Aleš Vaněk

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.

Potential and drawbacks of EDDS-enhanced phytoextraction of copper from contaminated soils.

Incubation and pot experiments using poplar (Populus nigra L. cv. Wolterson) were performed in order to evaluate the questionable efficiency of EDDS-enhanced phytoextraction of Cu from contaminated soils. Despite the promising conditions of the experiment (low contamination of soils with a single metal with a high affinity for EDDS, metal tolerant poplar species capable of producing high biomass yields, root colonization by mycorrhizal fungi), the phytoextraction efficiency was not sufficient. The EDDS concentrations used in this study (3 and 6 mmol kg(-1)) enhanced the mobility (up to a 100-fold increase) and plant uptake of Cu (up to a 65-fold increase). However, despite EDDS degradation and the competition of Fe and Al for the chelant, Cu leaching cannot be omitted during the process. Due to the low efficiency, further research should be focused on other environment-friendly methods of soil remediation.

Retention of copper originating from different fungicides in contrasting soil types

This work described the retention of Cu from two different commonly used pesticides, the Bordeaux mixture (CuSO(4)+Ca(OH)(2)) and Cu-oxychloride (3Cu(OH)(2).CuCl(2)), and from Cu(NO(3))(2) in contrasting soil types (Leptosol, Chernozem, Cambisol). Thermodynamic modeling showed that Cu speciation was similar in all fungicide solutions. However, the retention of Cu differed with the fungicide used (maximum retention from the Bordeaux mixture) which indicates that different retention processes occurred in the studied soils. The suggested mechanisms include: specific and non-specific adsorption (especially on soil organic matter), precipitation of newly formed phases, such as CuO, Cu(OH)(2), Cu(2)(OH)(3)NO(3), CuCO(3)/Cu(2)(OH)(2)CO(3) and in the case of the Bordeaux mixture, precipitation of various Cu-hydroxysulfates. These phases were identified by the speciation model. The retention of fungicide-derived Cu in the studied soil types followed well the Freundlich isotherm and was directly controlled by the chemical form of Cu. This fact should be taken into account for both environmental and practical applications.

Interactions of EDDS with Fe- and Al-(hydr)oxides.

The efficiency of EDDS ([S,S]-ethylenediaminedisuccinate) in metal (phyto) extraction has been discussed in many recent papers. This study demonstrated that the presence of Fe- and Al-(hydr)oxides in soils influences the speciation of EDDS and thus can decrease the extraction of the targeted metallic contaminants (e.g., Pb, Cu, Zn). Above all, amorphous and poorly crystalline oxides (e.g., ferrihydrite) seem to significantly control dissolved Fe and Al concentrations in soils in the presence of metal-EDDS complexes and especially uncomplexed EDDS. Metals released from these minerals compete for the chelating agent and the extraction efficiency of the targeted metals is lowered. The formation of stable Cu-EDDS complexes, which are preferentially formed in soils with high Cu concentrations, results into a lower dissolution of ferrihydrite and goethite compared to free EDDS and Al-EDDS. Information about the contents of amorphous and poorly crystalline oxides in the treated soils would thus be beneficial for choosing efficient EDDS dosages.

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.

Thallium uptake by white mustard (Sinapis alba L.) grown on moderately contaminated soils—Agro-environmental implications

The work focused on Tl uptake by white mustard (Sinapis alba L.) grown on moderately contaminated soils with different characteristics. The data presented here clearly demonstrate the ability of white mustard to (hyper)accumulate Tl. Substantially higher Tl levels were was found in mustard grown on the Arenosol as compared to the carbonate-rich Leptosol; a relationship between the content of labile Tl (adsorbed, bound to carbonates etc.) in soil and its uptake by the plant is suggested. Approximately 3-fold lower concentrations of Tl in roots and stems of the mature mustard (compared to the young plant) indicate a decreasing trend of Tl uptake with the age of the plant. The exchangeable/acid-extractable and reducible Tl fractions were evaluated as the dominant fractions controlling Tl transfer from both contrasting soils. Thallium associated with the residual fraction (e.g., incorporated into silicates) was rather stable in the rhizosphere, proving a negligible influence of root exudates on Tl release from such an operationally defined fraction, despite the anthropogenic origin of Tl. Regarding our results, when mustard is cultivated for nutrition purposes and/or as green manure, it may pose an important source of Tl introduction into the food chain.

Effect of illite and birnessite on thallium retention and bioavailability in contaminated soils.

The influence of illite and birnessite (δ-MnO(2)) amendments on the retention and bioavailability of Tl in contaminated soils was investigated. The efficiency of both phases was evaluated using Tl uptake by white mustard (Sinapis alba L.), sequential extraction and sorption experiments. The obtained data demonstrate that the application of birnessite can effectively transform Tl from the labile (easily mobilizable) fraction to its reducible form, thus lowering Tl bioavailability in soil and subsequent accumulation by plants. The Mn oxide added to the soils reduced substantially Tl uptake; Tl levels in the plants decreased by up to 50%, compared to the non-amended soil. The effect of illite on the immobilization and uptake of Tl was less pronounced, and in the carbonate-rich Leptosol has not been proved at all, suggesting the importance of bulk soil mineralogy and nature of the soil sorption complex on the behavior of this amendment. Therefore, the general applicability of illite for Tl stabilization in soils seems to be limited and strongly dependent on soil composition. In contrast, the use of birnessite like soil additive might be an efficient and environment-friendly solution for soil systems contaminated with Tl.

The effect of beverage preparation method on aluminium content in coffee infusions

Seven types of coffee were prepared by four methods. Three of them - simple coffee infusion, preparation in ibrick and moka pot - are very often used to prepare coffee at home. The fourth one - a single-cup filter is typical for Vietnam. Cookware used for each method was made from glass, aluminium, stainless steel and two types of alloys. Amounts of Al leaching to coffee infusions were determined. On average, the highest amount of Al was in coffee infusions brewed in aluminium single-cup filter, and the lowest in infusions prepared by simple extraction. Other brewing methods in combination with different tool materials resulted in similar Al content. The type of brewing method significantly influences the Al content in final infusion. Aluminium content varies in infusions in relation to the method of choice, especially when using single-cup filter. Despite the fact that coffee is considered to be a poor source of Al for humans, in some cases, Al content in infusions can even reach the values reported for tea infusions.

Combined Chemical and Mineralogical Evidence for Heavy Metal Binding in Mining-and Smelting-Affected Alluvial Soils

The binding of metallic contaminants (Pb, Cd, and Zn) and As on soil constituents was studied on four highly contaminated alluvial soil profiles from the mining/smelting district of Přibram (Czech Republic) using a combination of mineralogical and chemical methods. Sequential extraction analysis (SEA) was supplemented by mineralogical investigation of both bulk samples and heavy mineral fractions using X-ray diffraction analysis (XRD) and scanning electron microscopy with an energy dispersive X-ray spectrometer (SEM/EDS). The mineralogy of Fe and Mn oxides was studied by voltammetry of microparticles (VMP) and diffuse reflectance spectrometry (DRS). Zinc and Pb were predominantly bound in the reducible fraction attributed to Fe oxides and Mn oxides (mainly birnessite, Na4Mn14O27•9H2O), which were detected in soils by XRD and SEM/EDS. In contrast, Cd was the most mobile contaminant and was predominantly present in the exchangeable fraction. Arsenic was bound to the residual and reducible fractions (corresponding to Fe oxides or to unidentified Fe-Pb arsenates). SEM/EDS observations indicate the predominant affinity of Pb for Mn oxides, and to a lesser extent, for Fe oxides. Thus, a more suitable SEA procedure should be used for these mining-affected soils to distinguish between the contaminant fraction bound to Mn oxides and Fe oxides.

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.