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: 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.