Destruction of chemical munitions from World War I has caused extensive local top soil contamination by arsenic and heavy metals. The biogeochemical behavior of toxic elements is poorly documented in this type of environment. Four soils were sampled presenting different levels of contamination. The range of As concentrations in the samples was 1937-72,820mg/kg. Concentrations of Zn, Cu and Pb reached 90,190mg/kg, 9113mg/kg and 5777mg/kg, respectively. The high clay content of the subsoil and large amounts of charcoal from the use of firewood during the burning process constitute an ample reservoir of metals and As-binding materials. However, SEM-EDS observations showed different forms of association for metals and As. In metal-rich grains, several phases were identified: crystalline phases, where arsenate secondary minerals were detected, and an amorphous phase rich in Fe, Zn, Cu, and As. The secondary arsenate minerals, identified by XRD, were adamite and olivenite (zinc and copper arsenates, respectively) and two pharmacosiderites. The amorphous material was the principal carrier of As and metals in the central part of the site. This singular mineral assemblage probably resulted from the heat treatment of arsenic-containing shells. Microbial characterization included total cell counts, respiration, and determination of As(III)-oxidizing activities. Results showed the presence of microorganisms actively contributing to metabolism of carbon and arsenic, even in the most polluted soil, thereby influencing the fate of bioavailable As on the site. However, the mobility of As correlated mainly with the availability of iron sinks.
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A mesocosm study was conducted to assess the impact of water saturation episodes and of the input of bioavailable organic matter on the biogeochemical cycles of C and N, and on the behavior of metal(loid)s in a soil highly contaminated by the destruction of arsenical shells. An instrumented mesocosm was filled with contaminated soil taken from the "Place-à-Gaz" site. Four cycles of dry and wet periods of about one month were simulated for 276days. After two dry/wet cycles, organic litter sampled on the site was added above the topsoil. The nitrogen cycle was the most impacted by the wet/dry cycles, as evidenced by a denitrification microbial process in the saturated level. The concentrations of the two most mobile pollutants, Zn and As, in the soil water and in the mesocosm leachate were, respectively, in the 0.3-1.6mM and 20-110μM ranges. After 8months of experiment, about 83g·m of Zn and 3.5g·m of As were leached from the soil. These important quantities represent <1% of the solid stock of this contaminant. Dry/wet cycles had no major effect on Zn mobility. However, soil saturation induced the immobilization of As by trapping As V but enhanced As III mobility. These phenomena were amplified by the presence of bioavailable organic matter. The study showed that the natural deposition of forest organic litter allowed a part of the soil's biological function to be restored but did not immobilize all the Zn and As, and even contributed to transport of As III to the surrounding environment. The main hazard of this type of site, contaminated by organo-arsenic chemical weapons, is the constitution of a stock of As that may leach into the surrounding environment for several hundred years.
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