Temporal evolution of surface and sub-surface geochemistry and microbial communities of Pb-rich mine tailings during phytostabilization: A one-year pilot-scale study.

Old mine waste repositories can present health and/or environmental issues linked to their erosion, inducing dissemination of metals and metalloids in air and water that can be attenuated through phytostabilization. Here, the effect of this widespread phytomanagement option on the biogeochemistry of a Pb-rich mine waste was evaluated with a laboratory pilot-scale experiment giving access to the non-saturated and saturated zones below the rhizosphere compartment. Amendment of the tailings surface with biochar, manure and iron-oxide-rich ochre promoted growth of the seeded Agrostis capillaris plants. These events were accompanied by an increase of pH and a decrease of Pb concentration in pore water of the surface layer, and by a transient increase of Pb, Zn, and Ba concentrations in the deeper saturated levels. Macroscopic and microscopic observations (SEM) suggest that Pb was immobilized in A. capillaris rhizosphere through mechanical entrapment of tailing particles. Microbial taxonomic and metabolic diversities increased in the amended phytostabilized surface levels, with a rise of the proportion of heterotrophic micro-organisms. Below the surface, a transient modification of microbial communities was observed in the non-saturated and saturated levels, however 11 months after seeding, the prokaryotic community of the deepest saturated zone was close to that of the initial tailings. pH and water saturation seemed to be the main parameters driving prokaryotic communities' structures. Results obtained at pilot-scale will help to precisely evaluate the impacts of phytostabilization on the temporal evolution of reactions driving the fate of pollutants inside the tailings dumps.

Mobility of Pb, Zn, Ba, As and Cd toward soil pore water and plants (willow and ryegrass) from a mine soil amended with biochar.

Mine soils often contain metal(loid)s that may lead to serious environmental problems. Phytoremediation, consisting in covering the soil with specific plants with the possible addition of amendments, represents an interesting way of enhancing the quality of mine soils by retaining contaminants and reducing soil erosion. In order to study the effect of an assisted phytoremediation (with willow and ryegrass) on the properties of soil pore water (SPW), we investigated the impact of amendment with biochar (BC) combined with the planting of willow and ryegrass on the behavior of several metal(loid)s (Pb, Zn, Ba, As, and Cd) in a mine soil. Data on the physicochemical parameters and concentrations of the different metal(loid)s in both SPW and in plant tissues of willow and ryegrass highlight the importance of BC for SPW properties in terms of reductions in soluble concentrations of Pb and Zn, although there was no effect on the behavior of As and Cd. BC also increased soluble concentrations of Ba, probably related to ion release by the BC. By improving major ions available in mine soil, BC improved the lifetime of plants and enhanced their growth. Plant development did not appear to significantly affect the physicochemical parameters of SPW. Willow and ryegrass growing on soil with BC incorporated Cd and Ba into their tissues. The influence of plants on the behavior of metal(loid)s was noticeable only for ryegrass growing in soil with 2% BC, where it modified the behavior of Pb and Ba.

Evaluation of antimony availability in a mining context: Impact for the environment, and for mineral exploration and exploitation.

This work aims to establish Sb mobility, its transfer to biota and its effect on soil health in a semi-arid climate. The results show the presence of stibnite (Sb2S3) as the main primary Sb compound, bindhemite (Pb2Sb2O6(O,OH)), and minor proportions of stibiconite (Sb3+(Sb5+)2O6(OH)) as oxidised Sb species. This research also observes very high total Sb contents in mining materials (max: 20,000 mg kg-1) and soils (400-3000 mg kg-1), with physical dispersion around mining materials restricted to 450 m. The soil-to-plant transfer is very low, (bioaccumulation factor: 0.0002-0.1520). Most Sb remains in a residual fraction (99.9%), a very low fraction is bound to Fe and Mn oxy-hydroxides or organic matter, and a negligible proportion of Sb is leachable. The higher Sb mobility rates has been found under oxidising conditions with a long contact time between solids and water. The main factors that explain the poor Sb mobility and dispersion in the mining area are the low annual rainfall rates that slow down the Sb mobilisation process and the scarce formation of oxidised Sb compounds. All these data suggest poor Sb (III) formation and a low toxicological risk in the area associated with past mining activities. The low mobility of Sb suggests advantages for future sustainable mining of such ore deposits in a semi-arid climate and is also indicative of the limitations of geochemical exploration in the search for new Sb deposits.

Mobility of antimony in contrasting surface environments of a mine site: influence of redox conditions and microbial communities.

Microbial processes can influence the complex geochemical behaviour of the toxic metalloid antimony (Sb) in mining environments. The present study is aimed to evaluate the influence of microbial communities on the mobility of Sb from solid phases to water in different compartments and redox conditions of a mining site in southwest (SW) Spain. Samples of surface materials presenting high Sb concentrations, from two weathered mining waste dumps, and an aquatic sediment were incubated in slurries comparing oxic and anoxic conditions. The initial microbial communities of the three materials strongly differed. Incubations induced an increase of microbial biomass and an evolution of the microbial communities' structures and compositions, which diverged in different redox conditions. The presence of active bacteria always influenced the mobility of Sb, except in the neutral pH waste incubated in oxic conditions. The effect of active microbial activities in oxic conditions was dependent on the material: Sb oxic release was biologically amplified with the acidic waste, but attenuated with the sediment. Different bacterial genera involved in Sb, Fe and S oxidation or reduction were present and/or grew during incubation of each material. The results highlighted the wide diversity of microbial communities and metabolisms at the small geographic scale of a mining site and their strong implication in Sb mobility.

Biogeochemical behaviour of geogenic As in a confined aquifer of the Sologne region, France.

Arsenic (As) is one of the main toxic elements of geogenic origin that impact groundwater quality and human health worldwide. In some groundwater wells of the Sologne region (Val de Loire, France), drilled in a confined aquifer, As concentrations exceed the European drinking water standard (10 µg L-1). The monitoring of one of these drinking water wells showed As concentrations in the range 20-25 µg L-1. The presence of dissolved iron (Fe), low oxygen concentration and traces of ammonium indicated reducing conditions. The δ34SSO4 was anticorrelated with sulphate concentration. Drilling allowed to collect detrital material corresponding to a Miocene floodplain and crevasse splay with preserved plant debris. The level that contained the highest total As concentration was a silty-sandy clay containing 26.9 mg kg-1 As. The influence of alternating redox conditions on the behaviour of As was studied by incubating this material with site groundwater, in biotic or inhibited bacterial activities conditions, without synthetic organic nutrient supply, in presence of H2 during the reducing periods. The development of both AsV-reducing and AsIII-oxidising microorganisms in biotic conditions was evidenced. At the end of the reducing periods, total As concentration strongly increased in biotic conditions. The microflora influenced As speciation, released Fe and consumed nitrate and sulphate in the water phase. Microbial communities observed in groundwater samples strongly differed from those obtained at the end of the incubation experiment, this result being potentially related to influence of the sediment compartment and to different physico-chemical conditions. However, both included major Operating Taxonomic Units (OTU) potentially involved in Fe and S biogeocycles. Methanogens emerged in the incubated sediment presenting the highest solubilised As and Fe. Results support the hypothesis of in-situ As mobilisation and speciation mediated by active biogeochemical processes.

Influence of agricultural amendments on arsenic biogeochemistry and phytotoxicity in a soil polluted by the destruction of arsenic-containing shells.

Agricultural soils can contain high arsenic (As) concentrations due to specific geological contexts or pollution. Fertilizer amendments could influence As speciation and mobility thus increasing its transfer to crops and its toxicity. In the present study, field-relevant amounts of fertilizers were applied to soils from a cultivated field that was a former ammunition-burning site. Potassium phosphate (KP), ammonium sulfate and organic matter (OM) were applied to these soils in laboratory experiments to assess their impact on As leaching, bioavailability to Lactuca sativa and microbial parameters. None of the fertilizers markedly influenced As speciation and mobility, although trends showed an increase of mobility with KP and a decrease of mobility with ammonium sulfate. Moreover, KP induced a small increase of As in Lactuca sativa, and the polluted soil amended with ammonium sulfate was significantly less phytotoxic than the un-amended soil. Most probable numbers of AsIII-oxidizing microbes and AsIII-oxidizing activity were strongly linked to As levels in water and soils. Ammonium sulfate negatively affected AsIII-oxidizing activity in the un-polluted soil. Whereas no significant effect on As speciation in water could be detected, amendments may have an impact in the long term.

Microbial community response to environmental changes in a technosol historically contaminated by the burning of chemical ammunitions.

The burning of chemical weapons in the 1926-1928 period produced polluted technosols with elevated levels of arsenic, zinc, lead and copper. During an eight-month mesocosm experiment, these soils were submitted to two controlled environmental changes, namely the alternation of dry and water-saturated conditions and the addition of fragmented organic forest litter to the surface soil. We investigated, by sequencing the gene coding 16S rRNA and 18S rRNA, (1) the structure of the prokaryotic and eukaryotic community in this polluted technosol and (2) their response to the simulated environmental changes, in the four distinct layers of the mesocosm. In spite of the high concentrations of toxic elements, microbial diversity was found to be similar to that of non-polluted soils. The bacterial community was dominated by Proteobacteria, Acidobacteria and Bacteroidetes, while the fungal community was dominated by Ascomicota. Amongst the most abundant bacterial Operational Taxonomic Units (OTUs), including Sphingomonas as a major genus, some were common to soil environments in general whereas a few, such as organisms related to Leptospirillum and Acidiferrobacter, seemed to be more specific to the geochemical context. Evolution of the microbial abundance and community structures shed light on modifications induced by water saturation and the addition of forest litter to the soil surface. Co-inertia analysis suggests a relationship between the physico-chemical parameters total organic carbon, Zn, NH4+ and As(III) concentrations and the bacterial community structure. Both these results imply that microbial community dynamics linked to environmental changes should be considered as factors influencing the behavior of toxic elements on former ammunition burning sites.

Influence of environmental changes on the biogeochemistry of arsenic in a soil polluted by the destruction of chemical weapons: A mesocosm study.

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.

Effect of water table variations and input of natural organic matter on the cycles of C and N, and mobility of As, Zn and Cu from a soil impacted by the burning of chemical warfare agents: A mesocosm study.

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-3 of Zn and 3.5g·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.

Characterization and mobility of arsenic and heavy metals in soils polluted by the destruction of arsenic-containing shells from the Great War.

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.