Abstract: As a result of the collapse of a mine tailing dam in april 1998 about 40 km of the Agrio and Guadiamar valleys were covered with a layer of pyrite sludge. Although most of the sludge was removed, a small amount remains in the soil of the Agrio valley and the aquifer remains polluted with acid water (ph<4) and metals (10 mg/L Zn, 5 mg/L Cu and Al). A permeable reactive barrier was build across the aquifer to increase the alcalinity and retain the metals. The barrier is made up of three sections of 30 m longX1.4 m thickX5 m deep (average) containing different proportions of limestone gravel, organic compost and zero-valent iron. The residence time of the water in the barrier is about two days. Within the barrier, the pH values increase to near neutral mainly due to calcite dissolution. Metals co-precipitate as oxyhydroxides, and they are also adsorbed on the organic matter surface. Down-stream the barrier, the total pollution removal is around 60-90% for Zn and Cu, and from 50 to 90% for Al and acidity.

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: When designing wetland treatment systems for trace metal removal, both aerobic and anaerobic processes can be incorporated into the final design. Aerobic processes such as adsorption and ion exchange can successfully treat neutral drainage in overlandflow systems. Acid drainage can be treated in anaerobic systems as a result of sulfate reduction processes which neutralize pH and precipitate metals.Test work on both aerobic and anaerobic systems has been conducted in Minnesota. For the past three years, overland flow test systems have successfully removed copper, cobalt, nickel and zinc from neutral mine drainage. Nickel, which is the major contaminant, has been reduced around 90 percent from 2 mg/L to 0.2 mg/L. A sulfate reduction system has successfully treated acid mine drainage for two years, increasing pH from 5 to over 7 and reducing concentrations of all metals by over 90 percent.Important factors to consider when designing wetlands to remove trace metals include not only the type of wetlandrequired but also the size of the system and the residence time needed to achieve the water quality standards.