Sediments from an arsenic（As） contaminated groundwater vent site were used to investigate As（ Ⅲ） binding, transformation and redistribution in native and iron oxide amended lake sediments using aging spiked batch...Sediments from an arsenic（As） contaminated groundwater vent site were used to investigate As（ Ⅲ） binding, transformation and redistribution in native and iron oxide amended lake sediments using aging spiked batch reactions and a sequential extraction procedure that maintains As（V） and As（ Ⅲ） speciation. In the native sediments, fractionation analysis revealed that 10% of the spiked As（ Ⅲ） remained intact after a 32-day aging experiment and was predominantly adsorbed to the strongly sorbed（NH4H2PO4 extractable） and amorphous Fe oxide bound（H3PO4 extractable） fractions. Kinetic modelling of the experimental results allowed identifying the dominant reaction path for depletion of dissolved As（ Ⅲ） to As（ Ⅲ）absorbed on to the solid phase, followed by oxidation in the solid phase. Arsenite was initially adsorbed primarily to the easily exchangeable fraction（（NH4）2SO4 extractable）, then rapidly transformed into As（V） and redistributed to the strongly sorbed and amorphous Fe oxide bound fractions. Oxidation of As（ Ⅲ） in recalcitrant fractions was less efficient. The iron oxide amendments illustrated the controls that iron oxides can have on As（ Ⅲ） binding and transformation rates. In goethite amended samples As（ Ⅲ） oxidation was faster and primarily occurred in the strongly sorbed and amorphous Fe oxide bound fractions. In these samples,19.3 μg Mn was redistributed（compared to the native sediment） from the easily exchangeable and crystalline Fe oxide bound fractions to the strongly sorbed and amorphous Fe oxide bound fractions, indicating that goethite may act as a catalyst for Mn（Ⅱ） oxidation, thereby producing sorbed Mn（ Ⅲ/Ⅳ ）, which then appears to be involved in rapidly oxidizing As（ Ⅲ）.展开更多
Asymmetric flow-field flow fractionation-inductively-coupled plasma-mass spectrometry was used to determine whether colloidal arsenic（As） exists in soil pore water and soil extract samples at two arsenic-contaminate...Asymmetric flow-field flow fractionation-inductively-coupled plasma-mass spectrometry was used to determine whether colloidal arsenic（As） exists in soil pore water and soil extract samples at two arsenic-contaminated abandoned gold mines（Montague and Goldenville, Nova Scotia）. Colloidal arsenic was found in 12 out of the 80 collected samples（= 15%）, and was primarily associated with iron（Fe） in the encountered colloids. The molar Fe/As ratios indicate that the colloids in some samples appeared to be discrete iron–arsenic minerals, whereas in other samples, they were more consistent with As-rich iron（oxy）hydroxides. Up to three discrete size fractions of colloidal As were encountered in the samples, with mean colloid diameters between 6 and 14 nm. The pore water samples only contained one size fraction of As-bearing colloids（around 6 nm diameter）, while larger As-bearing colloids were only encountered in soil extracts.展开更多
A freshwater microalga, Chlorella vulgaris, was grown in the presence of varying phosphate concentrations（〈 10–500 μg/L P） and environmentally realistic concentrations of arsenate（As（Ⅴ））（5–50 μg/L As）. A...A freshwater microalga, Chlorella vulgaris, was grown in the presence of varying phosphate concentrations（〈 10–500 μg/L P） and environmentally realistic concentrations of arsenate（As（Ⅴ））（5–50 μg/L As）. Arsenic speciation in the culture medium and total cellular arsenic were measured using AEC-ICP-MS and ICP-DRC-MS, respectively, to determine arsenic biotransformation and uptake in the various phosphorus scenarios. At high phosphate concentration in the culture medium, 〉 100 μg/L P, the uptake and biotransformation of As（Ⅴ） was minimal and dimethylarsonate（DMAs（Ⅴ）） was the dominant metabolite excreted by C. vulgaris, albeit at relatively low concentrations. At common environmental P concentrations, 0–50 μg/L P, the uptake and biotransformation of As（Ⅴ） increased. At these higher As-uptake levels, arsenite（As（Ⅲ）） was the predominant metabolite excreted from the cell. The concentrations of As（Ⅲ） in these low P conditions were much higher than the concentrations of methylated arsenicals observed at the various P concentrations studied. The switchover threshold between the（small） methylation and（large） reduction of As（Ⅴ） occurred around a cellular As concentration of 1 fg/cell. The observed nearly quantitative conversion of As（Ⅴ） to As（Ⅲ） under low phosphate conditions indicates the importance of As（Ⅴ） bio-reduction at common freshwater P concentrations. These findings on the influence of phosphorus on arsenic uptake, accumulation and excretion are discussed in relation to previously published research. The impact that the two scenarios of As（Ⅴ） metabolism, As（Ⅲ） excretion at high As（Ⅴ）-uptake and methylarsenical excretion at low As（Ⅴ）-uptake, have on freshwater arsenic speciation is discussed.展开更多
文摘Sediments from an arsenic（As） contaminated groundwater vent site were used to investigate As（ Ⅲ） binding, transformation and redistribution in native and iron oxide amended lake sediments using aging spiked batch reactions and a sequential extraction procedure that maintains As（V） and As（ Ⅲ） speciation. In the native sediments, fractionation analysis revealed that 10% of the spiked As（ Ⅲ） remained intact after a 32-day aging experiment and was predominantly adsorbed to the strongly sorbed（NH4H2PO4 extractable） and amorphous Fe oxide bound（H3PO4 extractable） fractions. Kinetic modelling of the experimental results allowed identifying the dominant reaction path for depletion of dissolved As（ Ⅲ） to As（ Ⅲ）absorbed on to the solid phase, followed by oxidation in the solid phase. Arsenite was initially adsorbed primarily to the easily exchangeable fraction（（NH4）2SO4 extractable）, then rapidly transformed into As（V） and redistributed to the strongly sorbed and amorphous Fe oxide bound fractions. Oxidation of As（ Ⅲ） in recalcitrant fractions was less efficient. The iron oxide amendments illustrated the controls that iron oxides can have on As（ Ⅲ） binding and transformation rates. In goethite amended samples As（ Ⅲ） oxidation was faster and primarily occurred in the strongly sorbed and amorphous Fe oxide bound fractions. In these samples,19.3 μg Mn was redistributed（compared to the native sediment） from the easily exchangeable and crystalline Fe oxide bound fractions to the strongly sorbed and amorphous Fe oxide bound fractions, indicating that goethite may act as a catalyst for Mn（Ⅱ） oxidation, thereby producing sorbed Mn（ Ⅲ/Ⅳ ）, which then appears to be involved in rapidly oxidizing As（ Ⅲ）.
基金NSERC for providing funding through the Strategic Grants Program
文摘Asymmetric flow-field flow fractionation-inductively-coupled plasma-mass spectrometry was used to determine whether colloidal arsenic（As） exists in soil pore water and soil extract samples at two arsenic-contaminated abandoned gold mines（Montague and Goldenville, Nova Scotia）. Colloidal arsenic was found in 12 out of the 80 collected samples（= 15%）, and was primarily associated with iron（Fe） in the encountered colloids. The molar Fe/As ratios indicate that the colloids in some samples appeared to be discrete iron–arsenic minerals, whereas in other samples, they were more consistent with As-rich iron（oxy）hydroxides. Up to three discrete size fractions of colloidal As were encountered in the samples, with mean colloid diameters between 6 and 14 nm. The pore water samples only contained one size fraction of As-bearing colloids（around 6 nm diameter）, while larger As-bearing colloids were only encountered in soil extracts.
基金provided by the Ontario Ministry of the Environment's ‘Best in Science’ program
文摘A freshwater microalga, Chlorella vulgaris, was grown in the presence of varying phosphate concentrations（〈 10–500 μg/L P） and environmentally realistic concentrations of arsenate（As（Ⅴ））（5–50 μg/L As）. Arsenic speciation in the culture medium and total cellular arsenic were measured using AEC-ICP-MS and ICP-DRC-MS, respectively, to determine arsenic biotransformation and uptake in the various phosphorus scenarios. At high phosphate concentration in the culture medium, 〉 100 μg/L P, the uptake and biotransformation of As（Ⅴ） was minimal and dimethylarsonate（DMAs（Ⅴ）） was the dominant metabolite excreted by C. vulgaris, albeit at relatively low concentrations. At common environmental P concentrations, 0–50 μg/L P, the uptake and biotransformation of As（Ⅴ） increased. At these higher As-uptake levels, arsenite（As（Ⅲ）） was the predominant metabolite excreted from the cell. The concentrations of As（Ⅲ） in these low P conditions were much higher than the concentrations of methylated arsenicals observed at the various P concentrations studied. The switchover threshold between the（small） methylation and（large） reduction of As（Ⅴ） occurred around a cellular As concentration of 1 fg/cell. The observed nearly quantitative conversion of As（Ⅴ） to As（Ⅲ） under low phosphate conditions indicates the importance of As（Ⅴ） bio-reduction at common freshwater P concentrations. These findings on the influence of phosphorus on arsenic uptake, accumulation and excretion are discussed in relation to previously published research. The impact that the two scenarios of As（Ⅴ） metabolism, As（Ⅲ） excretion at high As（Ⅴ）-uptake and methylarsenical excretion at low As（Ⅴ）-uptake, have on freshwater arsenic speciation is discussed.
