In the French West Indies, the chlordecone (organochloride pesticide) pollution is now diffuse becoming new contamination source for crops and environment (water, trophic chain). Decontamination by bioremediation and chemical degradation are still under development but the physical limitations of these approaches are generally not taken into account. These physical limitations are related to the poor physical accessibility to the pesticides in soils because of the peculiar structural properties of the contaminated clays (pore volume, transport properties, permeability, and diffusion). Some volcanic soils (andosols), which represent the half of the contaminated soils in Martinique, contain nanoclay (allophane) with a unique structure and porous properties. Andosols are characterized by pore size distribution in the mesoporous range, a high specific surface area, a large pore volume, and a fractal structure. Our hypothesis is that the clay microstructure characteristics are crucial physico-chemical factors strongly limiting the remediation of the pesticide. Our results show that allophane microstructure (small pore size, hierarchical microstructure, and tortuosity) favors accumulation of chlordecone, in andosols. Moreover, the clay microporosity limits the accessibility of microorganisms and chemical species able to decontaminate because of poor transport properties (permeability and diffusion). We model the transport properties by two approaches: (1) we use a numerical model to simulate the structure of allophane aggregates. The algorithm is based on a cluster–cluster aggregation model. From the simulated data, we derived the pore volume, specific surface area, tortuosity, permeability, and diffusion. We show that transport properties strongly decrease because of the presence of allophane. (2) The fractal approach. We characterize the fractal features (size of the fractal aggregate, fractal dimension, tortuosity inside allophane aggregates) and we calculate that transport properties decrease of several order ranges inside the clay aggregates. These poor transport properties are important parameters to explain the poor accessibility to pollutants in volcanic soils and should be taken into account by future decontamination process. We conclude that for andosols, this inaccessibility could render inefficient some of the methods proposed in the literature.

In the French West Indies, the chlordecone (organochloride pesticide) pollution is now diffuse becoming new contamination source for crops and environment (water, trophic chain). Decontamination by bioremediation and chemical degradation are still under development but the physical limitations of these approaches are generally not taken into account. These physical limitations are related to the poor physical accessibility to the pesticides in soils because of the peculiar structural properties of the contaminated clays (pore volume, transport properties, permeability, and diffusion). Some volcanic soils (andosols), which represent the half of the contaminated soils in Martinique, contain nanoclay (allophane) with a unique structure and porous properties. Andosols are characterized by pore size distribution in the mesoporous range, a high specific surface area, a large pore volume, and a fractal structure. Our hypothesis is that the clay microstructure characteristics are crucial physico-chemical factors strongly limiting the remediation of the pesticide. Our results show that allophane microstructure (small pore size, hierarchical microstructure, and tortuosity) favors accumulation of chlordecone, in andosols. Moreover, the clay microporosity limits the accessibility of microorganisms and chemical species able to decontaminate because of poor transport properties (permeability and diffusion). We model the transport properties by two approaches: (1) we use a numerical model to simulate the structure of allophane aggregates. The algorithm is based on a cluster–cluster aggregation model. From the simulated data, we derived the pore volume, specific surface area, tortuosity, permeability, and diffusion. We show that transport properties strongly decrease because of the presence of allophane. (2) The fractal approach. We characterize the fractal features (size of the fractal aggregate, fractal dimension, tortuosity inside allophane aggregates) and we calculate that transport properties decrease of several order ranges inside the clay aggregates. These poor transport properties are important parameters to explain the poor accessibility to pollutants in volcanic soils and should be taken into account by future decontamination process. We conclude that for andosols, this inaccessibility could render inefficient some of the methods proposed in the literature.

In Guadeloupe, the use between 1972 and 1993 of chlordecone, an organochlorine insecticide, has permanently contaminated the island's soil, thus contaminating the food chain at its very beginning. There is today a strong societal requirement for an improved mapping of the contaminated zones. Given the extent of the areas to be covered, carrying out soil tests on each plot of the territory would be a long and expensive process. In this article, we explore a method of demarcating polluted areas. The approach adopted consists in carrying out, using surface water analyses, a hydrological delimitation that makes it possible to distinguish contaminated watersheds from uncontaminated ones. The selection of sampling points was based on the spatial analysis of the actual and potential contamination data existing at the beginning of the study. The approach was validated by soil analyses, after having compared the contamination data of the watersheds with the soil contamination data of the plots within them. The study thus made it possible to highlight new contaminated areas and also those at risk of contamination and to identify the plots to be targeted as a priority during future analysis campaigns by State services.

In Guadeloupe, the use between 1972 and 1993 of chlordecone, an organochlorine insecticide, has permanently contaminated the island’s soil, thus contaminating the food chain at its very beginning. There is today a strong societal requirement for an improved mapping of the contaminated zones. Given the extent of the areas to be covered, carrying out soil tests on each plot of the territory would be a long and expensive process. In this article, we explore a method of demarcating polluted areas. The approach adopted consists in carrying out, using surface water analyses, a hydrological delimitation that makes it possible to distinguish contaminated watersheds from uncontaminated ones. The selection of sampling points was based on the spatial analysis of the actual and potential contamination data existing at the beginning of the study. The approach was validated by soil analyses, after having compared the contamination data of the watersheds with the soil contamination data of the plots within them. The study thus made it possible to highlight new contaminated areas and also those at risk of contamination and to identify the plots to be targeted as a priority during future analysis campaigns by State services.

International audience | In Guadeloupe, the use between 1972 and 1993 of chlordecone, an organochlorine insecticide, has permanently contaminated the island’s soil, thus contaminating the food chain at its very beginning. There is today a strong societal requirement for an improved mapping of the contaminated zones. Given the extent of the areas to be covered, carrying out soil tests on each plot of the territory would be a long and expensive process. In this article, we explore a method of demarcating polluted areas. The approach adopted consists in carrying out, using surface water analyses, a hydrological delimitation that makes it possible to distinguish contaminated watersheds from uncontaminated ones. The selection of sampling points was based on the spatial analysis of the actual and potential contamination data existing at the beginning of the study. The approach was validated by soil analyses, after having compared the contamination data of the watersheds with the soil contamination data of the plots within them. The study thus made it possible to highlight new contaminated areas and also those at risk of contamination and to identify the plots to be targeted as a priority during future analysis campaigns by State services.

Plants were sampled from four different types of chlordecone-contaminated land in Guadeloupe (West Indies). The objective was to investigate the importance of biological and agri-environmental parameters in the ability of plants to bioaccumulate chlordecone. Among the plant traits studied, only the growth habit significantly affected chlordecone transfer, since prostrate plants concentrated more chlordecone than erect plants. In addition, intensification of land use has led to a significant increase in the amount of chlordecone absorbed by plants. The use of Bayesian networks uncovers some hypothesis and identifies paths for reflection and possible studies to identify and quantify relationships that explain our data.

Plants were sampled from four different types of chlordecone-contaminated land in Guadeloupe (West Indies). The objective was to investigate the importance of biological and agri-environmental parameters in the ability of plants to bioaccumulate chlordecone. Among the plant traits studied, only the growth habit significantly affected chlordecone transfer, since prostrate plants concentrated more chlordecone than erect plants. In addition, intensification of land use has led to a significant increase in the amount of chlordecone absorbed by plants. The use of Bayesian networks uncovers some hypothesis and identifies paths for reflection and possible studies to identify and quantify relationships that explain our data. Graphical abstract

International audience | Plants were sampled from four different types of chlordecone-contaminated land in Guadeloupe (West Indies). The objective was to investigate the importance of biological and agri-environmental parameters in the ability of plants to bioaccumulate chlordecone. Among the plant traits studied, only the growth habit significantly affected chlordecone transfer, since prostrate plants concentrated more chlordecone than erect plants. In addition, intensification of land use has led to a significant increase in the amount of chlordecone absorbed by plants. The use of Bayesian networks uncovers some hypothesis and identifies paths for reflection and possible studies to identify and quantify relationships that explain our data.

Concentrations of organohalogenated contaminants (OHCs) can show significant temporal and spatial variation in the environment and wildlife. Most of the variation is due to changes in use and production, but environmental and biological factors may also contribute to the variation. Nestlings of top predators are exposed to maternally transferred OHCs in the egg and through their dietary intake after hatching. The present study investigated spatial and temporal variation of OHCs and the role of age and diet on these variations in plasma of Norwegian white-tailed eagle (Haliaeetus albicilla) nestlings. The nestlings were sampled at two locations, Smøla and Steigen, in 2015 and 2016. The age of the nestlings was recorded (range: 44 - 87 days old) and stable carbon and nitrogen isotopes (δ13C and δ15N) were applied as dietary proxies for carbon source and trophic position, respectively. In total, 14 polychlorinated biphenyls (PCBs, range: 0.82 - 59.05 ng/mL), 7 organochlorinated pesticides (OCPs, range: 0.89 - 52.19 ng/mL), 5 polybrominated diphenyl ethers (PBDEs, range: 0.03 - 2.64 ng/mL) and 8 perfluoroalkyl substances (PFASs, range: 4.58 - 52.94 ng/mL) were quantified in plasma samples from each location and year. The OHC concentrations, age and dietary proxies displayed temporal and spatial variations. The age of the nestlings was indicated as the most important predictor for OHC variation as the models displayed significantly decreasing plasma concentrations of PCBs, OCPs, and PBDEs with increasing age, while concentrations of PFASs were significantly increasing with age. Together with age, the variations in PCB, OCP and PBDE concentrations were also explained by δ13C and indicated decreasing concentrations with a more marine diet. Our findings emphasise age and diet as important factors to consider when investigating variations in plasma OHC concentrations in nestlings. | acceptedVersion

peer reviewed | Concentrations of organohalogenated contaminants (OHCs) can show significant temporal and spatial variation in the environment and wildlife. Most of the variation is due to changes in use and production, but environmental and biological factors may also contribute to the variation. Nestlings of top predators are exposed to maternally transferred OHCs in the egg and through their dietary intake after hatching. The present study investigated spatial and temporal variation of OHCs and the role of age and diet on these variations in plasma of Norwegian white-tailed eagle (Haliaeetus albicilla) nestlings. The nestlings were sampled at two locations, Smøla and Steigen, in 2015 and 2016. The age of the nestlings was recorded (range: 44 – 87 days old) and stable carbon and nitrogen isotopes (δ13C and δ15N) were applied as dietary proxies for carbon source and trophic position, respectively. In total, 14 polychlorinated biphenyls (PCBs, range: 0.82 – 59.05 ng/mL), 7 organochlorinated pesticides (OCPs, range: 0.89 – 52.19 ng/mL), 5 polybrominated diphenyl ethers (PBDEs, range: 0.03 – 2.64 ng/mL) and 8 perfluoroalkyl substances (PFASs, range: 4.58 – 52.94 ng/mL) were quantified in plasma samples from each location and year. The OHC concentrations, age and dietary proxies displayed temporal and spatial variations. The age of the nestlings was indicated as the most important predictor for OHC variation as the models displayed significantly decreasing plasma concentrations of PCBs, OCPs, and PBDEs with increasing age, while concentrations of PFASs were significantly increasing with age. Together with age, the variations in PCB, OCP and PBDE concentrations were also explained by δ13C and indicated decreasing concentrations with a more marine diet. Our findings emphasise age and diet as important factors to consider when investigating variations in plasma OHC concentrations in nestlings. © 2018 Elsevier Ltd | 230465

Concentrations of organohalogenated contaminants (OHCs) can show significant temporal and spatial variation in the environment and wildlife. Most of the variation is due to changes in use and production, but environmental and biological factors may also contribute to the variation. Nestlings of top predators are exposed to maternally transferred OHCs in the egg and through their dietary intake after hatching. The present study investigated spatial and temporal variation of OHCs and the role of age and diet on these variations in plasma of Norwegian white-tailed eagle (Haliaeetus albicilla) nestlings. The nestlings were sampled at two locations, Smøla and Steigen, in 2015 and 2016. The age of the nestlings was recorded (range: 44 – 87 days old) and stable carbon and nitrogen isotopes (δ¹³C and δ¹⁵N) were applied as dietary proxies for carbon source and trophic position, respectively. In total, 14 polychlorinated biphenyls (PCBs, range: 0.82 – 59.05 ng/mL), 7 organochlorinated pesticides (OCPs, range: 0.89 – 52.19 ng/mL), 5 polybrominated diphenyl ethers (PBDEs, range: 0.03 – 2.64 ng/mL) and 8 perfluoroalkyl substances (PFASs, range: 4.58 – 52.94 ng/mL) were quantified in plasma samples from each location and year. The OHC concentrations, age and dietary proxies displayed temporal and spatial variations. The age of the nestlings was indicated as the most important predictor for OHC variation as the models displayed significantly decreasing plasma concentrations of PCBs, OCPs, and PBDEs with increasing age, while concentrations of PFASs were significantly increasing with age. Together with age, the variations in PCB, OCP and PBDE concentrations were also explained by δ¹³C and indicated decreasing concentrations with a more marine diet. Our findings emphasise age and diet as important factors to consider when investigating variations in plasma OHC concentrations in nestlings.

Contrasting soil profiles (coarse-textured and fine-textured) treated with brilliant blue (BB) dye tracer, inorganic nitrogen (N) and phosphorus (P) concentrations along and between stained preferential flow pathways were examined for an irrigated and overfertilised maize monoculture system at the Mediterranean central Chile. The PO4-P concentrations were 2- to 10-fold higher in areas with BB than in areas without BB below 0.5-m soil depth in both soils. This elevated concentration was attributed to transport through cracks in fine-textured soil and finger flow in coarse-textured soil. The highest PO4-P value (13 mg kg(-1)) was found in areas with BB at the fine-textured soil. There were no significant differences in inorganic N concentration between areas with and without BB for both soils, which suggest that the effects of preferential flow are less important for inorganic N forms. There was a strong significant (p < 0.01) positive correlation between PO4-P and NH4-N concentrations in the fine-textured soil, and the amounts retained were clearly proportional to the clay content. Strategies for reducing N and P losses must be placed on good agronomic management of irrigated maize cropping system including accurate calculation of N and P fertiliser rates and establishment of suitable mitigation measures such as cover cropping. | FONDECYT 1150572

Contrasting soil profiles (coarse-textured and fine-textured) treated with brilliant blue (BB) dye tracer, inorganic nitrogen (N) and phosphorus (P) concentrations along and between stained preferential flow pathways were examined for an irrigated and overfertilised maize monoculture system at the Mediterranean central Chile. The PO4-P concentrations were 2- to 10-fold higher in areas with BB than in areas without BB below 0.5-m soil depth in both soils. This elevated concentration was attributed to transport through cracks in fine-textured soil and finger flow in coarse-textured soil. The highest PO4-P value (13 mg kg⁻¹) was found in areas with BB at the fine-textured soil. There were no significant differences in inorganic N concentration between areas with and without BB for both soils, which suggest that the effects of preferential flow are less important for inorganic N forms. There was a strong significant (p < 0.01) positive correlation between PO4-P and NH4-N concentrations in the fine-textured soil, and the amounts retained were clearly proportional to the clay content. Strategies for reducing N and P losses must be placed on good agronomic management of irrigated maize cropping system including accurate calculation of N and P fertiliser rates and establishment of suitable mitigation measures such as cover cropping.

publishedVersion | Paid Open Access

The effects of petroleum aromatic hydrocarbons (PAHs) on the embryonic and larval life stages of teleosts have been extensively examined. However, very little work has been conducted on how spilled oil affects fish sperm and there is no related knowledge concerning oil dispersing agents. The objective of our study was to determine sperm performance of a teleost fish under direct exposure to different concentrations of WAF (water accommodated fraction) and CEWAF (chemically enhanced water accommodated fraction). Capelin sperm motility, swimming behaviour, and sperm fertilization ability were evaluated in a scenario of an oil spill untreated (WAF) and treated (CEWAF) with the dispersant Corexit® EC9500A. Sperm fertilizing ability was lower when exposed to CEWAF concentrations of 16.1 × 103 μg/L total petroleum hydrocarbons and 47.9 μg/L PAH, and when exposed to the dispersant alone. The mechanism responsible for this reduced fertilizing ability is not clear. However, it is not related to the percentage of motile sperm or sperm swimming behaviour, as these were unaffected. WAF did not alter sperm swimming characteristics nor the fertilizing ability. We suggest the dispersant rather than the dispersed oil is responsible for the decrease in the sperm fertilizing ability and hypothesize that the surfactants present in the dispersant affect sperm membrane functionality.

Mercury (Hg) concentrations in freshwater fish relates to aquatic Hg concentrations, which largely derives from soil stores of accumulated atmospheric deposition. Hg in catchment soils as a source for aquatic Hg is poorly studied. Here we test if i) peatland soils produce more methylmercury (MeHg) than forest soils; ii) total Hg (THg) concentrations in top soils are determined by atmospheric inputs, while MeHg is produced in the soils; and iii) soil disturbance promotes MeHg production. In two small boreal catchments, previously used in a paired-catchment forest harvest manipulation study, forest soils and peatlands were sampled and analysed for Hg species and additional soil chemistry. In the undisturbed reference catchment, soils were sampled in different vegetation types, of varying productivity as reflected in tree density, where historical data on precipitation and throughfall Hg and MeHg fluxes were available. Upper soil THg contents were significantly correlated to throughfall inputs of Hg, i.e. lowest in the tree-less peatland and highest in the dense spruce forest. For MeHg, top layer concentrations were similar in forest soils and peatlands, likely related to atmospheric input and local production, respectively. The local peatland MeHg production was documented through significantly higher MeHg-to-THg ratios in the deeper soil layer samples. In the disturbed catchment, soils were sampled in and just outside wheeltracks in an area impacted by forest machinery. Here, MeHg concentrations and the MeHg-to-THg ratios in the upper 5 cm were weakly significantly (p = 0.07) and significantly (p = 0.04) different in and outside of the wheeltracks, respectively, suggesting that soil disturbance promotes methylation. Differences in catchment Hg and MeHg streamwater concentrations were not explained by soil Hg and MeHg information, perhaps because hydrological pathways are a stronger determinant of streamwater chemistry than small variations in soil chemistry driven by disturbance and atmospheric inputs of Hg. | acceptedVersion

Mercury (Hg) concentrations in freshwater fish relates to aquatic Hg concentrations, which largely derives from soil stores of accumulated atmospheric deposition. Hg in catchment soils as a source for aquatic Hg is poorly studied. Here we test if i) peatland soils produce more methylmercury (MeHg) than forest soils; ii) total Hg (THg) concentrations in top soils are determined by atmospheric inputs, while MeHg is produced in the soils; and iii) soil disturbance promotes MeHg production. In two small boreal catchments, previously used in a paired-catchment forest harvest manipulation study, forest soils and peatlands were sampled and analysed for Hg species and additional soil chemistry. In the undisturbed reference catchment, soils were sampled in different vegetation types, of varying productivity as reflected in tree density, where historical data on precipitation and throughfall Hg and MeHg fluxes were available. Upper soil THg contents were significantly correlated to throughfall inputs of Hg, i.e. lowest in the tree-less peatland and highest in the dense spruce forest. For MeHg, top layer concentrations were similar in forest soils and peatlands, likely related to atmospheric input and local production, respectively. The local peatland MeHg production was documented through significantly higher MeHg-to-THg ratios in the deeper soil layer samples. In the disturbed catchment, soils were sampled in and just outside wheeltracks in an area impacted by forest machinery. Here, MeHg concentrations and the MeHg-to-THg ratios in the upper 5 cm were weakly significantly (p = 0.07) and significantly (p = 0.04) different in and outside of the wheeltracks, respectively, suggesting that soil disturbance promotes methylation. Differences in catchment Hg and MeHg streamwater concentrations were not explained by soil Hg and MeHg information, perhaps because hydrological pathways are a stronger determinant of streamwater chemistry than small variations in soil chemistry driven by disturbance and atmospheric inputs of Hg.