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Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia

  • Mining and the Environment - Understanding Processes, Assessing Impacts and Developing Remediation
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Abstract

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Markušovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite > pyrite > tetrahedrite > arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu > Sb > Hg > As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.

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Acknowledgments

We thank three anonymous reviewers for their constructive criticism and Ray Marshall for checking the English language of the manuscript. This study was financially supported by the Slovak Research and Development Agency under the contract no. APVV-03/VMSP-P-0115-09. Financial support for this study was also obtained by the Scientific Grant Agency of the Ministry of Education of Slovak Republic and the Academy of Sciences (VEGA 1/0219/10), the Comenius University grant no. UK/258/2012, and the grant from the Society of Economic Geologists (SEGF SGR 12-74). We acknowledge the ANKA Angströmquelle Karlsruhe for the provision of the beamline at the SUL-X beamline.

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Authors and Affiliations

  1. Department of Geochemistry, Comenius University, Mlynská dolina, 842 15, Bratislava, Slovak Republic

    Edgar Hiller, Roman Tóth & Ľubomír Jurkovič

  2. Department of Geology of Mineral Deposits, Comenius University, Mlynská dolina, 842 15, Bratislava, Slovak Republic

    Marián Petrák & Peter Šottník

  3. Department of Mineralogy and Petrology, Comenius University, Mlynská dolina, 842 15, Bratislava, Slovak Republic

    Bronislava Lalinská-Voleková, Gabriela Kučerová & Anežka Radková

  4. Ecological Laboratories, EL Ltd., Radlinského 17A, 052 01, Spišská Nová Ves, Slovak Republic

    Jaroslav Vozár

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  1. Edgar Hiller
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  2. Marián Petrák
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  3. Roman Tóth
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Correspondence to Edgar Hiller.

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Responsible editor: Philippe Garrigues

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Fig. S1

Macroscopic description of tailings profile for borehole BH-1 (JPEG 143 kb)

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Fig. S2

Field photographs from the studied impoundment showing a) hydrous ferric oxyhydroxides (O-1 and O-2) precipitating from drainage waters, b) discharge of treatment water (TW-1) into the water pond, c) manually excavated pit (T-2) in tailings oxidation zone and d) tailings sample taken from the borehole BH-1 at depth of more than 8 m (water-saturated zone) (JPEG 80 kb)

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Hiller, E., Petrák, M., Tóth, R. et al. Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia. Environ Sci Pollut Res 20, 7627–7642 (2013). https://doi.org/10.1007/s11356-013-1581-5

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