Relations among pH, sulfate, and metals concentrations in anthracite and bituminous coal-mine discharges, Pennsylvania

Water-quality data for discharges from 140 abandoned mines in the Bituminous and Anthracite Coalfields of Pennsylvania illustrate relations among pH, sulfate, and dissolved metal concentrations. The pH for the 140 samples ranged from 2.7 to 7.3, with two modes at pH 2.5 to 4 (acidic) and 6 to 7 (near neutral). Generally, flow rates were smaller and solute concentrations were greater for low-pH samples; flow rates increased with pH. Although the pH distribution was similar for the bituminous and anthracite subsets, the bituminous discharges had smaller median flow rates, greater concentrations of sulfate, iron, and aluminum, and smaller concentrations of barium and lead than anthracite discharges with the same pH values. The observed relations between the pH and constituent concentrations can be attributed to (1) dilution of acidic water by alkaline ground water; (2) solubility control of aluminum, iron, manganese, barium, and lead by hydroxide, sulfate, and/or carbonate minerals; and (3) aqueous sulfate-complex formation. The formation of AlSO₄⁺ and AlHSO₄⁺² complexes adds to the total dissolved aluminum concentration at pH of equilibrium with aluminum hydroxide or hydroxysulfate minerals and can account for 10 to 20 times greater concentrations of dissolved aluminum in bituminous discharges compared to anthracite discharges at similar pH. Sulfate complexation also can account for 10 to 30 times greater concentrations of dissolved ferric iron concentrations at equilibrium with ferrihydrite (Fe(OH)₃) and/or schwertmannite (Fe₈O₈(OH)_4.5(SO₄)_1.75) at pH of 3 to 5. In contrast, lower barium and lead concentrations in bituminous than anthracite discharges indicates elevated sulfate concentration could decrease mobility of these metals by the formation of insoluble minerals such as barite (BaSO₄) or anglesite (PbSO₄). Most samples were saturated with barite, but none were saturated with anglesite. Hence, lead concentrations could be controlled by coprecipitation with barite and/or by adsorption to schwertmannite or another sulfate-bearing oxide.