Mercury is responsible for serious episodes of environmental pollution throughout the world, especially in the Amazon. This toxicity has led regulatory agencies to focus on fish as the target organism for protecting the health of humans and other sensitive organisms. Unfortunately, in the Amazon area, different sampling strategies and the wide variety of sampling areas and fish species make it extremely difficult to determine relationships across geographic regions or over time to ascertain historical trends. Thus, the aim of this work was to achieve three main objectives: a comparative study of mercury contamination in fish of Itaituba (Tapajós, located downstream of the largest gold-mining region in Amazon) and Belém (an area non-exposed to mercury pollution of anthropogenic origin), perform an analysis of inorganic mercury (IHg) versus monomethylmercury (MeHg) contents, and, finally, compare mercury contamination in Tapajós over time. Five piscivorous species were obtained in Itaituba and Belém. Also, four non-piscivorous species were collected in Itaituba. For the first time, mercury speciation showed that (1) current MeHg levels in piscivorous species in Tapajós are higher than those of the non-exposed area, (2) piscivorous species from Itaituba (dourada, filhote, and sarda) contained mercury levels above the World Health Organization safety limit (~17 %) and/or above the US Environmental Protection Agency tissue residue criterion (40 %), (3) increased MeHg is usually accompanied by increased IHg, and (4) the mean total mercury concentrations for piscivorous species in Itaituba were within the same range and, associated uncertainties as those previously reported, although a remarkable decreasing trend over time was observed for mean total Hg concentrations in non-piscivorous species from Itaituba. The present study supports the importance of continuous monitoring of both populations in the Amazon Rivers. Our results will better assist the development of preventive strategies and governmental actions to confront the problem of mercury contamination in the Amazon.

Mercury is responsible for serious episodes of environmental pollution throughout the world, especially in the Amazon. This toxicity has led regulatory agencies to focus on fish as the target organism for protecting the health of humans and other sensitive organisms. Unfortunately, in the Amazon area, different sampling strategies and the wide variety of sampling areas and fish species make it extremely difficult to determine relationships across geographic regions or over time to ascertain historical trends. Thus, the aim of this work was to achieve three main objectives: a comparative study of mercury contamination in fish of Itaituba (Tapajós, located downstream of the largest gold-mining region in Amazon) and Belém (an area non-exposed to mercury pollution of anthropogenic origin), perform an analysis of inorganic mercury (IHg) versus monomethylmercury (MeHg) contents, and, finally, compare mercury contamination in Tapajós over time. Five piscivorous species were obtained in Itaituba and Belém. Also, four non-piscivorous species were collected in Itaituba. For the first time, mercury speciation showed that (1) current MeHg levels in piscivorous species in Tapajós are higher than those of the non-exposed area, (2) piscivorous species from Itaituba (dourada, filhote, and sarda) contained mercury levels above the World Health Organization safety limit (~17 %) and/or above the US Environmental Protection Agency tissue residue criterion (40 %), (3) increased MeHg is usually accompanied by increased IHg, and (4) the mean total mercury concentrations for piscivorous species in Itaituba were within the same range and, associated uncertainties as those previously reported, although a remarkable decreasing trend over time was observed for mean total Hg concentrations in non-piscivorous species from Itaituba. The present study supports the importance of continuous monitoring of both populations in the Amazon Rivers. Our results will better assist the development of preventive strategies and governmental actions to confront the problem of mercury contamination in the Amazon.

Exposure to specific metallic compounds can cause severe deleterious modifications in organisms. Fishes are particularly prone to toxic effects from exposure to metallic compounds via their environment. Species that inhabit estuaries or freshwater environments can be chronically affected by persistent exposure to a large number of metallic compounds, particularly those released by industrial activities. In this study, we exposed yellow eels (European eel, Anguilla anguilla) for 28 days to environmentally relevant concentrations of four specific metals; lead (300, 600, and 1,200 μg/l), copper (40, 120, and 360 μg/l), zinc (30, 60, and 120 μg/l) and cadmium (50, 150, and 450 μg/l). The selected endpoints to assess the toxicological effects were neurotransmission (cholinesterasic activity in nervous tissue), antioxidant defense, and phase II metabolism (glutathione-S-transferase [GST] activity, in both gills and liver tissues), and peroxidative damage. The results showed an overall lack of effects on acetylcholinesterase for all tested metals. Lead, copper, and cadmium exposure caused a significant, dose-dependent, increase in GST activity in gill tissue. However, liver GST only significantly increased following zinc exposure. No statistically significant effects were observed for the thiobarbituric acid reactive substances assay, indicating the absence of peroxidative damage. These findings suggest that, despite the occurrence of an oxidative-based response after exposure to lead, copper, and cadmium, this had no consequence in terms of peroxidative membrane damage; furthermore, cholinergic neurotoxicity caused by lead, copper, and cadmium did not occur. The implications of these results are further discussed.

Exposure to specific metallic compounds can cause severe deleterious modifications in organisms. Fishes are particularly prone to toxic effects from exposure to metallic compounds via their environment. Species that inhabit estuaries or freshwater environments can be chronically affected by persistent exposure to a large number of metallic compounds, particularly those released by industrial activities. In this study, we exposed yellow eels (European eel, Anguilla anguilla) for 28 days to environmentally relevant concentrations of four specific metals; lead (300, 600, and 1,200 μg/l), copper (40, 120, and 360 μg/l), zinc (30, 60, and 120 μg/l) and cadmium (50, 150, and 450 μg/l). The selected endpoints to assess the toxicological effects were neurotransmission (cholinesterasic activity in nervous tissue), antioxidant defense, and phase II metabolism (glutathione-S-transferase [GST] activity, in both gills and liver tissues), and peroxidative damage. The results showed an overall lack of effects on acetylcholinesterase for all tested metals. Lead, copper, and cadmium exposure caused a significant, dose-dependent, increase in GST activity in gill tissue. However, liver GST only significantly increased following zinc exposure. No statistically significant effects were observed for the thiobarbituric acid reactive substances assay, indicating the absence of peroxidative damage. These findings suggest that, despite the occurrence of an oxidative-based response after exposure to lead, copper, and cadmium, this had no consequence in terms of peroxidative membrane damage; furthermore, cholinergic neurotoxicity caused by lead, copper, and cadmium did not occur. The implications of these results are further discussed.

The efficacy of a wastewater treatment lagoon (WWTL) at preventing the spread of Pseudomonas aeruginosa into natural aquatic habitats was investigated. A WWTL and its connected combined sewer and brook were exhaustively sampled. Physico-chemical analyses showed a stratification of the first pond according to pH, temperature and oxygen content. The P. aeruginosa counts partially matched this stratification with higher values among the bottom anaerobic waters of the first half of this pond. Genotyping of 494 WWTL P. aeruginosa strains was performed and led to the definition of 85 lineages. Dominant lineages were observed, with some being found all over the WWTL including the connected brook. IS5 was used as an indicator of genomic changes, and 1 to 12 elements were detected among 16 % of the strains. IS-driven lasR (genetic regulator) disruptions were detected among nine strains that were not part of the dominant lineages. These insertional mutants did not show significant elastase activities but showed better growth than the PAO1 reference strain in WWTL waters. Differences in growth patterns were related to a better survival of these mutants at an alkaline pH and a better ability at using some C-sources such as alanine. The opportunistic colonization of a WWTL by P. aeruginosa can involve several metabolic strategies which appeared lineage specific. Some clones appeared more successful than others at disseminating from a combined sewer toward the overflow of a WWTL.

International audience | The efficacy of a wastewater treatment lagoon (WWTL) at preventing the spread of Pseudomonas aeruginosa into natural aquatic habitats was investigated. A WWTL and its connected combined sewer and brook were exhaustively sampled. Physico-chemical analyses showed a stratification of the first pond according to pH, temperature and oxygen content. The P. aeruginosa counts partially matched this stratification with higher values among the bottom anaerobic waters of the first half of this pond. Genotyping of 494 WWTL P. aeruginosa strains was performed and led to the definition of 85 lineages. Dominant lineages were observed, with some being found all over the WWTL including the connected brook. IS5 was used as an indicator of genomic changes, and 1 to 12 elements were detected among 16 % of the strains. IS-driven lasR (genetic regulator) disruptions were detected among nine strains that were not part of the dominant lineages. These insertional mutants did not show significant elastase activities but showed better growth than the PAO1 reference strain in WWTL waters. Differences in growth patterns were related to a better survival of these mutants at an alkaline pH and a better ability at using some C-sources such as alanine. The opportunistic colonization of a WWTL by P. aeruginosa can involve several metabolic strategies which appeared lineage specific. Some clones appeared more successful than others at disseminating from a combined sewer toward the overflow of a WWTL.

A natural sediment spiked with three individual polycyclic aromatic hydrocarbons (PAHs; pyrene, phenanthrene and benzo[a]pyrene) was used to expose zebrafish embryos and larvae during 4 days. The total PAH concentration was 4.4 μg g⁻¹which is in the range found in sediment from contaminated areas. Quantification of metabolites in the larvae after exposure confirmed the actual contamination of the larvae and indicated an active metabolism especially for pyrene and benzo[a]pyrene. After a transfer in a clean medium, the larvae were reared to adulthood and evaluated for survival, growth, reproduction, and behavior. Measured endpoints revealed a late disruption of growth (appearing at 5 months) and a trend toward a lower reproductive ability. Adults of embryos exposed to sediment spiked with PAHs displayed lethargic and/or anxiety-like behaviors. This latter behavior was also identified in offspring at larval stage. All together, these effects could have detrimental consequences on fish performances and contribution to recruitment.

A natural sediment spiked with three individual polycyclic aromatic hydrocarbons (PAHs; pyrene, phenanthrene and benzo[a]pyrene) was used to expose zebrafish embryos and larvae during 4 days. The total PAH concentration was 4.4 μg g−1 which is in the range found in sediment from contaminated areas. Quantification of metabolites in the larvae after exposure confirmed the actual contamination of the larvae and indicated an active metabolism especially for pyrene and benzo[a]pyrene. After a transfer in a clean medium, the larvae were reared to adulthood and evaluated for survival, growth, reproduction, and behavior. Measured endpoints revealed a late disruption of growth (appearing at 5 months) and a trend toward a lower reproductive ability. Adults of embryos exposed to sediment spiked with PAHs displayed lethargic and/or anxiety-like behaviors. This latter behavior was also identified in offspring at larval stage. All together, these effects could have detrimental consequences on fish performances and contribution to recruitment.

A natural sediment spiked with three individual polycyclic aromatic hydrocarbons (PAHs; pyrene, phenanthrene and benzo[a]pyrene) was used to expose zebrafish embryos and larvae during 4 days. The total PAH concentration was 4.4 μg g−1 which is in the range found in sediment from contaminated areas. Quantification of metabolites in the larvae after exposure confirmed the actual contamination of the larvae and indicated an active metabolism specially for pyrene and benzo[a]pyrene. After a transfer in a clean medium, the larvae were reared to adulthood and valuated for survival, growth, reproduction, and behavior. Measured endpoints revealed a late disruption of growth (appearing at 5 months) and a trend toward a lower reproductive ability. Adults of embryos exposed to sediment spiked with PAHs displayed lethargic and/or anxiety-like behaviors. This latter behavior was also identified in offspring at larval stage. All together, these effects could have detrimental consequences on fish performances and contribution to recruitment.

The aim of this work was the evaluation of QuEChERS extraction method for polycyclic aromatic hydrocarbon (PAH) determination in various types of tea. In the experiment, different kinds of extraction solvents, sorbents and a final method of sample preparation were compared. The final extracts were analysed by gas chromatography-selected ion monitoring-mass spectrometry. The results suggest that acetonitrile extraction, clean up with SAX and final liquid–liquid extraction was the best combination giving the most purified extracts and acceptable compound recoveries for different types of teas. In the study of real samples, compounds belonging to light PAHs were mostly detected, and heavy polycyclic aromatic hydrocarbons, including benzo[a]pyrene, were not identified in any of samples.

The aim of this work was the evaluation of QuEChERS extraction method for polycyclic aromatic hydrocarbon (PAH) determination in various types of tea. In the experiment, different kinds of extraction solvents, sorbents and a final method of sample preparation were compared. The final extracts were analysed by gas chromatography-selected ion monitoring-mass spectrometry. The results suggest that acetonitrile extraction, clean up with SAX and final liquid–liquid extraction was the best combination giving the most purified extracts and acceptable compound recoveries for different types of teas. In the study of real samples, compounds belonging to light PAHs were mostly detected, and heavy polycyclic aromatic hydrocarbons, including benzo[a]pyrene, were not identified in any of samples. | GC-MS, Extraction, PAHs, Tea, QuEChERS, SPE sorbents | 30 | 1326-1338 | 2

Methods for simulating air pollution due to road traffic and the associated effects on stormwater runoff quality in an urban environment are examined with particular emphasis on the integration of the various simulation models into a consistent modelling chain. To that end, the models for traffic, pollutant emissions, atmospheric dispersion and deposition, and stormwater contamination are reviewed. The present study focuses on the implementation of a modelling chain for an actual urban case study, which is the contamination of water runoff by cadmium (Cd), lead (Pb), and zinc (Zn) in the Grigny urban catchment near Paris, France. First, traffic emissions are calculated with traffic inputs using the COPERT4 methodology. Next, the atmospheric dispersion of pollutants is simulated with the Polyphemus line source model and pollutant deposition fluxes in different subcatchment areas are calculated. Finally, the SWMM water quantity and quality model is used to estimate the concentrations of pollutants in stormwater runoff. The simulation results are compared to mass flow rates and concentrations of Cd, Pb and Zn measured at the catchment outlet. The contribution of local traffic to stormwater contamination is estimated to be significant for Pb and, to a lesser extent, for Zn and Cd; however, Pb is most likely overestimated due to outdated emissions factors. The results demonstrate the importance of treating distributed traffic emissions from major roadways explicitly since the impact of these sources on concentrations in the catchment outlet is underestimated when those traffic emissions are spatially averaged over the catchment area.

The authors thank the "Ville numérique" and "OPUR" research programmes, IFSTTAR and École des Ponts ParisTech/Cerea for their financial support, SIVOA for providing the data on the catchment and DRIEA for providing the traffic data. | International audience | Methods for simulating air pollution due to road traffic and the associated effects on stormwater runoff quality in an urban environment are examined with particular emphasis on the integration of the various simulation models into a consistent modelling chain. To that end, the models for traffic, pollutant emissions, atmospheric dispersion and deposition, and stormwater contamination are reviewed. The present study focuses on the implementation of a modelling chain for an actual urban case study, which is the contamination of water runoff by cadmium (Cd), lead (Pb), and zinc (Zn) in the Grigny urban catchment near Paris, France. First, traffic emissions are calculated with traffic inputs using the COPERT4 methodology. Next, the atmospheric dispersion of pollutants is simulated with the Polyphemus line source model and pollutant deposition fluxes in different subcatchment areas are calculated. Finally, the SWMMwater quantity and quality model is used to estimate the concentrations of pollutants in stormwater runoff. The simulation results are compared to mass flow rates and concentrations of Cd, Pb and Zn measured at the catchment outlet. The contribution of local traffic to stormwater contamination is estimated to be significant for Pb and, to a lesser extent, for Zn and Cd; however, Pb is most likely overestimated due to outdated emissions factors. The results demonstrate the importance of treating distributed traffic emissions from major roadways explicitly since the impact of these sources on concentrations in the catchment outlet is underestimated when those traffic

The stock of the European eel (Anguilla anguilla L.) continues to decline and has reached a new minimum in 2011. Poor health status of the spawners due to organic contaminants is one of the possible causes for this dramatic situation. Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants, which are rapidly metabolized in vertebrates. EROD (ethoxyresorufin-O-deethylase) and GST (glutathione-S-transferase) are two enzymes involved in PAH detoxification in fish. In this study, PAH metabolites as well as EROD and GST activity in a large, comprising dataset of more than 260 migratory and pre-migratory eels from five large German river basin districts were used to describe PAH exposure and its metabolism as possible indicators for the habitat quality for eels. Eel from the river Elbe appear to be moderately contaminated with PAH. Highest mean values of PAH metabolites were analysed in fish from the river Rhine. However, the results suggest that contaminants such as PAH are metabolized in the fish and may have contributed to EROD activity in eels caught from the Elbe estuary to 600 km upstream. Since the eel’s onset of cessation of feeding is closely linked to maturation and migration, we propose bile pigments as new indicators contributing to identify the proportion of migratory eel, which is crucial information for eel management plans. We showed that PAH metabolites normalized to bile pigments as well as EROD could be used to describe the habitat quality and might be suitable parameters in search for suitable stocking habitats.

The stock of the European eel (Anguilla anguilla L.) continues to decline and has reached a new minimum in 2011. Poor health status of the spawners due to organic contaminants is one of the possible causes for this dramatic situation. Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants, which are rapidly metabolized in vertebrates. EROD (ethoxyresorufin-O-deethylase) and GST (glutathione-S-transferase) are two enzymes involved in PAH detoxification in fish. In this study, PAH metabolites as well as EROD and GST activity in a large, comprising dataset of more than 260 migratory and pre-migratory eels from five large German river basin districts were used to describe PAH exposure and its metabolism as possible indicators for the habitat quality for eels. Eel from the river Elbe appear to be moderately contaminated with PAH. Highest mean values of PAH metabolites were analysed in fish from the river Rhine. However, the results suggest that contaminants such as PAH are metabolized in the fish and may have contributed to EROD activity in eels caught from the Elbe estuary to 600 km upstream. Since the eel’s onset of cessation of feeding is closely linked to maturation and migration, we propose bile pigments as new indicators contributing to identify the proportion of migratory eel, which is crucial information for eel management plans. We showed that PAH metabolites normalized to bile pigments as well as EROD could be used to describe the habitat quality and might be suitable parameters in search for suitable stocking habitats.

The biosorption characteristics of Cd (II) ions using the living biomass of the marine diatom Phaeodactylum tricornutum were investigated. This microalga is a highly tolerant species to cadmium toxicity; for this reason, it is interesting to know its potential for use in the removal of this metal. The use of living biomass offers better possibilities than that of dead biomass since cadmium can also be bioaccumulated inside the cells. For this purpose, tolerant species are necessary. P. tricornutum is within this category with an EC₅₀,₉₆ₕof 19.1 ± 3.5 mg Cd (II)/L, and in the present manuscript, it is demonstrated that this microalga has a very good potential for bioremediation of Cd (II) ions in saline habitats. Cadmium removed by the cells was divided into three fractions: total, intracellular and bioadsorbed. The experiments were conducted for 96 h in natural seawater with a concentration range of 1–100 mg Cd (II)/L. Each fraction was characterized every 24 h by sorption isotherms. The experimental isotherm data were analyzed using the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin equations. The biosorption was well described by Langmuir isotherm followed by Freundlich. The worst model was Temkin. The biosorption capacity of this microalga for Cd (II) ions was found to be 67.1 ± 3.2 mg/g after 96 h with approximately 40 % of this capacity in the intracellular fraction. The bioconcentration factor determined was 2,204.7 after 96 h and with an initial Cd (II) concentration of 1 mg/L.

The biosorption characteristics of Cd(II) ions using the living biomass of the marine diatom Phaeodactylum tricornutum were investigated. This microalga is a highly tolerant species to cadmium toxicity, for this reason is interesting to know its potential for use in the removal of Cd(II) ions. The use of living biomass offers better possibilities than dead biomass since cadmium can also be bioaccumulated inside the cells. For this purpose, tolerant species are necessary. P. tricornutum is within this category and in the present manuscript is demonstrated that this microalga has a very good potential for bioremediation of Cd(II) ions. Cadmium removed by the cells was divided into three fractions: total, intracellular and bioadsorbed. The experiments were conducted for 96 h in a concentration range of 1-100 mg Cd(II)/L. Each fraction was characterized every 24 h by sorption isotherms. The experimental isotherm data were analysed using the Langmuir, Freundlinch, Dubinin-Radushkevich and Temkin equations. The biosorption was well described by Langmuir isotherm followed by Freundlich. The worst model was Temkin. The biosorption capacity of this microalga for Cd(II) ions was found to be 67.140 ± 3.247 mg/g after 96 h with approximately 40% of this capacity in the intracellular fraction. The bioconcentration factor determined was 2204.7 after 96 h and with an initial Cd(II) concentration of 1 mg/L.

Phthalates are common atmospheric contaminants used in the plastic industry. Ants have been shown to constitute good bioindicators of phthalate pollution. Hence, phthalates remain trapped on ant cuticles which are mostly coated with long-chain hydrocarbons. In this study, we artificially contaminated Lasius niger ants with four phthalates: dibutyl phthalate (DBP), diisobutyl phthalate (DiBP), di(2-ethylhexyl) phthalate (DEHP), and benzyl butyl phthalate (BBP). The first three have previously been found on ants in nature in Touraine (France), while the fourth has not. The four phthalates disappeared rapidly (less than 5 days) from the cuticles of live ants. In contrast, on the cuticles of dead ants, DEHP quantities remained unchanged over time. These results indicate that phthalates are actively absorbed by the cuticles of live ants. Cuticular absorption of phthalates is nonspecific because eicosane, a nonnatural hydrocarbon on L. niger cuticle, was similarly absorbed. Ants are important ecological engineers and may serve as bioindicators of ecosystem health. We also suggest that ants and more generally terrestrial arthropods may contribute to the removal of phthalates from the local environment.

International audience | Phthalates are common atmospheric contaminantsused in the plastic industry. Ants have been shown to constitutegood bioindicators of phthalate pollution. Hence,phthalates remain trapped on ant cuticles which are mostlycoated with long-chain hydrocarbons. In this study, we artificiallycontaminated Lasius niger ants with four phthalates:dibutyl phthalate (DBP), diisobutyl phthalate (DiBP), di(2-ethylhexyl) phthalate (DEHP), and benzyl butyl phthalate(BBP). The first three have previously been found on ants innature in Touraine (France), while the fourth has not. The fourphthalates disappeared rapidly (less than 5 days) from thecuticles of live ants. In contrast, on the cuticles of dead ants,DEHP quantities remained unchanged over time. These resultsindicate that phthalates are actively absorbed by thecuticles of live ants. Cuticular absorption of phthalates isnonspecific because eicosane, a nonnatural hydrocarbon onL. niger cuticle, was similarly absorbed. Ants are importantecological engineers and may serve as bioindicators of ecosystemhealth. We also suggest that ants and more generallyterrestrial arthropods may contribute to the removal ofphthalates from the local environment

Accurate monitoring of degradation levels in soils is essential in order to understand and achieve complete degradation of petroleum hydrocarbons in contaminated soils. We aimed to develop the use of multivariate methods for the monitoring of biodegradation of diesel in soils and to determine if diesel contaminated soils could be remediated to a chemical composition similar to that of an uncontaminated soil. An incubation experiment was set up with three contrasting soil types. Each soil was exposed to diesel at varying stages of degradation and then analysed for key hydrocarbons throughout 161 days of incubation. Hydrocarbon distributions were analysed by Principal Coordinate Analysis and similar samples grouped by cluster analysis. Variation and differences between samples were determined using permutational multivariate analysis of variance. It was found that all soils followed trajectories approaching the chemical composition of the unpolluted soil. Some contaminated soils were no longer significantly different to that of uncontaminated soil after 161 days of incubation. The use of cluster analysis allows the assignment of a percentage chemical similarity of a diesel contaminated soil to an uncontaminated soil sample. This will aid in the monitoring of hydrocarbon contaminated sites and the establishment of potential endpoints for successful remediation.

Accurate monitoring of degradation levels in soils is essential in order to understand and achieve complete degradation of petroleum hydrocarbons in contaminated soils. We aimed to develop the use of multivariate methods for the monitoring of biodegradation of diesel in soils and to determine if diesel contaminated soils could be remediated to a chemical composition similar to that of an uncontaminated soil. An incubation experiment was set up with three contrasting soil types. Each soil was exposed to diesel at varying stages of degradation and then analysed for key hydrocarbons throughout 161 days of incubation. Hydrocarbon distributions were analysed by Principal Coordinate Analysis and similar samples grouped by cluster analysis. Variation and differences between samples were determined using permutational multivariate analysis of variance. It was found that all soils followed trajectories approaching the chemical composition of the unpolluted soil. Some contaminated soils were no longer significantly different to that of uncontaminated soil after 161 days of incubation. The use of cluster analysis allows the assignment of a percentage chemical similarity of a diesel contaminated soil to an uncontaminated soil sample. This will aid in the monitoring of hydrocarbon contaminated sites and the establishment of potential endpoints for successful remediation.