industrial soil. Water granulodensimetric fractionation was applied to obtain five water-stable material fractions. These were characterized by elemental, molecular and mineral analysis, and microscopic observations. Among the different fractions, fine silts distinguished themselves by higher carbon and nitrogen contents, lower C/N ratio, an enrichment in total PAH and especially high molecular weight compounds, a coal tar signature and the lowest PAH availability. This fine silt fraction seemed to play a protective role for PAH that might be explained by its size and/or its specific reactivity. The mineral phases present in this fraction were proposed to explain the protection of organic matter. This led to a specific molecular signature of OM, having higher sorption properties both processes (sorption and mineral-bound protection) resulting in a lower PAH availability. (C) 2013 Elsevier Ltd. All rights reserved.

The comet assay and micronucleous test were used to assess the genotoxicity of organic compounds associated with particulate material collected in the city of Córdoba, Argentina. Samples were collected on fiber glass filters and their organic extracts were analyzed by GC-MS. These extracts were used for the comet assay on human lymphocytes and for the MCN test with Tradescantia pallida. The concentrations of polycyclic aromatic hydrocarbons as well as some of their nitro derivates were higher during winter. Their composition suggested that their main emission sources were gasoline and diesel vehicles. We observed genotoxic effects of these organic extracts due to the presence of both direct and indirect acting mutagens. We found a good agreement between the two test systems employed, which encourages the further use of plant bioassays for air pollution monitoring, especially in developing countries, due to their flexibility, low cost and efficiency.

The comet assay and micronucleous test were used to assess the genotoxicity of organic compounds associated with particulate material collected in the city of Córdoba, Argentina. Samples were collected on fiber glass filters and their organic extracts were analyzed by GC-MS. These extracts were used for the comet assay on human lymphocytes and for the MCN test with Tradescantia pallida. The concentrations of polycyclic aromatic hydrocarbons as well as some of their nitro derivates were higher during winter. Their composition suggested that their main emission sources were gasoline and diesel vehicles. We observed genotoxic effects of these organic extracts due to the presence of both direct and indirect acting mutagens. We found a good agreement between the two test systems employed, which encourages the further use of plant bioassays for air pollution monitoring, especially in developing countries, due to their flexibility, low cost and efficiency. | Fil: Carreras, Hebe Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto Multidisciplinario de Biología Vegetal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto Multidisciplinario de Biología Vegetal; Argentina | Fil: Calderon Segura, María Elena. Universidad Nacional Autónoma de México; México | Fil: Gomez Arroyo, Sandra. Universidad Nacional Autónoma de México; México | Fil: Murillo Tovar, Mario A.. Universidad Nacional Autónoma de México; México | Fil: Amador Munoz, Omar. Universidad Nacional Autónoma de México; México

This study investigates the metabolism and mode of action of galaxolide (HHCB) in the European sea bass -Dicentrarchus labrax- following a single intraperitoneal injection of 50 mg HHCB/kg body weight. In addition, a group of fish was injected with 50 mg/kg of ketoconazole (KCZ), a fungicide that is known to interfere with different Cyp isoenzymes. HHCB was actively metabolised by sea bass and acted as a weak inhibitor of the synthesis of oxyandrogens in gonads of male fish. Both, HHCB and a hydroxylated metabolite were detected in bile. The fungicide ketoconazole was a strong inhibitor of Cyp11β and Cyp3a-catalyzed activities. The work contributes to the better understanding of the impact of synthetic musks on fish and proposes the determination of HHCB and/or its hydroxylated metabolite in bile as a tool to assess environmental exposure in wild fish.

This study investigates the metabolism and mode of action of galaxolide (HHCB) in the European sea bass -Dicentrarchus labrax- following a single intraperitoneal injection of 50 mg HHCB/kg body weight. In addition, a group of fish was injected with 50 mg/kg of ketoconazole (KCZ), a fungicide that is known to interfere with different Cyp isoenzymes. HHCB was actively metabolised by sea bass and acted as a weak inhibitor of the synthesis of oxyandrogens in gonads of male fish. Both, HHCB and a hydroxylated metabolite were detected in bile. The fungicide ketoconazole was a strong inhibitor of Cyp11β and Cyp3a-catalyzed activities. The work contributes to the better understanding of the impact of synthetic musks on fish and proposes the determination of HHCB and/or its hydroxylated metabolite in bile as a tool to assess environmental exposure in wild fish. © 2012 Elsevier Ltd. All rights reserved. | This study was supported by the Spanish Ministry of Science and Innovation under Project CGL2008-01888/BOS and CSIC project PIE 200930I037. Denise Fernandes acknowledges a postdoctoral fellowship (SFRH/BPD/34289/2006) from the Portuguese Fundaçao para a Ciencia e Tecnologia (FCT), and Giorgio Dimastrogiovanni a predoctoral fellowship (BES-2009-025271) from the Spanish Ministry of Science and Education. | Peer Reviewed

The increasing use of silver (Ag) nanoparticles [containing either elemental Ag (Ag-NPs) or AgCl (AgCl-NPs)] in commercial products such as textiles will most likely result in these materials reaching wastewater treatment plants. Previous studies indicate that a conversion of Ag-NPs to Ag2S is to be expected during wastewater transport/treatment. However, the influence of surface functionality, the nature of the core structure and the effect of post-processing on Ag speciation in sewage sludge/biosolids has not been investigated. This study aims at closing these knowledge gaps using bench scale anaerobic digesters spiked with Ag nitrate, three different types of Ag-NPs, and AgCl-NPs at environmentally realistic concentrations. The results indicate that neither surface functionality nor the different compositions of the NP prevented the formation of Ag2S. Silver sulfides, unlike the sulfides of other metals present in sewage sludge, were stable over a six month period simulating composting/stockpiling.

Data source: Supplementary data, http://ars.els-cdn.com/content/image/1-s2.0-S0269749113000444-mmc1.docx | Abstract not available. | Enzo Lombi, Erica Donner, Shima Taheri, Ehsan Tavakkoli, Åsa K. Jämting, Stuart McClure, Ravi Naidu, Bradley W. Miller, Kirk G. Scheckel, Krasimir Vasilev

Nitrous oxide is a potent greenhouse gas, with a global warming potential 298 times greater than that of CO2. In agricultural soils, N2O emissions are influenced by a large number of environmental characteristics and crop management techniques that are not systematically reported in experiments. Random Forest (RF) is a machine learning method that can handle missing data and ranks input variables on the basis of their importance. We aimed to predict N2O emission on the basis of local information, to rank environmental and crop management variables according to their influence on N2O emission, and to compare the performances of RF with several regression models. RF outperformed the regression models for predictive purposes, and this approach led to the identification of three important input variables: N fertilization, type of crop, and experiment duration. This method could be used in the future for prediction of N2O emissions from local information.

Nitrous oxide is a potent greenhouse gas, with a global warming potential 298 times greater than that of CO2. In agricultural soils, N2O emissions are influenced by a large number of environmental characteristics and crop management techniques that are not systematically reported in experiments. Random Forest (RF) is a machine learning method that can handle missing data and ranks input variables on the basis of their importance. We aimed to predict N2O emission on the basis of local information, to rank environmental and crop management variables according to their influence on N2O emission, and to compare the performances of RI: with several regression models. RF outperformed the regression models for predictive purposes, and this approach led to the identification of three important input variables: N fertilization, type of crop, and experiment duration. This method could be used in the future for prediction of N2O emissions from local information. (c) 2013 Elsevier Ltd. All rights reserved.

Bioaccessibility tests can be used to improve contaminated land risk assessments. For organic pollutants a ‘sink’ is required within these tests to better mimic their desorption under the physiological conditions prevailing in the intestinal tract, where a steep diffusion gradient for the removal of organic pollutants from the soil matrix would exist. This is currently ignored in most PBET systems. By combining the CEPBET bioaccessibility test with an infinite sink, the removal of PAH from spiked solutions was monitored. Less than 10% of spiked PAH remained in the stomach media after 1 h, 10% by 4 h in the small intestine compartment and c.15% after 16 h in the colon. The addition of the infinite sink increased bioaccessibility estimates for field soils by a factor of 1.2–2.8, confirming its importance for robust PBET tests. TOC or BC were not the only factors controlling desorption of the PAH from the soils.

Bioaccessibility tests can be used to improve contaminated land risk assessments. For organic pollutants a ‘sink’ is required within these tests to better mimic their desorption under the physiological conditions prevailing in the intestinal tract, where a steep diffusion gradient for the removal of organic pollutants from the soil matrix would exist. This is currently ignored in most PBET systems. By combining the CEPBET bioaccessibility test with an infinite sink, the removal of PAH from spiked solutions was monitored. Less than 10% of spiked PAH remained in the stomach media after 1 h, 10% by 4 h in the small intestine compartment and c.15% after 16 h in the colon. The addition of the infinite sink increased bioaccessibility estimates for field soils by a factor of 1.2–2.8, confirming its importance for robust PBET tests. TOC or BC were not the only factors controlling desorption of the PAH from the soils.

Embryo toxicity of particles generated by combustion processes is of special concern for human health. A significant part of these toxic effects is linked to the binding of some pollutants (like polycyclic aromatic hydrocarbons or PAHs) to the Aryl hydrocarbon Receptor (AhR) and the activation of target genes, like the cytochrome P4501A. This activity was analyzed for ambient air and coal-combustion particle extracts in zebrafish embryos (the cyp1aDarT assay) and in two single-cell bioassays: the yeast-based YCM-RYA and the DR-luc (rat cells) assay. Observed AhR ligand activity of samples generally correlated to the predicted toxic effect according to their PAH composition, except for one of the coal combustion samples with an anomalously high activity in the cyp1aDarT assay. This sample induced deformities in zebrafish embryos. We concluded that the combination of morphological and molecular assays may detect embryonic toxic effects that cannot be predicted from chemical analyses or single-cell bioassays.

Embryo toxicity of particles generated by combustion processes is of special concern for human health. A significant part of these toxic effects is linked to the binding of some pollutants (like polycyclic aromatic hydrocarbons or PAHs) to the Aryl hydrocarbon Receptor (AhR) and the activation of target genes, like the cytochrome P4501A. This activity was analyzed for ambient air and coal-combustion particle extracts in zebrafish embryos (the cyp1aDarT assay) and in two single-cell bioassays: the yeast-based YCM-RYA and the DR-luc (rat cells) assay. Observed AhR ligand activity of samples generally correlated to the predicted toxic effect according to their PAH composition, except for one of the coal combustion samples with an anomalously high activity in the cyp1aDarT assay. This sample induced deformities in zebrafish embryos. We concluded that the combination of morphological and molecular assays may detect embryonic toxic effects that cannot be predicted from chemical analyses or single-cell bioassays. | This work has been funded by the Spanish Ministry of Economy and Competitiveness (CTM2011-30471-C02-01, CGL2011-29621), and the Generalitat de Catalunya (grant number 2009 SGR 924). We also acknowledge Michael Denison (UC Davis) for providing the DR-LUC cells, and Xavier Querol (IDAEA-CSIC) for the coal waste gob samples and for his comments. | Peer reviewed

This study compares the effectiveness of two different thickness of green roof substrate with respect to nutrient and heavy metal retention and release. To understand and evaluate the long term behaviour of green roofs, substrate columns with the same structure and composition as the green roofs, were exposed in laboratory to artificial rain. The roofs act as a sink for C, N, P, zinc and copper for small rain events if the previous period was principally dry. Otherwise the roofs may behave as a source of pollutants, principally for carbon and phosphorus. Both field and column studies showed an important retention for Zn and Cu. The column showed, however, lower SS, DOC and metal concentrations in the percolate than could be observed in the field even if corrected for run-off. This is most probably due to the difference in exposition history and weathering processes.

International audience | This study compares the effectiveness of two different thickness of green roof substrate with respect to nutrient and heavy metal retention and release. To understand and evaluate the long term behaviour of green roofs, substrate columns with the same structure and composition as the green roofs, were exposed in laboratory to artificial rain. The roofs act as a sink for C, N, P, zinc and copper for small rain events if the previous period was principally dry. Otherwise the roofs may behave as a source of pollutants, principally for carbon and phosphorus. Both field and column studies showed an important retention for Zn and Cu. The column showed, however, lower SS, DOC and metal concentrations in the percolate than could be observed in the field even if corrected for run-off. This is most probably due to the difference in exposition history and weathering processes. (C) 2013 Elsevier Ltd. All rights reserved.

This study addressed the relative importance of particle coating, sewage sludge amendment, and aging on aggregation and dissolution of manufactured Ag nanoparticles (Ag MNPs) in soil pore water. Ag MNPs with citrate (CIT) or polyvinylpyrrolidone (PVP) coatings were incubated with soil or municipal sewage sludge which was then amended to soil (1% or 3% sludge (w/w)). Pore waters were extracted after 1 week and 2 and 6 months and analyzed for chemical speciation, aggregation state and dissolution. Ag MNP coating had profound effects on aggregation state and partitioning to pore water in the absence of sewage sludge, but pre-incubation with sewage sludge negated these effects. This suggests that Ag MNP coating does not need to be taken into account to understand fate of AgMNPs applied to soil through biosolids amendment. Aging of soil also had profound effects that depended on Ag MNP coating and sludge amendment.

International audience | This study addressed the relative importance of particle coating, sewage sludge amendment, and aging on aggregation and dissolution of manufactured Ag nanoparticles (Ag MNPs) in soil pore water. Ag MNPs with citrate (CIT) or polyvinylpyrrolidone (PVP) coatings were incubated with soil or municipal sewage sludge which was then amended to soil (1% or 3% sludge (w/w)). Pore waters were extracted after 1 week and 2 and 6 months and analyzed for chemical speciation, aggregation state and dissolution. Ag MNP coating had profound effects on aggregation state and partitioning to pore water in the absence of sewage sludge, but pre-incubation with sewage sludge negated these effects. This suggests that Ag MNP coating does not need to be taken into account to understand fate of AgMNPs applied to soil through biosolids amendment. Aging of soil also had profound effects that depended on Ag MNP coating and sludge amendment. (C) 2013 Elsevier Ltd. All rights reserved.

Nanoscale zerovalent iron (nZVI) has potential for the remediation of organochlorine-contaminated environments. Environmental safety concerns associated with in situ deployment of nZVI include potential negative impacts on indigenous microbes whose biodegradative functions could contribute to contaminant remediation. With respect to a two-step polychlorinated biphenyl remediation scenario comprising nZVI dechlorination followed by aerobic biodegradation, we examined the effect of polyacrylic acid (PAA)-coated nZVI (mean diameter = 12.5 nm) applied at 10 g nZVI kg−1 to Aroclor-1242 contaminated and uncontaminated soil over 28 days. nZVI had a limited effect on Aroclor congener profiles, but, either directly or indirectly via changes to soil physico-chemical conditions (pH, Eh), nZVI addition caused perturbation to soil bacterial community composition, and reduced the activity of chloroaromatic mineralizing microorganisms. We conclude that nZVI addition has the potential to inhibit microbial functions that could be important for PCB remediation strategies combining nZVI treatment and biodegradation.

Nanoscale zerovalent iron (nZVI) has potential for the remediation of organochlorine-contaminated environments. Environmental safety concerns associated with in situ deployment of nZVI include potential negative impacts on indigenous microbes whose biodegradative functions could contribute to contaminant remediation. With respect to a two-step polychlorinated biphenyl remediation scenario comprising nZVI dechlorination followed by aerobic biodegradation, we examined the effect of polyacrylic acid (PAA)-coated nZVI (mean diameter = 12.5 nm) applied at 10 g nZVI kg−1 to Aroclor-1242 contaminated and uncontaminated soil over 28 days. nZVI had a limited effect on Aroclor congener profiles, but, either directly or indirectly via changes to soil physico-chemical conditions (pH, Eh), nZVI addition caused perturbation to soil bacterial community composition, and reduced the activity of chloroaromatic mineralizing microorganisms. We conclude that nZVI addition has the potential to inhibit microbial functions that could be important for PCB remediation strategies combining nZVI treatment and biodegradation.