Abstract: In nature, pyrite is initially oxidized by atmospheric O2, releasing acidity and Fe2+. At pH below 3.5, Fe2+ is rapidly oxidized by T. ferrooxidans to Fe3+, which oxidizes pyrite at a much faster rate than O2. Commonly, limestone is used to prevent pyrite oxidation. This approach, however, has a short span of effectiveness because after treatment the surfaces of pyrite particles remain exposed to atmospheric O2 and oxidation continuous abiotically. Currently, a proposed mechanism for explaining non-microbial pyrite oxidation in high pH environments is the involvement of OH- in an inner-sphere electron-OH exchange between pyrite/surface-exposed disulfide and pyrite/surface-Fe(III)(OH)n3-n complex and/or formation of a weak electrostatic pyrite/surface-CO3 complex which enhances the chemical oxidation of Fe2+. The above infer that limestone application to pyritic geologic material treats only the symptoms of pyrite oxidation through acid mine drainage neutralization but accelerates non-microbial pyrite oxidation. Therefore, only a pyrite/surface coating capable of inhibiting O2 diffusion is expected to control long-term oxidation and acid drainage production. The objective of this study was to examine the feasibility in controlling pyrite oxidation by creating, on pyrite surfaces, an impermeable phosphate or silica coating that would prevent either O2 or Fe3+ from further oxidizing pyrite. The mechanism underlying this coating approach involves leaching mine waste with a coating solution composed of H2O2 or hypochlorite, KH2PO4 or H4SiO4, and sodium acetate (NaAC) or limestone. During the leaching process, H2O2 or hypochlorite oxidizes pyrite and produces Fe3+ so that iron phosphate or iron silicate precipitates as a coating on pyrite surfaces. The purpose of NaAC or limestone is to eliminate the inhibitory effect of the protons (produced during pyrite oxidation) on the precipitation of iron phosphate or silicate and to generate iron-oxide pyrite coating, which is also expected to inhibit pyrite oxidation. The results showed that iron phosphate or silicate coating could be established on pyrite by leaching it with a solution composed of: (1) H2O2 0.018-0.16 M; (2) phosphate or silicate 10-3 to 10-2 M; (3) coating-solution pH [approximate]5-6; and (4) NaAC as low as 0.01 M. Leachates from column experiments also showed that silicate coatings produced the least amount of sulfate relative to the control, limestone and phosphate treatments. On the other hand, limestone maintained the leachate near neutral pH but produced more sulfate than the control.

Abstract: Phosphate-induced metal stabilization involving the reactive medium Apatite II(TM) [Ca10-xNax(PO4)6-x(CO3)x(OH)2], where x < 1, was used in a subsurface permeable reactive barrier (PRB) to treat acid mine drainage in a shallow alluvial groundwater containing elevated concentrations of Zn, Pb, Cd, Cu, SO4 and NO3. The groundwater is treated in situ before it enters the East Fork of Ninemile Creek, a tributary to the Coeur d'Alene River, Idaho. Microbially mediated SO4 reduction and the subsequent precipitation of sphalerite [ZnS] is the primary mechanism occurring for immobilization of Zn and Cd. Precipitation of pyromorphite [Pb10(PO4)6(OH,Cl)2] is the most likely mechanism for immobilization of Pb. Precipitation is occurring directly on the original Apatite II. The emplaced PRB has been operating successfully since January of 2001, and has reduced the concentrations of Cd and Pb to below detection (2 μg L-1), has reduced Zn to near background in this region (about 100 μg L-1), and has reduced SO4 by between 100 and 200 mg L-1 and NO3 to below detection (50 μg L-1). The PRB, filled with 90 tonnes of Apatite II, has removed about 4550 kg of Zn, 91 kg of Pb and 45 kg of Cd, but 90% of the immobilization is occurring in the first 20% of the barrier, wherein the reactive media now contain up to 25 wt% Zn. Field observations indicate that about 30% of the Apatite II material is spent (consumed).

Abstract: Permeable reactive barriers are an emerging alternative to traditional pump and treat systems for groundwater remediation. This technique has progressed rapidly over the past decade from laboratory bench-scale studies to full-scale implementation. Laboratory studies indicate the potential for treatment of a large number of inorganic contaminants, including As, Cd, Cr, Cu, Hg, Fe, Mn, Mo, Ni, Pb, Se, Tc, U, V, NO3, PO4 and SO4. Small-scale field studies have demonstrated treatment of Cd, Cr, Cu, Fe, Ni, Pb, NO3, PO4 and SO4. Permeable reactive barriers composed of zero-valent iron have been used in full-scale installations for the treatment of Cr, U, and Tc. Solid-phase organic carbon in the form of municipal compost has been used to remove dissolved constituents associated with acid-mine drainage, including SO4, Fe, Ni, Co and Zn. Dissolved nutrients, including NO3 and PO4, have been removed from domestic septic-system effluent and agricultural drainage.