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.

Effects of biochar, ochre and manure amendments associated with a metallicolous ecotype of Agrostis capillaris on As and Pb stabilization of a former mine technosol.

Metal(loid) soil pollution is a major environmental and health issue, requiring these areas to be remediated, for example through phytoremediation processes. In order to allow proper plant establishment and growth, amendments must be applied to highly contaminated and poorly fertile soils. Amendments are diverse, but many studies have shown the beneficial effects of biochar, manure and ochre, although studies on their combined use are scarce. Moreover, no studies have evaluated the effect of these combined amendments on endemic plant growth. Endemic plants growing on contaminated soils showed higher tolerance toward pollutants compared to plants coming from unpolluted areas. Therefore, the aim of the present study was to evaluate both the effect of amendments (single or combined) on the physicochemical properties of a former mining technosol, and the growth and metal(loid) accumulation ability of endemic Agrostis capillaris plants. This study revealed an improvement in the soil physicochemical properties following the application of amendments, with combined amendments showing better results than the application of just one. On top of this, Agrostis plants performed better on the amended technosols, especially the ones receiving manure, due to its high nutrient content. Finally, based on soil properties, plant growth and the metal(loid) accumulation profile, the use of biochar combined with manure seems to be the most appropriate treatment. Indeed, this treatment showed an improvement in both soil fertility and plant growth. Moreover, Agrostis plants grown in these conditions were among those showing higher root metal(loid) concentration associated with a lower translocation toward aerial parts.

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.

Structure and Dynamics of Nonionic Surfactant Aggregates in Layered Materials.

The aggregation of surfactants on solid surfaces as they are adsorbed from solution is the basis of numerous technological applications such as colloidal stabilization, ore flotation, and floor cleaning. The understanding of both the structure and the dynamics of surfactant aggregates applies to the development of alternative ways of preparing hybrid layered materials. For this purpose, we study the adsorption of the triethylene glycol mono n-decyl ether (C10E3) nonionic surfactant onto a synthetic montmorillonite (Mt), an aluminosilicate clay mineral for organoclay preparation with important applications in materials sciences, catalysis, wastewater treatment, or as drug delivery. The aggregation mechanisms follow those observed in an analogous natural Mt, with the condensation of C10E3 in a bilayer arrangement once the surfactant self-assembles in a lamellar phase beyond the critical micelle concentration, underlining the importance of the surfactant state in solution. Solid-state 1H nuclear magnetic resonance (NMR) at fast magic-angle spinning (MAS) and high magnetic field combined with1H-13C correlation experiments and different types of 13C NMR experiments selectively probes mobile or rigid moieties of C10E3 in three different aggregate organizations: (i) a lateral monolayer, (ii) a lateral bilayer, and (iii) a normal bilayer. High-resolution 1H{27Al} CP-1H-1H spin diffusion experiments shed light on the proximities and dynamics of the different fragments and fractions of the intercalated surfactant molecules with respect to the Mt surface. 23Na and 1H NMR measurements combined with complementary NMR data, at both molecular and nanometer scales, precisely pointed out the location of the C10E3 ethylene oxide hydrophilic group in close contact with the Mt surface interacting through ion-dipole or van der Waals interactions.

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.

High temperature behavior of electrostatic precipitator ash from municipal solid waste combustors.

Municipal solid waste (MSW) flue gas residues require further treatment prior to disposal or reuse, and vitrification is one of the main solidification-stabilization processes. This paper investigates the high temperature behavior of MSW flue gas residues, performed in laboratory experiments up to 1400 degrees C, and coupled with thermogravimetric analyses, X-ray diffraction, chemical and electron microprobe analyses. Melting temperatures of electrostatic precipitator (ESP) ash are in the range of 1202-1272 degrees C, whereas semi-dry scrubber residues melt between 1900 and 2300 degrees C. We show that the mean liquidus temperature of flue gas residues can be simply evaluated from their CaO content, by using the CaOSiO2Al2O3 ternary diagram. For ESP ash, the liquidus phase is a Zn-rich aluminous spinel, followed by anorthite at 1225 degrees C, and melilite at 1190 degrees C. The total mass loss reaches 18 wt.% at 1300 degrees C. Moreover, 90% of evaporation takes place below 1000 degrees C, linked to evaporation of C, Cl, S, Na, K, and of the toxic metals Hg, Cd, Pb, Cu. Due to the high partial pressure of chlorine during heating, chloride is the most probable form of evaporation for Cd, Pb, and Cu. However, most of Zn, Cr, Ni, Sb and Sn remain in the vitrified product.

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.

Pb(II) and Zn(II) adsorption onto Na- and Ca-montmorillonites in acetic acid/acetate medium: experimental approach and geochemical modeling.

Smectites are usually used as a clay barrier at the bottom of subsurface waste landfills due to their low permeability and their capacity to retain pollutants. The Na- and Ca-saturated SWy2 montmorillonites were interacted with initial Zn(NO(3))(2) or Pb(NO(3))(2) concentrations ranging from 10(-6) to 10(-2)M with a solid/liquid ratio of 10 g L(-1) and using acetic acid/acetate as buffer at pH 5 in order to reproduce a biodegradable leachate of a young landfill. These experiments revealed that Zn and Pb sorption onto Na-SWy2 is higher than that onto Ca-SWy2 in the whole range of concentrations. Metal retention into both montmorillonites increases with the decrease in acetic acid/acetate concentration. The two-site protolysis model with no electrostatic term (2SPNE model) was used to model these experiments. As the experimental data of Zn sorption were well fitted, this model was validated and has been improved by taking into account the metal-acetate complexation in solution. In order to validate the model for Pb sorption, new selectivity coefficients have been determined, namely logK(c)(PbNa)=0.5 for Na-montmorillonite and logK(c)(PbCa)=0.3 for Ca-montmorillonite.

Lead isotopic composition of fly ash and flue gas residues from municipal solid waste combustors in France: implications for atmospheric lead source tracing.

Fly ash and flue gas residues from eight municipal solid waste combustors (MSWC) in France (1992--93 and 1998/ 2002) were analyzed for their Pb isotopic composition. Fly ashes are more representative of solid residual particles, whereas flue gas residues reflect mostly the composition of gas phases. Both sample types contain hundreds to thousands of micrograms of metals per gram. Leaching experiments showed that metals are present in condensed phases, probably as sulfates and chlorides, and suggest that Cd, Pb, and Zn are highly fractionated from one another during volatilization/condensation processes occurring during combustion. Although all the samples analyzed define a fairly restricted range in Pb isotopic compositions (206Pb/207Pb = 1.148-1.158 and 208Pb/206Pb = 2.101-2.114) compared to other environmental samples, some MSWC produce materials having distinct isotopic compositions, whereas others display very similar ones. Isotopic heterogeneity is also measured between samples from a single MSWC. This is interpreted as resulting from the heterogeneity of the waste source materials. The range of Pb isotopic composition of incinerator materials form a well-defined linear array in the 208Pb/206Pb versus 206Pb/207Pb diagram. This array is compatible with the previously reported European standard pollution (ESP) line and most probably represent the average lead isotopic composition of industrial atmospheric emissions in France, with the following ratios: 206Pb/207Pb = 1.154+/-0.003 and 208Pb/206Pb = 2.107+/-0.003 (1sigma).