Search

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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 276 days. 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 0.3–1.6 mM and 20–110 μM ranges. After 8 months of experiment, about 83 g·m − 3 of Zn and 3.5 g·m − 3 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. [ABSTRACT FROM AUTHOR]

Thermal destruction of chemical munitions from World War I led to the formation of a heavily contaminated residue that contains an unexpected mineral association in which a microbial As transformation has been observed. A mesocosm study was conducted to assess the impact of water saturation episodes and input of bioavailable organic matter (OM) on pollutant behavior in relation to biogeochemical parameters. Over a period of about eight (8) months, the contaminated soil was subjected to cycles of dry and wet periods corresponding to water table level variations. After the first four (4) months, fragmented litter from the nearby forest was placed on top of the soil. The mesocosm solid phase was sampled by three rounds of coring: at the beginning of the experiment, after four (4) months (before the addition of OM), and at the end of the experiment. Scanning electron microscopy coupled to energy dispersive X-ray spectroscopy observations showed that an amorphous phase, which was the primary carrier of As, Zn, and Cu, was unstable under water-saturated conditions and released a portion of the contaminants in solution. Precipitation of a lead arsenate chloride mineral, mimetite, in soils within the water saturated level caused the immobilization of As and Pb. Mimetite is a durable trap because of its large stability domain; however, this precipitation was limited by a low Pb concentration inducing that high amounts of As remained in solution. The addition of forest litter modified the quantities and qualities of soil OM. Microbial As transformation was affected by the addition of OM, which increased the concentration of both As(III)-oxidizing and As(V)-reducing microorganisms. The addition of OM negatively impacted the As(III) oxidizing rate, however As(III) oxidation was still the dominant reaction in accordance with the formation of arsenate-bearing minerals. [ABSTRACT FROM AUTHOR]

Mine tailings are major sources of metals and metalloids in the environment, making the physical and geochemical stabilization of tailings a serious environmental challenge. With a view to facilitate the development of covering vegetation and of decreasing the mobility of Pb in the acid tailings of a former Ag–Pb mine, laboratory microcosm experiments were performed to enable comparison of the effectiveness of several treatments. Tailings were mixed with 5% by weight of ochre, an iron-rich material produced during the treatment of a coal mine water, and with cow manure (0, 0.15, 1 and 2% by weight), either solely or in combination. They were then submitted to weekly watering over 84 days. All treatments raised the pH values from 4 to values between 7 and 8 and induced a strong decrease in the total dissolved Pb concentration in the percolating water (from 13 to 15 mg.L−1 to less than 0.5 mg.L−1). Several processes seemed to be involved in the immobilization of Pb by the amendments: precipitation as hydroxide, sulfate, carbonate and phosphate, and adsorption on iron hydroxides. A transient increase was observed in both Pb mobility and functional microbial diversity with 1% and 2% manure, with a peak after 28 days of incubation. This peak corresponded to an Average Well Color Development (AWCD) in Biolog™ Ecoplates increase from 0.5 to 0.8 with 1% manure and from 0.6 to 1.5 with 2% manure. However, at the end of experiment, Pb immobilization was strengthened by 2% manure and microbial functional biodiversity fell back, with AWCD values of 0.5 and 0.8 for 1% and 2% manure, respectively. Other toxic elements present in the tailings, namely As, Zn and Ba, were not strongly mobilized by the treatments, although cow manure slightly increased the leaching of Ba and As, which maximum concentrations in the leaching water reached 65 μg.L−1 Ba and 9 μg.L−1 As. All amendments improved the growth of ryegrass, which maximum dry biomass ranged from 38 mg/microcosm without amendment to 155 mg/microcosm with 0.15% manure. The results provide key information about the biogeochemical processes driving the mobility of Pb, As, Zn and Ba in acid mine tailings during the first 84 days following their amendment with iron-rich ochre and manure. • Ochre from coal mine water treatment increases pH of acid tailings. • Pb is stabilized and As is not mobilized in tailings by ochre and manure amendment. • Manure induces mobilization of Pb for 35 days then its stabilization. • Microbial functional biodiversity is transiently increased by amendment. • Ochre favors short-term growth of ray-grass on tailings. [ABSTRACT FROM AUTHOR]