Martin Mihaljevič

Bioaccumulation of silver in ectomycorrhizal and saprobic macrofungi from pristine and polluted areas

Macrofungi are effective accumulators of Ag. This study provides a comprehensive review of this phenomenon supported by original data on the Ag concentrations of macrofungi from pristine and Ag-polluted areas. In pristine areas, the median Ag concentrations of ectomycorrhizal (ECM) and saprobic (SAP) macrofungi were 0.79 and 2.94 mg kg(-1), respectively. In these areas, hyperaccumulation thresholds for Ag in ECM and SAP macrofungi are proposed as 100 and 300 mg kg(-1), respectively. In a Ag-polluted area, the Ag concentrations in macrofungi (ECM and SAP) were significantly elevated with the median value of 24.7 mg kg(-1) and the highest concentrations in Amanita spp. of the section Vaginatae (304-692 mg kg(-1)). The intracellular speciation of Ag in fruit-bodies of the Ag-accumulator Amanita submembranacea was inspected by size exclusion chromatography followed by sulfhydryl-specific fluorimetric assays of ligands using reverse phase high-performance liquid chromatography and improved polyacrylamide gel electrophoresis. Virtually all Ag was found to be intracellular and sequestered in the major 7 kDa and minor 3.3 kDa complexes. The lack of glutathione and phytochelatins and the presence of a single 3 kDa sulfhydryl-containing peptide in the isolated Ag-complexes suggest that detoxification of Ag in A. submembranacea may rely on metallothionein. Vertical distribution of Ag in a polluted forest soil profile has shown substantial enrichment in organic horizons; in polluted technosol, the highest Ag concentrations were found in surface layers. Standardized EDTA extraction of Ag in both the investigated soil profiles showed relatively low Ag extractibility, generally within the range of 2.2-7.7% of total Ag content.

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals. The highest concentrations of dissolved As were found in groundwater (up to 1141 microg L(-1)), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S(-2,0) in the solid phase and a lower dissolved As concentration (70-80 microg L(-1)) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 microg L(-1) in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.

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.

Primary and secondary phases in copper-cobalt smelting slags from the Copperbelt Province, Zambia

Abstract Pyrometallurgical slags from three Cu-Co smelters (Nkana, Mufulira, Chambishi) in the Copperbelt Province, Zambia, were studied from mineralogical and chemical points of view. The slags were enriched in metals and metalloids, mainly Cu (up to 35 wt.%), Co (up to 2.4 wt.%) and As (up to 3650 ppm). The following primary phases were observed in slags: Ca-Fe silicates (clinopyroxene, olivine) and leucite, oxides (spinel-series phases), ubiquitous silicate glass and sulphide/metallic droplets of various sizes. The presence of glass and skeletal/dendritic crystal shapes indicated rapid cooling of the slag melt. Copper and cobalt were found in low concentrations in the majority of silicates (olivine, clinopyroxene) and oxides, substituting for Fe in their structures (up to 7.15 wt.% CoO in olivine, 4.11 wt.% CuO in spinel). Similarly, up to 0.91 wt.% CoO and 6.90 wt.% CuO were observed in the interstitial glass. Nevertheless, the main carriers of these metals in the slags studied were Cu sulphides (digenite, chalcocite, bornite, chalcopyrite), Co-Fe sulphides (cobaltpentlandite), Co-bearing intermetallic phases ((Fe,Co)2As) and alloys. Weathering features corresponding to the presence of secondary metal-bearing phases, such as malachite (Cu2(CO3)(OH)2), brochantite (Cu4SO4(OH)6) and sphaerocobaltite (CoCO3), were observed on the slag surfaces. They indicate that the slags studied are reactive on contact with water/atmosphere and that their environmental stability and release of potentially harmful metals and metalloids must be evaluated further.

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.

Arsenopyrite and As-bearing pyrite from the Roudny deposit, Bohemian Massif

Abstract The major- and trace-element chemistry of pyrite and arsenopyrite from the mesothermal Roudný gold deposits was studied by electron microprobe and laser ablation ICP-MS techniques. In total, four generations of pyrite and two of arsenopyrite were distinguished. The pyrite is enriched in As through an Fe (AsxS1−x)2 substitution mechanism. The As-rich zones of pyrite-2 (up to 4.5 wt.% As) are also enriched in gold (up to 20 ppm), lead (commonly up to 220 ppm, exceptionally up to 1500 ppm) and antimony (commonly <600 ppm, rarely up to 1350 ppm). Positive correlation of As and Au in the studied pyrites is not coupled with an Fe deficiency, in contrast to Au-rich As-bearing pyrites in Carlintype gold deposits. The As-rich pyrite-2 coprecipitated with the Sb-rich (1−4.2 wt.%) and Au-rich (40−150 ppm) arsenopyrite-1. The younger arsenopyrite-2 is significantly less enriched in these elements (0−70 ppm of Au). The chemical zonality of pyrites in the Roudný gold deposits reflects the chemical evolution of ore-bearing fluids that are not observed in any other mineral phases. The data available suggest relatively high activity of sulphur and low activities of arsenic and gold during crystallization of the older pyrite generation (pyrite-1). Later, after particular dissolution of pyrite-1, Au-rich As-bearing pyrite-2 and arsenopyrite precipitated. These facts suggest a marked increase in the arsenic and gold activities in ore-bearing fluids. The As-content of pyrite-2 decreases in an oscillatory manner from the core to the rim, reflecting changes in the As activity or/and in the P-T conditions. The As-bearing pyrites were formed at temperatures of at least 320-330ºC, based on arsenopyrite thermometers and fluid inclusion data.

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.

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.

Eutrophication of deciduous forests in the Bohemian Karst (Czech Republic): the role of nitrogen and phosphorus

Abstract In this study, we examined certain plant species for their high need of nitrogen (N>6, Ellenberg’s scale) and identified both conditions of soil nutrients, contents of N and P in leaves and light availability in permanent plots of deciduous forests in the Bohemian Karst (Central Bohemia) between 1997 and 1999. For comparison, a similar habitat was studied in SW-Slovenia. According to our results, factors limiting a development of the ground-layer vegetation of deciduous forests were soil moisture, soil NO3− content and light. The nitrophilic plant cover of the study area required for its development a readily available supply of nitrogen (mainly NO3−). In our opinion, an increase in the quantity of soil-available nitrogen may have been caused by an enhanced deposition of nitrogen. On the other hand, an analysis of leaf N and P indicated that the most of deciduous forests in the Bohemian Karst are still limited less by P than N. Therefore, a successful establishment of nitrophilic species seemed to be dependent on both an adequate supply of N and P in these soils. We observed that soil-extractable P contents were lower in plots covered with less than l% of nitrophilic plants than in all other plots. Diversity of nitrophilic species, i.e., the number of species per plot, was significantly increased in the presence of soil-extractable P. A positive effect of P on both nitrogen mineralisation and nutrition of nitrophilic plants has been reported earlier in the literature. Thus, a successful utilisation of increased N in soils of these ecosystems could occur only in the presence of a sufficiently high P content.