Geochemical processes in mine waste subjected to a changing chemical environment: Fe speciation in leachate water from column experiments

Oxidation of sulfidic mine waste is of significant environmental concern due to the consequent formation of acid rock drainage (ARD), deteriorating the water quality of natural water systems. Iron (Fe) and sulfur (S) are two major redox elements involved in these reactions and typically the major redox-sensitive elements (whose solubility, speciation, and mobility are affected by pH and Eh) in water affected by ARD. Measurements of Fe and S species concentrations may reveal valuable information about geochemical processes in mine waste but are typically included when analyzing the chemical composition of ARD. In this study, robust and portable methods for the determination of Fe and S species concentrations in leachate water affected by sulfidic mine waste were tested and evaluated. The leachate water resulting from interaction with high- and low-sulfide waste rock was collected from three leaching columns, each reflecting different geochemical environments that could occur during mine waste management: (1) fully oxidized conditions (reference column), (2) gradual oxygen depletion from atmospheric level to <1% (anoxic column), (3) treatment with alkaline industrial residual material (alkaline column). The leachate water was analyzed for its pH, Eh, electric conductivity (EC), and major and trace elements. UV-Vis spectrophotometric ferrozine method was tested and applied for Fe speciation and concentration analysis, allowing determination of Fe(II) and Fetot and further calculation of Fe(III) as a difference. The method was found to achieve accurate and reliable results. Turbidimetry was tested and evaluated for dissolved sulfate analysis, and even though the analytical precision was poorer, ca. ±20%, the method provides useful semi-quantitative estimations of dissolved sulfate concentrations. Both spectrophotometry and turbidimetry are easy to perform and utilizes robust, cheap and portable instrumentation. Leachate water from the high and low sulfide experiments had pH and Eh in the range of pH 2.6 – 12 and Eh 200 – 720 mV and pH 3.5 – 4 and Eh 550 – 700 mV, respectively. Measurements of iron species and sulfate concentrations revealed that sulfate was the dominating S species and during the background leachate Fe(II) was the predominant Fe oxidation state. Upon decreasing oxygen saturation and pH in the anoxic column, Fe speciation in the reference and anoxic column differed, with the relative importance of Fe(III) increasing in the anoxic column. Total Fe, pH and Eh potential measured in the leachate water did not respond to decreasing oxygen saturation, but changes in the Fe redox speciation coincided with this decrease. Under alkaline conditions, total Fe and sulfate concentrations decreased in the alkaline environment, indicating their immobilization in the solid phase. Geochemical calculations were carried out to gain further understanding of the dominant reactions in the columns. Theoretical values of Fe(II) and Fe(III) concentrations were calculated from the measured redox potential, and these were found to deviate from the measured concentrations. Therefore, estimation of Fe species distribution from redox measurements using a Pt-electrode is not considered sufficient in these systems. Mineral saturation indices of common secondary minerals associated with ARD indicated dissolution of ferrihydrite, jarosite and schwertmannite in the leachate water from the anoxic column. This suggests that these minerals are the probable source of the Fe and sulfate, as well as As and Cu released to the leachate water.