Barton, C. D., & Karathanasis, A. D. (1997). Aerobic and anaerobic metal attenuation processes in a constructed wetland treating acid mine drainage. In AAPG Eastern Section and the Society for Organic Petrology joint meeting; abstracts (1545). 81: AAPG Bulletin.
Abstract: The use of constructed wetlands for acid mine drainage amelioration has become a popular alternative to conventional treatment methods, however, the metal attenuation processes of these systems are poorly understood. Precipitates from biotic and abiotic zones of a staged constructed wetland treating high metal load (approx. equal to 1000 mg L (super -1) ) and low pH (approx. 3.0) acid mine drainage were characterized by chemical dissolution, x-ray diffraction, thermal analysis and scanning electron microscopy. Characterization of abiotic/aerobic zones within the treatment system suggest the presence of crystalline iron oxides and hydroxides such as hematite, lepidocrocite, goethite, and jarosite. At the air/water interface of initial abiotic treatment zones, SO (sub 4) /Fe ratios were low enough (<2.0) for the formation of jarosite and goethite, but as the ratio increased due to treatment and subsequent reductions in iron concentration, jarosite was transformed to other Fe-oxyhydroxysulfates and goethite formation was inhibited. In addition, elevated pH conditions occurring in the later stages of treatment promoted the formation of amorphous iron oxyhydroxides. Biotic wetland cell substrate characterizations suggest the presence of amorphous iron minerals such as ferrihydrite and Fe(OH) (sub 3) . Apparently, high Fe (super 3+) activity, low Eh and low oxygen diffusion rates in the anaerobic subsurface environment inhibit the kinetics of crystalline iron precipitation. Some goethite, lepidocrocite and hematite, however, were observed near the surface in biotic areas and are most likely attributable to increased oxygen levels from surface aeration and/or oxygen transport by plant roots. Alkalinity generation from limestone dissolution within the substrate and bacterially mediated sulfate reduction also has a significant role on the mineral retention process. The formation of gypsum, rhodochrocite and siderite are by-products of alkalinity generating reactions in this system and may have an impact on S, Mn, and Fe solubility controls. Moreover, the buffering of acidity through excess alkalinity appears to facilitate the precipitation and retention of metals within the system.
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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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Dill, S., Cowan, J., Wood, A., & Bowell, R. J. (1998). (L. Nel Petrus Johannes, Ed.). Mine Water and Environmental Impacts. 2: Proceedings International Mine Water Association Symposium.
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Dillard, G. (2000). A win-win way to clean up by changing ionic state, new process can precipitate heavy metals. Pay Dirt, 734, 10–11.
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Rammlmair, D., & Grissemann, C. (2000). Natural attenuation in slag heaps versus remediation. In D. Rammlmair, J. Mederer, T. Oberthuer, R. B. Heimann, & H. J. Pentinghaus (Eds.), Applied mineralogy in research, economy, technology, ecology and culture (pp. 645–648).
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