International audience | Introduction: The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium. Methods: The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH 3. 0 were determined by the competitive kinetics method. Results and discussion: The hydroxylation absolute rate constant (kabs) values of both TRK herbicides ranged from 8. 20 × 108 (sulcotrione) to 1. 01 × 109 (mesotrione) L mol-1 s-1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione, (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5. 90 × 108 and 3. 29 × 109 L mol-1 s-1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97-98% were reached in optimal conditions for a 6-h electro-Fenton treatment time. Conclusions: The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.

INTRODUCTION: The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium. METHODS: The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH 3.0 were determined by the competitive kinetics method. RESULTS AND DISCUSSION: The hydroxylation absolute rate constant (k abs) values of both TRK herbicides ranged from 8.20 × 108 (sulcotrione) to 1.01 × 109 (mesotrione) L mol−1 s−1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione , (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90 × 108 and 3.29 × 109 L mol−1 s−1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97–98% were reached in optimal conditions for a 6-h electro-Fenton treatment time. CONCLUSIONS: The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.

International audience | * Introduction : Acidic and metal(oid)-rich topsoils resulted after 34 years of continuous operations of a copper smelter in the Puchuncaví valley, central Chile. Currently, large-scale remediation actions for simultaneous in situ immobilization of metals and As are needed to reduce environmental risks of polluted soils. Aided phytostabilization is a cost-effective alternative, but adequate local available soil amendments have to be identified and management options have to be defined. * Materials and methods : Efficacy of seashell grit (SG), biosolids (B), natural zeolite (Z), and iron-activated zeolite (AZ), either alone or in mixtures, was evaluated for reducing metal (Cu and Zn) and As solubilization in polluted soils under laboratory conditions. Perennial ryegrass was used to test phytotoxicity of experimental substrates. * Results : Soil neutralization to a pH of 6.5 with SG, with or without incorporation of AZ, significantly reduces metal (Cu and Zn) solubilization without affecting As solubilization in soil pore water; furthermore, it eliminates phytotoxicity and excessive metal(oid) accumulation in aerial plant tissues. Addition of B or Z to SG-amended soil does not further reduce metal solubilization into soil pore water, but increase As solubilization due to excessive soil neutralization (pH > 6.5); however, no significant As increase occurs in aerial plant tissues. * Conclusion : Simultaneous in situ immobilization of metal(oid) in acidic topsoils is possible through aided phytostabilization.

INTRODUCTION: Acidic and metal(oid)-rich topsoils resulted after 34 years of continuous operations of a copper smelter in the Puchuncaví valley, central Chile. Currently, large-scale remediation actions for simultaneous in situ immobilization of metals and As are needed to reduce environmental risks of polluted soils. Aided phytostabilization is a cost-effective alternative, but adequate local available soil amendments have to be identified and management options have to be defined. MATERIALS AND METHODS: Efficacy of seashell grit (SG), biosolids (B), natural zeolite (Z), and iron-activated zeolite (AZ), either alone or in mixtures, was evaluated for reducing metal (Cu and Zn) and As solubilization in polluted soils under laboratory conditions. Perennial ryegrass was used to test phytotoxicity of experimental substrates. RESULTS: Soil neutralization to a pH of 6.5 with SG, with or without incorporation of AZ, significantly reduces metal (Cu and Zn) solubilization without affecting As solubilization in soil pore water; furthermore, it eliminates phytotoxicity and excessive metal(oid) accumulation in aerial plant tissues. Addition of B or Z to SG-amended soil does not further reduce metal solubilization into soil pore water, but increase As solubilization due to excessive soil neutralization (pH > 6.5); however, no significant As increase occurs in aerial plant tissues. CONCLUSION: Simultaneous in situ immobilization of metal(oid) in acidic topsoils is possible through aided phytostabilization.

Chantier qualité GA | International audience | Introduction: High concentrations of hexabromocyclododecane (HBCD) sometimes recorded in free-range hens' eggs are thought to be due to soil ingestion. Of the three stereoisomers of HBCD (α-, β-, and γ-HBCD), γ-HBCD is the main component in the commercial mixture, as well as in environmental matrices, whereas the isomer profile is α-dominated in biota. In fish and in mammals, this shift is thought to be due to a rapid elimination of γ-HBCD and to its bioisomerization to the more persistent α-HBCD. The aim of the current controlled study was to better understand the fate of ingested HBCD in laying hens. The isomer profile in soil being γ-dominated, excretion kinetics of γ-HBCD into egg yolk, and accumulation in liver and in abdominal fat were investigated. Materials and methods: Forty-eight laying hens were individually housed and fed with a spiked diet containing 1.1-ng γ-HBCD per gram for 21 days and with a clean diet for the following 18 days. Hens were sequentially slaughtered throughout the 39-day experiment. α-, β-, and γ-HBCD were analyzed in egg yolk, in abdominal fat, and in liver by LC-MS/MS. α- and γ-HBCD were quantified in the three tissues, while β-HBCD was never quantified. Results and conclusion: Kinetics of the two isomers suggests that γ-HBCD is rapidly biotransformed and eliminated, and partly isomerized into the more persistent α-HBCD. Carry-over rate of ingested γ-HBCD to egg yolk was estimated at 1.2%. Estimated half-lives of γ-HBCD in egg yolk, in abdominal fat, and in liver were 2.9, 13, and 0.41 days, respectively.

INTRODUCTION: High concentrations of hexabromocyclododecane (HBCD) sometimes recorded in free-range hens' eggs are thought to be due to soil ingestion. Of the three stereoisomers of HBCD (α-, β-, and γ-HBCD), γ-HBCD is the main component in the commercial mixture, as well as in environmental matrices, whereas the isomer profile is α-dominated in biota. In fish and in mammals, this shift is thought to be due to a rapid elimination of γ-HBCD and to its bioisomerization to the more persistent α-HBCD. The aim of the current controlled study was to better understand the fate of ingested HBCD in laying hens. The isomer profile in soil being γ-dominated, excretion kinetics of γ-HBCD into egg yolk, and accumulation in liver and in abdominal fat were investigated. MATERIALS AND METHODS: Forty-eight laying hens were individually housed and fed with a spiked diet containing 1.1-ng γ-HBCD per gram for 21 days and with a clean diet for the following 18 days. Hens were sequentially slaughtered throughout the 39-day experiment. α-, β-, and γ-HBCD were analyzed in egg yolk, in abdominal fat, and in liver by LC-MS/MS. α- and γ-HBCD were quantified in the three tissues, while β-HBCD was never quantified. RESULTS AND CONCLUSION: Kinetics of the two isomers suggests that γ-HBCD is rapidly biotransformed and eliminated, and partly isomerized into the more persistent α-HBCD. Carry-over rate of ingested γ-HBCD to egg yolk was estimated at 1.2%. Estimated half-lives of γ-HBCD in egg yolk, in abdominal fat, and in liver were 2.9, 13, and 0.41 days, respectively.