The ability of the free ion activity model (FIAM), the terrestrial biotic ligand model (TBLM), the diffusive gradients in thin films (DGT) technique and a plant-based biotest, the RHIZOtest, to predict root copper (Cu) concentration in field-grown durum wheat (Triticum turgidum durum L.) was assessed on 44 soils varying in pH (3.9e7.8) and total Cu (32e184 mg kg_1). None of the methods adequately predicted root Cu concentration, which was mainly correlated with total soil Cu. Results from DGT measurements and even more so FIAM prediction were negatively correlated with soil pH and over-estimated root Cu concentration in acidic soils. TBLM implementation improved numerically FIAM prediction but still failed to predict adequately root Cu concentration as the TBLM formalism did not considered the rhizosphere alkalisation as observed in situ. In contrast, RHIZOtest measurements accounted for rhizosphere alkalisation and were mainly correlated with total soil Cu. (Résumé d'auteur)

International audience | The ability of the free ion activity model (FIAM), the terrestrial biotic ligand model (TBLM), the diffusive gradients in thin films (DGT) technique and a plant-based biotest, the RHIZOtest, to predict root copper (Cu) concentration in field-grown durum wheat (Triticum turgidum durum L) was assessed on 44 soils varying in pH (3.9-7.8) and total Cu (32-184 mg kg(-1)). None of the methods adequately predicted root Cu concentration, which was mainly correlated with total soil Cu. Results from DGT measurements and even more so FIAM prediction were negatively correlated with soil pH and over-estimated root Cu concentration in acidic soils. TBLM implementation improved numerically FIAM prediction but still failed to predict adequately root Cu concentration as the TBLM formalism did not considered the rhizosphere alkalisation as observed in situ. In contrast, RHIZOtest measurements accounted for rhizosphere alkalisation and were mainly correlated with total soil Cu.

The aim of this study was to identify primary flow paths involved in the chlordecone (CLD) river contamination and quantify the CLD fluxes to assess CLD pollution levels and duration according to a typical catchment of the banana cropping area in the French Indies (Guadeloupe): the Pérou Catchment (12 km2) characterized by heavy rainfall (5686 mm year?1). Three sub-catchments (SC1, SC2 and SC3) were studied during the hydrological year 2009–2010: a pedological survey combined with a spatialized hydrochemical approach was conducted. The average soil concentration is higher in the Pérou Catchment (3400 ?g kg?1) than in the entire banana cropping area in Guadeloupe (2100 ?g kg?1). The results showed that CLD stocks in soils vary largely among soil types and farming systems: the weakest stocks are located upstream in SC1 (5 kg ha?1), where a majority of the area is non-cultivated; medium stocks are located in Nitisols downstream in SC3 (9 kg ha?1); and the greatest stocks are observed in SC2 on Andosols (12 kg ha?1) characterized by large farms. The annual water balance and the hydro-chemical analysis revealed that the three sub-catchments exhibited different behaviors. Pérou River contamination was high during low flows, which highlighted that contamination primarily originated from groundwater contributions. The results showed that only a small part of the catchment (SC2), contributing little to the water flow, comprises a major CLD contribution, which is in agreement with the highly contaminated andosol soils observed there. Another significant result considers that at least 50 years would be required to export the totality of the actual CLD soil stocks retained in the topsoil layer. The actual time for soil remediation will however be much longer considering (i) the necessary time for the chlordecone to percolate and be stored in the shallow aquifers and (ii) its travel time to reach the river. (Résumé d'auteur)

The aim of this study was to identify primary flow paths involved in the chlordecone (CLD) river contamination and quantify the CLD fluxes to assess CLD pollution levels and duration according to a typical catchment of the banana cropping area in the French Indies (Guadeloupe): the Perou Catchment (12 km(2)) characterized by heavy rainfall (5686 mm year(-1)). Three sub-catchments (SC1, SC2 and SC3) were studied during the hydrological year 2009-2010: a pedological survey combined with a spatialized hydrochemical approach was conducted. The average soil concentration is higher in the Perou Catchment (3400 mu g kg(-1)) than in the entire banana cropping area in Guadeloupe (2100 mu g kg(-1)). The results showed that CLD stocks in soils vary largely among soil types and farming systems: the weakest stocks are located upstream in SC1 (5 kg ha(-1)), where a majority of the area is non-cultivated; medium stocks are located in Nitisols downstream in SC3 (9 kg ha(-1)); and the greatest stocks are observed in SC2 on Andosols (12 kg ha(-1)) characterized by large farms. The annual water balance and the hydro-chemical analysis revealed that the three sub-catchments exhibited different behaviors. Perou River contamination was high during low flows, which highlighted that contamination primarily originated from groundwater contributions. The results showed that only a small part of the catchment (SC2), contributing little to the water flow, comprises a major CLD contribution, which is in agreement with the highly contaminated andosol soils observed there. Another significant result considers that at least 50 years would be required to export the totality of the actual CLD soil stocks retained in the topsoil layer. The actual time for soil remediation will however be much longer considering (i) the necessary time for the chlordecone to percolate and be stored in the shallow aquifers and (ii) its travel time to reach the river.rights reserved.

When field pollution is heterogeneous due to localized pesticide application, as is the case of chlordecone (CLD), the mean level of pollution is difficult to assess. Our objective was to design a decision support tool to optimize soil sampling. We analyzed the CLD heterogeneity of soil content at 0-30- and 30-60-cm depth. This was done within and between nine plots (0.4 to 1.8 ha) on andosol and ferralsol. We determined that 20 pooled subsamples per plot were a satisfactory compromise with respect to both cost and accuracy. Globally, CLD content was greater for andosols and the upper soil horizon (0-30 cm). Soil organic carbon cannot account for CLD intra-field variability. Cropping systems and tillage practices influence the CLD content and distribution; that is CLD pollution was higher under intensive banana cropping systems and, while upper soil horizon was more polluted than the lower one with shallow tillage (<40 cm), deeper tillage led to a homogenization and a dilution of the pollution in the soil profile. The decision tool we proposed compiles and organizes these results to better assess CLD soil pollution in terms of sampling depth, distance, and unit at field scale. It accounts for sampling objectives, farming practices (cropping system, tillage), type of soil, and topographical characteristics (slope) to design a relevant sampling plan. This decision support tool is also adaptable to other types of heterogeneous agricultural pollution at field level. (Résumé d'auteur)

The online version of this article (doi:10.1007/s11356-013-2095-x) contains supplementary material, which is available to authorized users. | International audience | When field pollution is heterogeneous due to localized pesticide application, as is the case of chlordecone (CLD), the mean level of pollution is difficult to assess. Our objective was to design a decision support tool to optimize soil sampling. We analyzed the CLD heterogeneity of soil content at 0-30- and 30-60-cm depth. This was done within and between nine plots (0.4 to 1.8 ha) on andosol and ferralsol. We determined that 20 pooled subsamples per plot were a satisfactory compromise with respect to both cost and accuracy. Globally, CLD content was greater for andosols and the upper soil horizon (0-30 cm). Soil organic carbon cannot account for CLD intra-field variability. Cropping systems and tillage practices influence the CLD content and distribution; that is CLD pollution was higher under intensive banana cropping systems and, while upper soil horizon was more polluted than the lower one with shallow tillage (< 40 cm), deeper tillage led to a homogenization and a dilution of the pollution in the soil profile. The decision tool we proposed compiles and organizes these results to better assess CLD soil pollution in terms of sampling depth, distance, and unit at field scale. It accounts for sampling objectives, farming practices (cropping system, tillage), type of soil, and topographical characteristics (slope) to design a relevant sampling plan. This decision support tool is also adaptable to other types of heterogeneous agricultural pollution at field level.

When field pollution is heterogeneous due to localized pesticide application, as is the case of chlordecone (CLD), the mean level of pollution is difficult to assess. Our objective was to design a decision support tool to optimize soil sampling. We analyzed the CLD heterogeneity of soil content at 0–30- and 30–60-cm depth. This was done within and between nine plots (0.4 to 1.8 ha) on andosol and ferralsol. We determined that 20 pooled subsamples per plot were a satisfactory compromise with respect to both cost and accuracy. Globally, CLD content was greater for andosols and the upper soil horizon (0–30 cm). Soil organic carbon cannot account for CLD intra-field variability. Cropping systems and tillage practices influence the CLD content and distribution; that is CLD pollution was higher under intensive banana cropping systems and, while upper soil horizon was more polluted than the lower one with shallow tillage (<40 cm), deeper tillage led to a homogenization and a dilution of the pollution in the soil profile. The decision tool we proposed compiles and organizes these results to better assess CLD soil pollution in terms of sampling depth, distance, and unit at field scale. It accounts for sampling objectives, farming practices (cropping system, tillage), type of soil, and topographical characteristics (slope) to design a relevant sampling plan. This decision support tool is also adaptable to other types of heterogeneous agricultural pollution at field level.

Insecticidal Cry, or Bt, proteins are produced by the soil-endemic bacterium, Bacillus thuringiensis and some genetically modified crops. Their environmental fate depends on interactions with soil. Little is known about the toxicity of adsorbed proteins and the change in toxicity over time. We incubated Cry1Ac and Cry2A in contrasting soils subjected to different treatments to inhibit microbial activity. The toxin was chemically extracted and immunoassayed. Manduca sexta was the target insect for biotests. Extractable toxin decreased during incubation for up to four weeks. Toxicity of Cry1Ac was maintained in the adsorbed state, but lost after 2 weeks incubation at 25 °C. The decline in extractable protein and toxicity were much slower at 4 °C with no significant effect of soil sterilization. The major driving force for decline may be time-dependent fixation of adsorbed protein, leading to a decrease in the extraction yield in vitro, paralleled by decreasing solubilisation in the larval gut. (Résumé d'auteur)

Insecticidal Cry, or Bt, proteins are produced by the soil-endemic bacterium, Bacillus thuringiensis and some genetically modified crops. Their environmental fate depends on interactions with soil. Little is known about the toxicity of adsorbed proteins and the change in toxicity over time. We incubated Cry1Ac and Cry2A in contrasting soils subjected to different treatments to inhibit microbial activity. The toxin was chemically extracted and immunoassayed. Manduca sexta was the target insect for biotests. Extractable toxin decreased during incubation for up to four weeks. Toxicity of Cry1Ac was maintained in the adsorbed state, but lost after 2 weeks incubation at 25 °C. The decline in extractable protein and toxicity were much slower at 4 °C with no significant effect of soil sterilization. The major driving force for decline may be time-dependent fixation of adsorbed protein, leading to a decrease in the extraction yield in vitro, paralleled by decreasing solubilisation in the larval gut.

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)

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.

This study aimed at determining the fate of trace elements (TE) following soil organic waste (OW) application. We used a unique combination of X-ray absorption spectroscopy analyses, to determine TE speciation, with incubation experiments for in situ monitoring of TE availability patterns over a time course with the technique of the diffusive gradients in thin films (DGT). We showed that copper (Cu) and zinc (Zn) availability were both increased in OW-amended soil, but their release was controlled by distinct mechanisms. Zn speciation in OW was found to be dominated by an inorganic species, i.e. Zn sorbed on Fe oxides. Zn desorption from Fe oxides could explain the increase in Zn availability in OW-amended soil. Cu speciation in OW was dominated by organic species. Cu release through the mineralization of organic carbon from OW was responsible for the increase in Cu availability. (Résumé d'auteur)

International audience | This study aimed at determining the fate of trace elements (TE) following soil organic waste (OW) application. We used a unique combination of X-ray absorption spectroscopy analyses, to determine TE speciation, with incubation experiments for in situ monitoring of TE availability patterns over a time course with the technique of the diffusive gradients in thin films (DGT). We showed that copper (Cu) and zinc (Zn) availability were both increased in OW-amended soil, but their release was controlled by distinct mechanisms. Zn speciation in OW was found to be dominated by an inorganic species, i.e. Zn sorbed on Fe oxides. Zn desorption from Fe oxides could explain the increase in Zn availability in OW amended soil. Cu speciation in OW was dominated by organic species. Cu release through the mineralization of organic carbon from OW was responsible for the increase in Cu availability. (C) 2016 Elsevier Ltd. All rights reserved.

This study aimed at determining the fate of trace elements (TE) following soil organic waste (OW) application. We used a unique combination of X-ray absorption spectroscopy analyses, to determine TE speciation, with incubation experiments for in situ monitoring of TE availability patterns over a time course with the technique of the diffusive gradients in thin films (DGT). We showed that copper (Cu) and zinc (Zn) availability were both increased in OW-amended soil, but their release was controlled by distinct mechanisms. Zn speciation in OW was found to be dominated by an inorganic species, i.e. Zn sorbed on Fe oxides. Zn desorption from Fe oxides could explain the increase in Zn availability in OW-amended soil. Cu speciation in OW was dominated by organic species. Cu release through the mineralization of organic carbon from OW was responsible for the increase in Cu availability.

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-?m diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments. (Résumé d'auteur)

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.

International audience | Abstract Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and \XAS\ analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and \XAS\ observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.