Groundwater quality and geochemistry of West Virginia’s southern coal fields
Coal mining has been the dominant industry and land use in West Virginia’s southern coal fields since the mid-1800s. Mortality rates for a variety of serious chronic conditions, such as diabetes, heart disease, and some forms of cancer in Appalachian coal mining regions, are higher than in areas lacking substantial coal mining activity within the Appalachian Region or elsewhere in the United States. Causes of the increased mortality and morbidity are not clear, but poor diet, high rates of smoking, socioeconomic factors, and the quality of groundwater used by area residents are all possible contributing factors. This study was conducted by the U.S. Geological Survey in cooperation with the West Virginia Department of Health and Human Resources and the West Virginia Department of Environmental Protection, with grant support from the Centers for Disease Control and Prevention (CDC) to assess the quality of groundwater in southern West Virginia. The data from this assessment of groundwater quality may be used by the CDC and other agencies to potentially investigate the role or lack thereof of groundwater quality with respect to mortality and morbidity rates in the region. The study was conducted in a region where a high density of current or past coal mining combined with a lack of advanced sewage treatment could affect concentrations of commonly occurring constituents plus contaminants, including nitrate, trace metals, major ions, indicator bacteria, radon, hydrogen sulfide, and dissolved hydrocarbons. Because rural residential wells and mine outfalls are considered private sources of water in the region, and are therefore unregulated and unmonitored, water-quality data are sparse. To fill the data gap and assess the groundwater quality in the region, water-quality samples were collected from 60 sites in a 10-county area. The 60 sites sampled included 46 rural residential homeowner wells and 14 mine outfall discharges used for residential supply. For this study, all samples were collected prior to any filtration or other treatments, typically at the pressure tank, and are indicative of total and dissolved constituents in the untreated water. Generally, data for the 60 sites indicate that most waters sampled do not exceed thresholds for most U.S. Environmental Protection Agency (EPA) drinking-water standards and U.S. Geological Survey (USGS) drinking-water screening criteria. However, there were several notable exceptions. Turbidity exceeded the 5-Nephelometric Turbidity Unit (NTU) EPA treatment technique (TT) drinking-water standard in 14 of 60 (23 percent) sites sampled and exceeded the 1-NTU TT standard in 51 of 60 (85 percent) sites sampled. Turbidity is common in many wells in southern West Virginia and may be attributed to iron oxyhydroxide precipitates, sediment carried into the aquifers from the shallow soil zone due to improperly constructed or cased wells or transported to the aquifer in shallow stress-relief fracture zones or through permeable bedding-plane partings. For the sites sampled, 31 of 60 (52 percent) had pH values at, above, or below the upper and lower range of the EPA Secondary Maximum Contaminant Level (SMCL, 6.5–8.5 standard units). Of those 31 sites, 28 (90 percent) were indicative of acidic corrosive water and 3 (10 percent) were indicative of alkaline water. The Langelier Saturation Index (LSI), which is a measure of the corrosivity of the water, was computed for all sites sampled for the study. Eighty-two percent of the sites sampled had waters that were classified as corrosive, based on a LSI less than −0.5. Corrosive water has the potential to leach lead, copper, and other metals from lead, copper, galvanized, or lead-tin soldered connections in water lines. The chloride to sulfate mass ratio also was assessed with the alkalinity to indicate the potential to promote galvanic corrosion (PPGC) of water lines and plumbing fixtures. Only one of the sites (1.7 percent) classified as a corrosive water site, had a PPGC considered high; the remaining sites were classified as having either a moderate (53.3 percent) or low (45 percent) PPGC. Therefore, the type of plumbing systems sampled for this study may be affected by corrosive water, but the potential for leaching trace metals and other constituents from residential plumbing systems containing older galvanized pipes or lead-tin soldered copper pipes is moderate to low. The indicator bacteria total coliform and Escherichia coli ( E. coli ) also were detected in groundwater samples to varying degrees. Total coliforms, which are a broad class of indicator bacteria, are common in groundwater in southern West Virginia and were detected in 39 of the 60 sites (65 percent) sampled. The presence of total coliform bacteria is a potential indicator of surface contamination, due to improperly constructed or cased wells, or infiltration of soil or other surface contaminants into the aquifer or well bore. E. coli bacteria, however, are much more indicative of fecal contamination of groundwater from either human or animal sources, and 14 of the 60 (23 percent) sites sampled had detections of E. coli . Although only a few strains of E. coli are known pathogens, their presence in groundwater may be an indicator of other related pathogens such as viruses and should be regarded as a serious potential issue. Water treatment such as chlorination, ozonation, or ultraviolet light may be appropriate to kill potential pathogenic bacteria or viruses in the source water. Manganese and iron were prevalent contaminants in the groundwater samples collected for this study, with 30 of 60 (50 percent) sites analyzed for manganese and 25 of 60 (42 percent) sites analyzed for iron exceeding the proposed 50- and 300-micrograms per liter (µg/L) SMCL drinking-water standards, respectively, for aesthetic criteria such as taste, odor, or staining of plumbing fixtures. Fourteen of the 60 sites sampled (23 percent) had concentrations of manganese that exceeded the 300-µg/L USGS health-based screening level, and 1 site exceeded the 1,600-µg/L EPA drinking-water equivalent level, which is based on a lifetime exposure level. Sodium is another common constituent in groundwater within the study area. Sodium has an EPA health-based value (HBV) of 20 milligrams per liter (mg/L) for individuals who are on a sodium-restricted diet for blood pressure or other health reasons. Sodium concentrations exceeded the 20-mg/L EPA HBV in 27 of 60 (45 percent) samples. Radon, a naturally occurring carcinogenic radioactive gas known to cause lung cancer, was detected at concentrations at or exceeding the proposed 300-picocuries per liter (pCi/L) EPA Maximum Contaminant Level (MCL) in 12 of the 60 (20 percent) sites sampled. Sites with radon gas concentrations exceeding the 300-pCi/L proposed MCL have the potential for airborne concentrations of radon to exceed the 4-pCi/L indoor air standard. Inhalation of radon can cause lung cancer, and the 4-pCi/L indoor air standard is based on an inhalation standard. Therefore, homeowners whose wells have radon gas concentrations exceeding 300 pCi/L may be advised to have their indoor air tested to determine if indoor air concentrations exceed the 4-pCi/L indoor air standard established by the EPA. Various factors were analyzed statistically and graphically to determine whether they have an influence on groundwater quality within the study area, including topographic setting, well depth, type of mining (surface or underground), type of site (well or mine outfall), and geologic formation. Only geologic formation and the type of site sampled had strong statistical correlations with one or more of the constituents of concern for this study. The overall chemistry of outfalls (mine outfalls) and wells was significantly different, with a much higher dissolved oxygen content in outfalls than in wells. The dissolved oxygen content is the primary component driving the oxidation and reduction of minerals, and the precipitation of minerals that are saturated or super saturated with respect to various cations and anions. Median dissolved oxygen concentrations for the outfalls sampled was 8.75 mg/L, and only 0.4 mg/L for the wells sampled. Median concentrations of sulfate and selenium were much higher in waters from the outfalls sampled, with median concentrations of 73.75 mg/L and 2.35 µg/L, respectively, compared to the wells sampled, which had median concentrations of 18.3 mg/L and less than (<) the 0.05-µg/L method detection limit, respectively. The maximum selenium concentration was for a well, with a concentration of 16.6 µg/L. The geochemical processes that control sulfate and selenium concentrations in groundwater are similar and are the result of the oxidation of sulfide minerals such as pyrite and ferroselite. Iron and manganese concentrations were elevated in most of the wells sampled, with median concentrations of 269.5 and 124.5 µg/L, respectively, but were rarely detected in the outfalls sampled, with median concentrations of < 4.0 and < 0.4 µg/L, respectively. The difference in iron and manganese between wells and outfalls is indicative of the role of dissolved oxygen on processes controlling groundwater chemistry in the region. Three principal geologic formations were assessed for the study, and the overall chemistry for the Pocahontas, New River, and Kanawha Formations varied substantially with respect to several constituents. Concentrations of calcium, magnesium, and total dissolved solids were highest for sites sampled in the Pocahontas Formation, with median concentrations of 41.9, 18.6, and 312 mg/L, respectively. For constituents that are commonly associated with mining activity, the highest concentrations were for sites sampled in the New River Formation, with median concentrations of iron and manganese of 2,450 µg/L and 482 µg/L, respectively, and a median pH of 6.35 standard units. Concentrations of barium also were elevated in samples collected from sites in the New River Formation, with a median barium concentration of 184 µg/L. The source of the barium is not fully known but may be associated with commingling of shallow groundwater with deeper brines or dissolution of the mineral barite. The highest median sulfate concentrations were from sites sampled in the Pocahontas Formation, with a median concentration of 64.0 mg/L. Of the 12 sites at or exceeding the 300-pCi/L proposed drinking-water standard for radon, 8 (67 percent of MCL exceedances) were for sites deriving water from the Kanawha Formation, 3 (25 percent of MCL exceedances) were for sites deriving water from the New River Formation, and only 1 site was for water from the Pocahontas Formation (8 percent of proposed MCL exceedances). Dissolved hydrocarbons, including methane, ethane, propane, propene, n - and i -butane, 1-butene, n - and i -pentane, pentane, 2- and 3-ethyl pentane, hexane, and benzene were analyzed in samples collected from 59 of the 60 sites to assess the potential occurrence and sources of these trace gases in groundwater within the study area. Results of the analysis indicate that most of the gas is of shallow biogenic origin, possibly associated with coal-bed methane, but a subset of samples has a gas signature and a chloride to bromide ratio indicative of potential mixing with deeper thermogenic gases. Only 2 of the 59 (3.3 percent) sites sampled had concentrations of methane gas, which is a highly combustible and explosive gas, exceeding the 10 milligrams per kilogram level of concern established by the U.S. Office of Surface Mining Reclamation and Enforcement. Principal components analysis was used to assess the primary geochemical processes occurring in the aquifers sampled. The first principal component had significant positive loadings for bromide, chloride, silica, ammonia, barium, iron, manganese, and arsenic, and significant negative loadings for dissolved oxygen, potassium, nitrate, and uranium, and reflects reduction and oxidation (redox) processes occurring in deeper anoxic groundwater or shallow oxic groundwater. The strong positive loadings for iron, manganese, barium, and arsenic are correlated with reducing conditions often found deeper in the aquifer. More oxic water is correlated with oxidation of nitrogen species to nitrate and environmental mobilization of uranium and sulfate in shallow wells and mine outfalls.