Stephen C. Peters Charles A. Cravotta III, Jill E. Burrows 2015 <p><span>Water quality data collected in 2012 for 10 above- and 14 below-drainage coal mine discharges (CMDs), classified by mining or excavation method, in the anthracite region of Pennsylvania, USA, are compared with data for 1975, 1991, and 1999 to evaluate long-term (37&nbsp;year) changes in pH, SO</span>₄^2&minus;<span>, and Fe concentrations related to geochemistry, hydrology, and natural attenuation processes. We hypothesized that CMD quality will improve over time because of diminishing quantities of unweathered pyrite, decreased access of O</span>₂<span>&nbsp;to the subsurface after mine closure, decreased rates of acid production, and relatively constant influx of alkalinity from groundwater. Discharges from shafts, slopes, and boreholes, which are vertical or steeply sloping excavations, are classified as below-drainage; these receive groundwater inputs with low dissolved O</span>₂<span>, resulting in limited pyrite oxidation, dilution, and gradual improvement of CMD water quality. In contrast, discharges from drifts and tunnels, which are nearly horizontal excavations into hillsides, are classified as above-drainage; these would exhibit less improvement in water quality over time because the rock surfaces continue to be exposed to air, which facilitates sustained pyrite oxidation, acid production, and alkalinity consumption. Nonparametric Wilcoxon matched-pair signed rank tests between 1975 and 2012 samples indicate decreases in Fe and SO</span>₄^2&minus;<span>&nbsp;concentrations were highly significant (</span><i>p</i><span>&nbsp;&lt;&nbsp;0.05) and increases in pH were marginally significant (</span><i>p</i><span>&nbsp;&lt;&nbsp;0.1) for below-drainage discharges. For above-drainage discharges, changes in Fe and SO</span>₄^2&minus;<span>concentrations were not significant, and increases in pH were highly significant between 1975 and 2012. Although a greater proportion of above-drainage discharges were net acidic in 2012 compared to below-drainage discharges, the increase in pH between 1975 and 2012 was greater for above- (median pH increase from 4.4 to 6.0) compared to below- (median pH increase from 5.6 to 6.1) drainage discharges. For cases where O</span>₂<span>&nbsp;is limited, transformation of aqueous Fe</span>^II<span>&nbsp;species to Fe</span>^III<span>&nbsp;may be kinetically limited. In contrast, where O</span>₂<span>&nbsp;is abundant, aqueous Fe concentrations may be limited by Fe</span>^III<span>mineral precipitation; thus, trends in Fe may not follow those for SO</span>₄^2&minus;<span>. In either case, when the supply of alkalinity is sufficient to buffer decreased acidity, the pH could increase by a step trend from strongly acidic (3&ndash;3.5) to near neutral (6&ndash;6.5) values. Modeled equilibrium with respect to Fe</span>^III<span>&nbsp;precipitates varies with pH and Fe and SO</span>₄^2&minus;<span>reconcentrations: increasing pH promotes the formation of ferrihydrite, while decreasing concentrations of Fe limit the formation of ferrihydrite, and decreasing Fe and SO</span>₄^2&minus;<span>concentrations limit the precipitation of schwertmannite and favor formation of Fe</span>^III<span>hydroxyl complexes and uncomplexed Fe</span>²⁺<span>&nbsp;and Fe</span>³⁺<span>. The analysis of the long-term geochemical changes in CMDs in the anthracite field and the effect of the hydrologic setting on water quality presented in this paper can help prioritize CMD remediation and facilitate selection and design of the most appropriate treatment systems.</span></p> application/pdf 10.1016/j.apgeochem.2015.02.010 en Elsevier Temporal geochemical variations in above- and below-drainage coal mine discharge article