Complex Speciation and Distribution of Iron, Sulfur, and Trace Metals in Coal Mine Soils Reflect Grain- and Sub-Grain-Scale Heterogeneity during Pyrite Oxidative Dissolution

Historical coal mining practices have caused various soil and water hazards, particularly through the dumping of mine waste. The primary environmental risk associated with this waste is the leaching of toxic metals from dumps of spoil or refuse into the subsurface soil or into nearby water resources. The extent of metal release is controlled via the oxidative dissolution of pyrite and potential re-sequestration through secondary Fe oxides. The characterization of the dominant Fe-bearing phase and the distribution of trace metals associated with these phases was determined via electron microscopy, synchrotron-based X-ray micro-fluorescence (μ-XRF) element and redox mapping from shallow mine soils from an impacted watershed in Appalachian Ohio. The dominant Fe-bearing phases were: (1) unweathered to partially weathered pyrite; (2) pseudomorphic replacement of pyrite with Fe(III) oxides; (3) fine-grained Fe oxide surface coatings; and (4) discrete Fe(III) oxide grains. Thicker secondary coatings and larger particles were sulfate rich, whereas smaller grains and thinner coatings were sulfate poor. The discrete Fe oxide grains exhibited the highest concentrations of Cr, Mn, Ni, and Cu, and sub-grain-scale concentration trends (Mn > Cr > Ni > Cu) were consistent with bulk soil properties. Predicting future metal transport requires an understanding of metal speciation and distribution from the sub-grain scale to the pedon scale.