Cravotta, C. A., III, & Trahan, M. K. (1999). Limestone drains to increase pH and remove dissolved metals from acidic mine drainage. Appl. Geochem., 14(5), 581–606.
Abstract: Despite encrustation by Fe and Al hydroxides, limestone can be effective for remediation of acidic mine drainage (AMD). Samples of water and limestone (CaCO3) were collected periodically for 1 a at 3 identical limestone-filled drains in Pennsylvania to evaluate the attenuation of dissolved metals and the effects of pH and Fe- and Al-hydrolysis products on the rate of CaCO3 dissolution. The influent was acidic and relatively dilute (pH < 4; acidity < 90 mg) but contained 1-4 mg . L-1 of O-2, Fe3+, Al3+ and Mn2+. The total retention time in the oxic limestone drains (OLDs) ranged from 1.0 to 3.1 hr. Effluent remained oxic (O-2 > 1 mg . L-1) but was near neutral (pH = 6.2-7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs, The hydrous oxides, nominally Fe(OH)(3) and Al(OH)(3), were visible as loosely bound, orange-yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)(3) and Al(OH)(3) particles were transported downflow. The accumulation of hydrous oxides and elevated pH (> 5) in the downflow part of the OLDs promoted sorption and coprecipitation of dissolved Mn, Cu, Co, Ni and Zn as indicated by decreased concentrations of the metals in effluent and their enrichment relative to Fe in hydrous-oxide particles and coatings on limestone. Despite thick (similar to 1 mm) hydrous-oxide coatings on limestone near the inflow, CaCO3 dissolution was more rapid near the inflow than at downflow points within and the OLD where the limestone was not coated. The high rates of CaCO3 dissolution and Fe(OH3) precipitation were associated with the relatively low pH and high Fe3+ concentration near the inflow. The rate of CaCO3 dissolution decreased with increased pH and concentrations of Ca2+ and HCO3- and decreased Pco(2). Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two-stagetreatment system consisting of an anoxic limestone drain and oxidation-settling pond or wetland. To facilitate removal of hydrous-oxide sludge, a perforated-pipe subdrain can be installed within an OLD. (C) 1999 Elsevier Science Ltd.
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Robbins, E. I., Cravotta, C. A., Savela, C. E., & Nord, G. L. (1999). Hydrobiogeochemical Interactions in 'anoxic' Limestone Drains for Neutralization of Acidic Mine Drainage. Fuel, 78(2), 259–270.
Abstract: Processes affecting neutralization of acidic coal mine drainage were evaluated within 'anoxic' limestone drains (ALDs). Influents had pH less than or equal to 3.5 and dissolved oxygen < 2 mg/l. Even though effluents were near neutral (pH > 6 and alkalinity > acidity), two of the four ALDs were failing due to clogging. Mineral-saturation indices indicated the potential for dissolution of calcite and gypsum, and precipitation of Al3+ and Fe3+ compounds. Cleavage mounts of calcite and gypsum that were suspended within the ALDs and later examined microscopically showed dissolution features despite coatings by numerous bacteria, biofilms, and Fe-Al-Si precipitates. In the drain exhibiting the greatest flow reduction, Al-hydroxysulfates had accumulated onlimestone surfaces and calcite etch points, thus causing the decline in transmissivity and dissolution. Therefore, where Al loadings are high and flow rates are low, a pre-treatment step is indicated to promote Al removal before diverting acidic mine water into alkalinity-producing materials. Published by Elsevier Science Ltd.
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Schwartz, M. O., & Ploethner, D. (1999). From mine water to drinking water; heavy-metal removal by carbonate precipitation in the Grootfontein-Omatako Canal, Namibia.. Hanover: Bundesanst. fuer Geowiss. und Rohstoffe.
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Simmons, J. A., Andrew, T., Arnold, A., Bee, N., Bennett, J., Grundman, M., et al. (2006). Small-Scale Chemical Changes Caused by In-stream Limestone Sand Additions to Streams. Mine Water Env., 25(4), 241–245.
Abstract: In-stream limestone sand addition (ILSA) has been employed as the final treatment for acid mine drainage discharges at Swamp Run in central West Virginia for six years. To determine the small-scale longitudinal variation in stream water and sediment chemistry and stream biota, we sampled one to three locations upstream of the ILSA site and six locations downstream. Addition of limestone sand significantly increased calcium and aluminum concentrations in sediment and increased the pH, calcium, and total suspended solids of the stream water. Increases in alkalinity were not significant. The number of benthic macroinvertebrate taxa was significantly reduced but there was no effect on periphyton biomass. Dissolved aluminum concentration in stream water was reduced, apparently by precipitation into the stream sediment.
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Sottnik, P., & Sucha, V. (2001). Moznosti upravy kysleho banskeho vytoku loziska Banska Stiavnica-Sobov. Remediation of acid mine drainage from Sobov Mine, Banska Stiavnica. Mineralia Slovaca, 33(1), 53–60.
Abstract: A waste dump formed during the exploitation of quartzite deposit in Sobov mine (Slovakia) produces large quantity of acid mine drainage (AMD) which is mainly a product of pyrite oxidation. Sulphuric acid--the most aggressive oxidation product--attacks gangue minerals, mainly clays, as well. This process lead to a sharp decrease of the pH values (2-2.5) and increase of Fe, Al and SO (super 2-) (sub 4) contents (TDS = 20-30 mg/1). Passive treatment system was designed to remediate AMD. Chemical redox reactions along with microbial activity cause a precipitation of mobile contamination into a more stable forms. The sulphides are formed in the anaerobic cell, under reducing conditions. Fe-, Al- oxyhydroxides are precipitated in the aerobic part of the system. Precipitation decreases the Fe and Al contents along with immobilization of some heavy metal closely related to oxyhydroxides. Besides oxidation, the wetland vegetation is an active part of on aerobic cell. The system has been working effectively since September 1999. The pH values of outflowing water are apparently higher (6.2-6.8) and contents of dissolved elements (Fe from 2.260 to 4.1; Al from 900 to 0.18; Mn from 51 to 23; Cu from 4.95 to 0.03 mg/l) is significantly lowers.
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