Priority pollutants and associated constituents in untreated and treated discharges from coal mining or processing facilities in Pennsylvania, USA

Abstract

Clean sampling and analysis procedures were used to quantify more than 70 inorganic constituents, including 35 potentially toxic or hazardous constituents, organic carbon, and other characteristics of untreated (influent) and treated (effluent) coal-mine discharges (CMD) at 38 permitted coal-mining or coal-processing facilities in the bituminous coalfield and 4 facilities in the anthracite coalfield of Pennsylvania. Of the 42 facilities sampled during 2011, 26 were surface mines, 11 were underground mines, and 5 were coal refuse disposal operations. Treatment of CMD with caustic soda (NaOH), lime (CaO or Ca(OH) 2 ), flocculent, or limestone was ongoing at 21%, 40%, 6%, and 4% of the facilities, respectively; no chemicals were added at the remaining facilities. All facilities with CMD treatment incorporated structures for active or passive aeration and settling of metal-rich precipitate. The untreated influent samples had wide ranges of pH (2.8&ndash;7.6), hot acidity (&minus;600 to 8000 mg/L as CaCO 3 ), specific conductance (SC; 253&ndash;13,000 &mu;S/cm), total dissolved solids (TDS; 168&ndash;18,100 mg/L), and associated dissolved (<0.45-&mu;m pore-size filter) constituents, including SO 4 (14.7&ndash;10,700 mg/L), Fe (<0.01 to 4100 mg/L), Mn (0.02&ndash;136 mg/L), Al (<0.01 to 128 mg/L), and Zn (<0.003 to 18.8 mg/L). Concentrations of Ag (<1 &mu;g/L), Hg (<1 &mu;g/L), Sn (<0.5 &mu;g/L), and CN (<0.01 mg/L) were below detection limits. Only one influent sample met permitted mine effluent (PME) limits plus dissolved-constituent criteria maximum concentration (CMC) thresholds for the protection of freshwater aquatic organisms. The pH of the treated effluent samples ranged from 5.5 to 11.9 and was greater than or equal to the pH of the corresponding influent at all sites. All the effluent samples met CMC levels for dissolved concentrations of Ag, As, Ba, Cd, Cl, Cr, Pb, Ni, Sb, Se, Tl, V, NH 3 , NO 2 , NO 3 , and CN; however, nine violated one or more of the PME limits for pH (<6, n = 1), net acidity (>0, n = 3), Fe (>7 mg/L, n = 1), or Mn (>5 mg/L, n = 8), plus one or more exceeded CMC levels for Al (>0.75 mg/L, n = 2), Co (>95 &mu;g/L, n = 5), Zn (>307 &mu;g/L, n = 1), Cu (>7.4 &mu;g/L, n = 1), or Se (>12.8 &mu;g/L, n = 3). Although CMC exceedances for Co and Zn were attributed to samples also violating the PME limit for pH or Mn, the samples that exceeded the CMC for Al, Cu, or Se met applicable PME limits for pH, Fe, and Mn. Furthermore, many of the pH-compliant effluents did not meet reference criteria for SO 4 and related measures of ionic strength, including TDS, SC, and osmotic pressure. The Wilcoxon matched-pair signed-ranks statistic was used to test if the overall difference between the effluent and influent pairs was equal to zero. Constituents that statistically were the same for effluent and influent ( p > 0.05) included flow rate, SC, osmotic pressure, hardness, alkalinity, total organic carbon (TOC), K, Cl, NO 3 , PO 4 , Sb, Sr, Br, Se, Mo, and V. Although temperature, dissolved oxygen, pH, Ca, and Na were greater in the effluent than the influent, most constituents decreased as a result of treatment, including TDS, acidity, SO 4 , Al, Fe, Mn, Mg, As, Ba, Be, Cd, Cr, Co, Cu, F, Pb, Ni, NH 3 , Tl, Ti, U, Zn, Zr, total phenols, total inorganic carbon (TIC), biological oxygen demand (BOD), and chemical oxygen demand (COD). Nevertheless, some constituents that decreased, such as SO 4 , still did not meet reference criteria. Findings from this study suggest that typical chemical or aerobic treatment of CMD to pH > 6 with removal of Fe to <7 mg/L and Mn to <5 mg/L may provide a reasonable measure of protection for aquatic life from priority pollutant metals and other toxic or hazardous constituents in effluent but may not be effective for achieving permissible or background levels for TDS, SC, osmotic pressure, or concentrations of SO 4 and some other pollutants, including Se, Br, and Cl, if present.