Vojtěch Ettler

Chemical stabilization of metals and arsenic in contaminated soils using oxides--a review.

Oxides and their precursors have been extensively studied, either singly or in combination with other amendments promoting sorption, for in situ stabilization of metals and As in contaminated soils. This remediation option aims at reducing the available fraction of metal(loid)s, notably in the root zone, and thus lowering the risks associated with their leaching, ecotoxicity, plant uptake and human exposure. This review summarizes literature data on mechanisms involved in the immobilization process and presents results from laboratory and field experiments, including the subsequent influence on higher plants and aided phytostabilization. Despite the partial successes in the field, recent knowledge highlights the importance of long-term and large-scale field studies evaluating the stability of the oxide-based amendments in the treated soils and their efficiency in the long-term.

Leaching of polished sections : an integrated approach for studying the liberation of heavy metals from lead-zinc metallurgical slags

Pb-Zn metallurgical slags are defined by European Community regulations either as waste (hazardous materials) or as secondary commercial substances. The knowledge of their stability is essential in order to assess strategies for their management. A scientific understanding of metal release requires (i) knowledge of the phases hosting the different hazardous metals (e.g., Pb) and (ii) knowledge of the relative solubility of these phases. This paper is devoted to a mineralogical characterisation of slags resulting from different processing technologies and to long-term static leaching experiments run under different pH-conditions. The main mineral phases of slags are spinel-family oxides, Ca-Fe aluminosilicates (clinopyroxene, olivine-type phases, melilite, garnet), silicate glass, sulphide (galena, wurtzite) and intermetallic droplets. Leaching experiments were conducted on polished sections, which were introduced into batch reactors and leached by the following solutions: (i) citric acid-sodium citrate buffer at pH ~ 3 (organic soil-simulating solution), (ii) deionised water without any pH control and (iii) calcium hydroxide saturated solution buffered at pH ~ 12.5 (concrete-simulating solution). Sulphide/metallic phases display an extremely low stability whatever the solution. Under organic-acid conditions, Ca-rich (melilite) and Fe-rich (fayalite) phases are preferentially dissolved. Spinel-family oxides are always extremely stable. SEM observations evidence the important role of citrate, which favours the extraction through chelation of metallic elements on the slag surface. The silicate glass and sulphide/metallic droplets are the most unstable phases under intermediate conditions (deionised water). However, under such conditions, the mobility of Pb, Zn and As is drastically limited by precipitation/adsorption processes, as shown by geochemical modelling (PHREEQC, EQ3NR). A preferential dissolution of glass, clinopyroxene and garnet occurs in alkaline environments. Additionally, lead is significantly released by the dissolution of galena and remains dissolved. On the contrary, zinc content is likely controlled by precipitation of secondary zincite (ZnO) or zinc hydroxide, as predicted by the EQ3NR calculations. The results of static leaching experiments under various conditions confirm that the disposal of slag in organic-rich environments (e.g., peat soil) or the use of slag in concrete technology should be avoided due to the high mobilisation of Pb and other toxic elements.

The pH-dependent leaching of inorganic contaminants from secondary lead smelter fly ash

The leaching behaviour of fly ash (FA) from a secondary Pb smelter was assessed using the pH-static leaching experiment according to prEN 14997 (pH range 3-11) coupled with mineralogical investigation of the leached FA by XRD and Rietveld analyses and thermodynamic modelling using PHREEQC-2. The procedure was performed on fresh FA and FA washed at a cumulative L/S ratio of 60l/kg to remove readily soluble salts. For both fresh and washed FA, high amounts of inorganic contaminants were released under acidic conditions, exhibiting L-shaped leaching patterns: up to 300g Pb/kg, 4.5g Cd/kg, 4g Zn/kg, 1.05g As/kg and 70mg Sb/kg. The washing of soluble salts significantly decreased the leachability of Cd, Zn, As and Sb and increased the release of Pb, especially under acidic conditions. The leaching of fresh FA removed part of primary caracolite and all the KPb(2)Cl(5) and NaCl. The Pb release was controlled by the precipitation of anglesite and PbSO(3) under acidic conditions and of laurionite and carbonates (hydrocerussite and phosgenite) under alkaline conditions. In contrast, the washed FA was composed mainly of anglesite and PbSO(3), both phases being the main solubility-controlling phases for Pb over the whole studied pH range.

Cadmium, lead and zinc leaching from smelter fly ash in simple organic acids—Simulators of rhizospheric soil solutions

Emissions from base-metal smelters are responsible for high contamination of the surrounding soils. Fly ash from a secondary Pb smelter was submitted to a batch leaching procedure (0.5-168 h) in 500 microM solutions of acetic, citric, or oxalic acids to simulate the release of toxic metals (Cd, Pb, Zn) in rhizosphere-like environments. Organic acids increased dissolution of fly ash by a factor of 1.3. Cadmium and Pb formed mobile chloro- and sulphate-complexes, whereas Zn partly present in a citrate (Zn-citrate(-)) complex is expected to be less mobile due to sorption onto the positively charged surfaces of hydrous ferric oxides (HFO) and organic matter (OM) in acidic soil.

Evaluating the potential of three Fe- and Mn-(nano)oxides for the stabilization of Cd, Cu and Pb in contaminated soils.

The potential of three Fe- and Mn-(nano)oxides for stabilizing Cd, Cu and Pb in contaminated soils was investigated using batch and column experiments, adsorption tests and tests of soil microbial activity. A novel synthetic amorphous Mn oxide (AMO), which was recently proposed as a stabilizing amendment, proved to be the most efficient in decreasing the mobility of the studied metals compared to nano-maghemite and nano-magnetite. Its application resulted in significant decreases of exchangeable metal fractions (92%, 92% and 93% decreases of Cd, Cu and Pb concentrations, respectively). The adsorption capacity of the AMO was an order of magnitude higher than those recorded for the other amendments. It was also the most efficient treatment for reducing Cu concentrations in the soil solution. No negative effects on soil microorganisms were recorded. On the other hand, the AMO was able to dissolve soil organic matter to some extent.

The leaching behaviour of lead metallurgical slag in high-molecular-weight (HMW) organic solutions

Abstract The reactivity of primary Pb metallurgical slags in high-molecular-weight (HMW) organic solutions has been studied in order to determine the processes of release and attenuation of metal and metalloid contaminants (Pb, Zn, Cu, As) in ‘soil-like’ environments. Slag was submitted to a 112-day batch leaching experiment in Suwannee River fulvic acid solution and peat water (~50 mg DOC 1-1). The leaching was coupled with investigation of the secondary phases (SEM/EDS, Raman microspectrometry) and thermodynamic speciation-solubility modelling using MINTEQA2. Metals and As are released in large amounts during the early stage of the experiment, followed by a decrease in the concentrations in the leachate as a result of adsorption on secondary (hydrous) ferric oxides (HFO/FO), predicted by MINTEQA2 calculations and confirmed on the leached slag surface by SEM and Raman spectrometry. Compared to other contaminants, Zn exhibits more pronounced mobility and is adsorbed on HFO/FO only at pH >7. Such a scavenging process may be predominant during the long-term interaction of slag with an HMW organic solution of real soil. As a result, the soil cover and subsequent re-vegetation of slag dumps may be considered as a possible scenario for slag management.

Surprisingly contrasting metal distribution and fractionation patterns in copper smelter-affected tropical soils in forested and grassland areas (Mufulira, Zambian Copperbelt)

Six soil profiles located near Mufulira (Zambian Copperbelt) were studied to evaluate and compare the extent of environmental pollution of Cu-ore mining and smelting in both forested and grassland areas. The highest metal concentrations were detected in the uppermost soil layers with the following maxima: Co 45.8 mg kg(-1), Cu 8,980 mg kg(-1), Pb 41.6 mg kg(-1), and Zn 97.0 mg kg(-1). Numerous anthropogenic metal-bearing particles were detected in the most polluted soil layers. The spherical smelter-derived particles were mainly composed of covellite (CuS) and chalcocite (Cu2S), while the angular mining-derived particles were mostly composed of chalcopyrite (CuFeS2). Additionally, Fe-Cu oxide particles predominantly corresponding to tenorite (CuO) and delafossite (Cu(1+)Fe(3+)O2), along with hydrated Fe-oxides corresponding to secondary weathering products, were detected. In contrast to smelter-affected soils in temperate climates, where forest soils are significantly more enriched in metals than tilled soils due to high canopy interception, our data indicate a higher proportion of metal-bearing anthropogenic particles and higher metal concentrations in soils from unforested sites. This phenomenon is probably related to the more frequent and intense bushfires in forested areas, leading to the mobilization of pollutants contained in the biomass-rich surface soils back into the atmosphere.

Experimental in situ transformation of Pb smelter fly ash in acidic soils.

Soils in the vicinity of nonferrous metal smelters are often highly polluted by inorganic contaminants released from particulate emissions. We used a technique with double polyamide experimental bags (1-μm mesh) to study the in situ transformation of fly ash (FA) from a secondary Pb smelter in acidic soil profiles. Between 62 and 66% of the FA dissolved after one years exposure in the soils, leading to complete dissolution of primary caracolite (Na(3)Pb(2)(SO(4))(3)Cl) and KPb(2)Cl(5), with formation of secondary anglesite (PbSO(4)), minor PbSO(3), and trace carbonates. Release of Pb was pH-dependent, whereas not for Cd and Zn. Significant amounts of metals (mainly Cd and Zn) partitioned into labile soil fractions. The field data agreed with laboratory pH-static leaching tests performed on FA, which was washed before the experiment to remove soluble salts. This indicates that appropriate laboratory leaching can accurately predict FA behavior in real-life scenarios (e.g., exposure in soil).

Alteration of arsenopyrite in soils under different vegetation covers.

The weathering of arsenopyrite (FeAsS) has been monitored in soils using an in situ experimental approach. Arsenopyrite in nylon experimental bags was placed in individual horizons in soils in spruce (litter, horizons A, B, and C), beech (litter, horizons A, B, and C) and unforested (horizons A, B, and C) areas and left in contact with the soil for a period of 1 year. The individual areas on the ridge of the Krusné hory Mts., Czech Republic, had the same lithology, climatic and environmental conditions. Scorodite (FeAsO(4).2H(2)O) was identified as a principal secondary mineral of arsenic (As) formed directly on the surface of the arsenopyrite. Scorodite was formed in all the areas in all soil horizons. The amount of scorodite formed decreased in the series beech, spruce and unforested areas. In forested areas, there was a larger amount of scorodite on arsenopyrites exposed in organic horizons (litter, A horizon). The greater rate of arsenopyrite alteration in organic horizons in the beech stand compared to spruce stand is probably a result of faster mineralization of organic material with resulting production of nitrate and better seepage conditions of soil in this area. Speciation of As determined using the sequential extraction technique demonstrated that As was bonded in the soils primarily in the residual fractions prior to the experiment. The As content in the mobile fractions increased in the organic horizon in the forested areas after the experiments.

Thallium contamination of soils/vegetation as affected by sphalerite weathering: a model rhizospheric experiment.

The environmental stability of Tl-rich sphalerite in two contrasting soils was studied. Rhizospheric conditions were simulated to assess the risk associated with sulfide microparticles entering agricultural (top)soils. The data presented here clearly demonstrate a significant effect of 500 μM citric acid, a model rhizospheric solution, on ZnS alteration followed by enhanced Tl and Zn release. The relative ZnS mass loss after 28 days of citrate incubation reached 0.05 and 0.03 wt.% in Cambisol and Leptosol samples respectively, and was up to 4 times higher, compared to H2O treatments. Incongruent (i.e., substantially increased) mobilization of Tl from ZnS was observed during the incubation time. Generally higher (long-term) stability of ZnS with lower Tl release is predicted for soils enriched in carbonates. Furthermore, the important role of silicates (mainly illite) in the stabilization of mobilized Tl, linked with structural (inter)layer Tl-K exchange, is suggested. Thallium was highly bioavailable, as indicated by its uptake by white mustard; maximum Tl amounts were detected in biomass grown on the acidic Cambisol. Despite the fact that sulfides are thought as relatively stable phases in soil environments, enhanced sulfide dissolution and Tl/trace element release (and bioaccumulation) can be assumed in rhizosphere systems.