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.

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.