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: Reactive treatment layers, containing labile organic carbon, were evaluated to determine their ability to promote sulfate reduction and metal sulfide precipitation within a tailings impoundment, thereby treating tailings effluent prior to discharge. Organic carbon materials, including woodchips and pulp waste, were mixed with the upper meter of tailings in two separate test cells, a third control cell contained only tailings. In the woodchip cell sulfate reduction rates were 500 mg L-1 a-1, (5.2 mmol L-1 a-1) this was coupled with the gradual removal of 350 mg L-1 Zn (5.4 mmol L-1). Decreased δ13CDIC values from -3‰ to as low as -12‰ indicated that sulfate reduction was coupled with organic carbon oxidation. In the pulp waste cell the most dramatic change was observed near the interface between the pulp waste amended tailings and the underlying undisturbed tailings. Sulfate reduction rates were 5000 mg L-1 a-1 (52 mmol L-1 a-1), Fe concentrations decreased by 80–99.5% (148 mmol L-1) and Zn was consistently <5 mg L-1. Rates of sulfate reduction and metal removal decreased as the pore water migrated upward into the shallower tailings. Increased rates of sulfate reduction in the pulp waste cell were consistent with decreased δ13CDIC values, to as low as -22‰, and increased populations of sulfate reducing bacteria. Lower concentrations of the nutrients, phosphorus, organic carbon and nitrogen in the woodchip material contribute to the lower sulfate reduction rates observed in the woodchip cell.