Zn and Pb release of sphalerite (ZnS)-bearing mine waste tailings

Background, aim, and scope  Contaminated mine drainage water has become a major hydrogeological and geochemical problem. Release of soluble metal contaminants and acidity from mining sites can pose serious chemical risks to surface and groundwater in the surrounding environment, and it is an important socio-economic factor addressed by working groups like SUITMA Morel and Heinrich (J Soils Sediments 8:206–207, 2008). The release of Zn and Pb from sulfide-bearing flotation residues of a small scale mine in Western Germany is investigated with focus on metal transfer to soil solution. Total contents of the soil material as well as soil water sampled with suction cups were analyzed. The influence of pH on leaching behavior was investigated with pH_stat tests. Isotopic analyses helped assessing seepage water velocity. The aim of this study was the assessment of the environmental behavior of zinc and lead caused by the weathering of sulfide-bearing mine tailings. Especially, we address in this paper the dissolution of sphalerite (ZnS) in contrast to the well-known dissolution processes of pyrite (FeS₂). Materials and methods  Total metal contents of the soil samples were analyzed by energy-dispersive X-ray fluorescence spectroscopy, total C concentration was measured using a CHNS elemental analyzer. X-ray diffraction (XRD) spectra were recorded from powdered soil samples. Soil water was sampled in nylon suction cups. Electrical conductivity (EC), pH, and temperature of the soil water samples were measured in the field immediately after sampling. Major anions (F, Cl, NO₂, NO₃, SO₄) were analyzed by ion chromatography, major cations (Ca, Na, K, Li) were analyzed by flame photometry, heavy metals (Zn, Pb, Fe, Mn, and Mg) by flame atomic absorption spectrometry. Tritium was analyzed by liquid scintillation counting (LSC), ¹⁸O and ²H were analyzed by isotope ratio mass spectrometry (IRMS). pH_stat tests were performed at four different pH values between 2 and 5. Results  Total Zn contents of the soil samples averaged 10 g kg⁻¹, Pb contents averaged 2.5 g kg⁻¹, Fe 22 g kg⁻¹, S 8.0 g kg⁻¹, and total carbon 4.0 g kg⁻¹. Below 2-m depth, soil samples had neutral pH values. Toward the surface, pH decreased down to pH 5.4 in P1 and P3, and to pH 5.9 in core P2, respectively. Dissolved contents of major ions (Mg, Ca, K, SO₄, and HCO₃) in the soil solution increased with depth. Metal concentrations (Fe, Mn, Zn) decreased with depth. The solution pH was neutral to slightly alkaline in samples below 2 m and slightly acidic (pH 6) at 1 m depth. Tritium values are around 7 TU and correspond to modern rain, i.e., after 1975. Stable isotope values plot on the global meteoric water line. The pH_stat tests provide two kinds of information, the acid neutralization capacity after 24 h (ANC24) and the release of metals depending on pH. The ANC24 increases linearly with decreasing pH from about 60 mmol(eq) kg⁻¹ at pH 5 to about 460 mmol(eq) kg⁻¹ at pH 2. Zn and Fe release show a strong increase with decreasing pH to 126 and 142 mmol(eq) kg⁻¹, respectively. Pb release increases at pH <4 and Mn release at pH <5, both to about 10 mmol(eq) kg⁻¹. Discussion  With an average of 10 g kg⁻¹, this field site is highly enriched in Zn. In the oxidized topsoil, Zn concentrations are significantly lower than in the anoxic subsoil. The distribution pattern of total Zn contents and soil pH values indicate that the topsoil, which is prone to oxidation and acidification, is already depleted in Zn. Only in soil core P2, Zn (and Fe) contents in the topsoil were higher than in the subsoil. Oxidation of the sulfidic material leads to redistribution into mobilizable species. High soil water concentrations (10 to 15 mg L⁻¹) can be found at acidic pH. The dominant Zn species in the soil solution is Zn²⁺. At neutral pH, Zn concentrations are below 0.001 mg L⁻¹. During the soil passage, the contaminated seepage water enters the anoxic subsoil with pH buffering carbonates. Results indicate that Zn is immobilized there. However, when the acid neutralization capacity is exhausted, a breakthrough of dissolved Zn to the groundwater has to be expected. Lead averages 2.5 g kg⁻¹ inside the flotation dump. In contrast to Zn, the first centimeters of the oxidized topsoil with high TOC contents show higher Pb contents than the anoxic subsoil. About 80% of the cation exchange capacity in the topsoil is occupied by Pb. In contrast to Zn, Pb is not abundant as aqueous species at slightly acidic pH. Values lower than pH 4 are necessary to mobilize Pb in higher amounts, as pH_stat experiments confirm. Hence, Pb is not expected to be leached out until the buffer capacity of the soil is exhausted. Conclusions  The environmental fate and behavior of Zn and Pb in the flotation dump is strongly depending on pH and redox conditions. Oxidation of sphalerite leads to a transfer of Zn from immobile to easily mobilizable species. Sulfide oxidation leads to an acidification of the topsoil where the buffer capacity is already exhausted due to the leaching of carbonates. At acidic pH, Zn is transferred to the aqueous phase and leached to the subsoil where soil pH is neutral. Electron supply and the buffer capacity of the material are found to be the main factors controlling the mobility of Zn. In contrast, the transfer of comparable amounts of Pb to the aqueous phase requires pH values <4. Since Pb is enriched in the topsoil, not leaching to the groundwater, but direct uptake (e.g., children, animals) and uptake by plants is the highest environmental risk. If the acidification of the soil proceeds with the same rate as in the last 40 years, it will reach the bottom of the tailing in about 200 years and a breakthrough of metals to the groundwater has to be expected. Recommendations and perspectives  The behavior of the different metals and their environmental impact depends on the different metal properties as well as on external conditions, e.g. pH, redox conditions, buffer capacity, and groundwater recharge. To assess the future release of metals from a flotation dump it is crucial to determine the main processes leading to acidification, the buffer capacity, and heavy metal binding forms. The release of heavy metals to the groundwater could be prevented by liming or other buffering techniques de Andrade et al. (J Soils Sediments 8:123–129, 2008). Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.