Abstract: Much work has been undertaken on the design of treatment systems to remove iron from ochreous mine water discharges. Unlike iron, manganese removal is far more difficult and generally requires active chemical dosing rather than passive treatment. The need for manganese removal can therefore significantly change the economics, management attention and sustainability of a site. Understanding natural attenuation of manganese in river systems is therefore key to deciding whether (active) manganese treatment is needed to protect downstream receptors. Nuttall (2002, this volume) describes the effectiveness of the passive treatment system at Whittle in reducing both iron and manganese concentrations in ochreous mine waters. This paper discusses the results of in-river monitoring and provides evidence for manganese removal downstream of the discharge point. In addition to dilution, attenuation appears to be in the order of 20 to 50%, depending on relative rates of mine water discharge and river flows. Such attenuation means that active treatment may not be needed for the long-term operation of the Whittle scheme. Operation of the scheme commenced in July 2002, with monitoring to further examine evidence for manganese attenuation and any impact on the ecology of the recipient watercourses.

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.