RESUMEN
Reducing and Alkalinity Producing Systems (RAPS) remediate net-acidic metalliferous mine drainage by creating anoxic conditions in which bacterial sulfate reduction (BSR) raises alkalinity and drives the precipitation of iron and other chalcophilic elements as sulfides. We report chemical and stable isotopic data from a study monitoring the biogeochemical processes involved in the generation of mine waters and their remediation by two RAPS. Sulfur isotopes show that sulfate in all mine waters has a common source (pyrite oxidation), whilst oxygen isotopes show that oxidation of pyritic sulfur is mediated by Fe(III)(aq). The isotopic composition of dissolved sulfide, combined with the sulfur and oxygen isotopic composition of sulfate in RAPS effluents, proves BSR and details its dual isotope systematics. The occurrence and isotopic composition of solid phase iron sulfides indicate the removal of reduced sulfur within the RAPS, with significant amounts of elemental sulfur indicating reoxidation steps. However, only 0 to 9% of solid phase iron occurs as Fe sulfides, with approximately 70% of the removed iron occurs as Fe(III) (hydr)oxides. Some of the (hydr)oxide is supplied to the wetland as solids and is simply filtered by the wetland substrate, playing no role in alkalinity generation or proton removal. However, the majority of iron is supplied as dissolved Fe(II), indicating that acid generating oxidation and hydrolysis reactions dominate iron removal. The overall contribution of BSR to the sulfur geochemistry in the RAPS is limited and sulfate retention is dominated by sulfate precipitation, comparable to aerobic treatment systems, and show that the proton acidity resulting from iron oxidation and hydrolysis must be subsequently neutralised by calcite dissolution and/or BSR deeper in the RAPS sediments. BSR is not as important as previously thought for metal removal in RAPS. The results have practical consequences for the design, treatment performance and long-term functionality of such systems.
Asunto(s)
Hierro/análisis , Azufre/análisis , Contaminantes del Agua/análisis , Purificación del Agua/métodos , Agua/química , Hierro/química , Isótopos , Oxidación-Reducción , Azufre/química , Isótopos de Azufre/análisis , Isótopos de Azufre/química , Contaminantes del Agua/químicaRESUMEN
A full-scale passive treatment system (PTS) was commissioned in 2003 to treat two net-acidic coal mine water discharges in the Durham coalfield, UK. The principal aim of the PTS was to decrease concentrations of iron (<177 mg L(-1)) and aluminium (<85 mg L(-1)) and to increase pH (>3.2) and alkalinity (> or =0 mg L(-1) CaCO(3) eq). Secondary objectives were to decrease zinc (<2.8 mg L(-1)), manganese (<20.5 mg L(-1)) and sulfate (<2120 mg L(-1)). Upon treatment, water qualities were improved by 84% in the case of Fe, 87% Al, 83% acidity, 51% Zn, 23% Mn and 29% SO(4)(2)(-). Alkalinity (74%) and pH (95% as H(+)) were increased. Area adjusted removal rates (Fe=1.49+/-0.66 g d(-1) m(-2); acidity=6.7+/-4.9 g d(-1) m(-2)) were low compared to design criteria, mainly due to load limitation. Disregarding seasonality effects, acidity removal and effluent pH were stable over time. A substantial temporal decrease in calcium and alkalinity generation suggests that limestone is increasingly armoured. Once pH is no longer buffered by the carbonate system, metals could be remobilized, putting treatment efficiency at risk.