Jennifer S. Harkness

Iodide, Bromide, and Ammonium in Hydraulic Fracturing and Oil and Gas Wastewaters: Environmental Implications

The expansion of unconventional shale gas and hydraulic fracturing has increased the volume of the oil and gas wastewater (OGW) generated in the U.S. Here we demonstrate that OGW from Marcellus and Fayetteville hydraulic fracturing flowback fluids and Appalachian conventional produced waters is characterized by high chloride, bromide, iodide (up to 56 mg/L), and ammonium (up to 420 mg/L). Br/Cl ratios were consistent for all Appalachian brines, which reflect an origin from a common parent brine, while the I/Cl and NH4/Cl ratios varied among brines from different geological formations, reflecting geogenic processes. There were no differences in halides and ammonium concentrations between OGW originating from hydraulic fracturing and conventional oil and gas operations. Analysis of discharged effluents from three brine treatment sites in Pennsylvania and a spill site in West Virginia show elevated levels of halides (iodide up to 28 mg/L) and ammonium (12 to 106 mg/L) that mimic the composition of OGW and mix conservatively in downstream surface waters. Bromide, iodide, and ammonium in surface waters can impact stream ecosystems and promote the formation of toxic brominated-, iodinated-, and nitrogen disinfection byproducts during chlorination at downstream drinking water treatment plants. Our findings indicate that discharge and accidental spills of OGW to waterways pose risks to both human health and the environment.

Enhanced Formation of Disinfection Byproducts in Shale Gas Wastewater-Impacted Drinking Water Supplies

The disposal and leaks of hydraulic fracturing wastewater (HFW) to the environment pose human health risks. Since HFW is typically characterized by elevated salinity, concerns have been raised whether the high bromide and iodide in HFW may promote the formation of disinfection byproducts (DBPs) and alter their speciation to more toxic brominated and iodinated analogues. This study evaluated the minimum volume percentage of two Marcellus Shale and one Fayetteville Shale HFWs diluted by fresh water collected from the Ohio and Allegheny Rivers that would generate and/or alter the formation and speciation of DBPs following chlorination, chloramination, and ozonation treatments of the blended solutions. During chlorination, dilutions as low as 0.01% HFW altered the speciation toward formation of brominated and iodinated trihalomethanes (THMs) and brominated haloacetonitriles (HANs), and dilutions as low as 0.03% increased the overall formation of both compound classes. The increase in bromide concentration associated with 0.01-0.03% contribution of Marcellus HFW (a range of 70-200 μg/L for HFW with bromide = 600 mg/L) mimics the increased bromide levels observed in western Pennsylvanian surface waters following the Marcellus Shale gas production boom. Chloramination reduced HAN and regulated THM formation; however, iodinated trihalomethane formation was observed at lower pH. For municipal wastewater-impacted river water, the presence of 0.1% HFW increased the formation of N-nitrosodimethylamine (NDMA) during chloramination, particularly for the high iodide (54 ppm) Fayetteville Shale HFW. Finally, ozonation of 0.01-0.03% HFW-impacted river water resulted in significant increases in bromate formation. The results suggest that total elimination of HFW discharge and/or installation of halide-specific removal techniques in centralized brine treatment facilities may be a better strategy to mitigate impacts on downstream drinking water treatment plants than altering disinfection strategies. The potential formation of multiple DBPs in drinking water utilities in areas of shale gas development requires comprehensive monitoring plans beyond the common regulated DBPs.

Brine Spills Associated with Unconventional Oil Development in North Dakota

The rapid rise of unconventional oil production during the past decade in the Bakken region of North Dakota raises concerns related to water contamination associated with the accidental release of oil and gas wastewater to the environment. Here, we characterize the major and trace element chemistry and isotopic ratios ((87)Sr/(86)Sr, δ(18)O, δ(2)H) of surface waters (n = 29) in areas impacted by oil and gas wastewater spills in the Bakken region of North Dakota. We establish geochemical and isotopic tracers that can identify Bakken brine spills in the environment. In addition to elevated concentrations of dissolved salts (Na, Cl, Br), spill waters also consisted of elevated concentrations of other contaminants (Se, V, Pb, NH4) compared to background waters, and soil and sediment in spill sites had elevated total radium activities ((228)Ra + (226)Ra) relative to background, indicating accumulation of Ra in impacted soil and sediment. We observed that inorganic contamination associated with brine spills in North Dakota is remarkably persistent, with elevated levels of contaminants observed in spills sites up to 4 years following the spill events.

Evidence for Coal Ash Ponds Leaking in the Southeastern United States

Coal combustion residuals (CCRs), the largest industrial waste in the United States, are mainly stored in surface impoundments and landfills. Here, we examine the geochemistry of seeps and surface water from seven sites and shallow groundwater from 15 sites in five states (Tennessee, Kentucky, Georgia, Virginia, and North Carolina) to evaluate possible leaking from coal ash ponds. The assessment for groundwater impacts at the 14 sites in North Carolina was based on state-archived monitoring well data. Boron and strontium exceeded background values of 100 and 150 μg/L, respectively, at all sites, and the high concentrations were associated with low δ(11)B (-9‰ to +8‰) and radiogenic (87)Sr/(86)Sr (0.7070 to 0.7120) isotopic fingerprints that are characteristic of coal ash at all but one site. Concentrations of CCR contaminants, including SO4, Ca, Mn, Fe, Se, As, Mo, and V above background levels, were also identified at all sites, but contamination levels above drinking water and ecological standards were observed in 10 out of 24 samples of impacted surface water. Out of 165 monitoring wells, 65 were impacted with high B levels and 49 had high CCR-contaminant levels. Distinct isotope fingerprints, combined with elevated levels of CCR tracers, provide strong evidence for the leaking of coal ash ponds to adjacent surface water and shallow groundwater. Given the large number of coal ash impoundments throughout the United States, the systematic evidence for leaking of coal ash ponds shown in this study highlights potential environmental risks from unlined coal ash ponds.

Pre-drill Groundwater Geochemistry in the Karoo Basin, South Africa

Enhanced production of unconventional hydrocarbons in the United States has driven interest in natural gas development globally, but simultaneously raised concerns regarding water quantity and quality impacts associated with hydrocarbon extraction. We conducted a pre-development assessment of groundwater geochemistry in the critically water-restricted Karoo Basin, South Africa. Twenty-two springs and groundwater samples were analyzed for major dissolved ions, trace elements, water stable isotopes, strontium and boron isotopes, hydrocarbons and helium composition. The data revealed three end-members: a deep, saline groundwater with a sodium-chloride composition, an old, deep freshwater with a sodium-bicarbonate-chloride composition and a shallow, calcium-bicarbonate freshwater. In a few cases, we identified direct mixing of the deep saline water and shallow groundwater. Stable water isotopes indicate that the shallow groundwater was controlled by evaporation in arid conditions, while the saline waters were diluted by apparently fossil meteoric water originated under wetter climatic conditions. These geochemical and isotopic data, in combination with elevated helium levels, suggest that exogenous fluids are the source of the saline groundwater and originated from remnant seawater prior to dilution by old meteoric water combined with further modification by water-rock interactions. Samples with elevated methane concentrations (>14 ccSTP/kg) were strongly associated with the sodium-chloride water located near dolerite intrusions, which likely provide a preferential pathway for vertical migration of deeply sourced hydrocarbon-rich saline waters to the surface. This pre-drill evaluation indicates that the natural migration of methane- and salt-rich waters provides a source of geogenic contamination to shallow aquifers prior to shale gas development in the Karoo Basin.

Naturally Occurring versus Anthropogenic Sources of Elevated Molybdenum in Groundwater: Evidence for Geogenic Contamination from Southeast Wisconsin, United States

Molybdenum (Mo) is an essential trace nutrient but has negative health effects at high concentrations. Groundwater typically has low Mo (<2 μg/L), and elevated levels are associated with anthropogenic contamination, although geogenic sources have also been reported. Coal combustion residues (CCRs) are enriched in Mo, and thus present a potential anthropogenic contamination source. Here, we use diagnostic geochemical tracers combined with groundwater residence time indicators to investigate the sources of Mo in drinking-water wells from shallow aquifers in a region of widespread CCR disposal in southeastern Wisconsin. Samples from drinking-water wells were collected in areas near and away from known CCR disposal sites, and analyzed for Mo and inorganic geochemistry indicators, including boron and strontium isotope ratios, along with groundwater tritium-helium and radiogenic 4He in-growth age-dating techniques. Mo concentrations ranged from <1 to 149 μg/L. Concentrations exceeding the U.S. Environmental Protection Agency health advisory of 40 μg/L were found in deeper, older groundwater (mean residence time >300 y). The B (δ11B = 22.9 ± 3.5‰) and Sr (87Sr/86Sr = 0.70923 ± 0.00024) isotope ratios were not consistent with the expected isotope fingerprints of CCRs, but rather mimic the compositions of local lithologies. The isotope signatures combined with mean groundwater residence times of more than 300 years for groundwater with high Mo concentrations support a geogenic source of Mo to the groundwater, rather than CCR-induced contamination. This study demonstrates the utility of a multi-isotope approach to distinguish between fossil fuel-related and natural sources of groundwater contamination.

Hydrocarbon-Rich Groundwater above Shale-Gas Formations: A Karoo Basin Case Study

Horizontal drilling and hydraulic fracturing have enhanced unconventional hydrocarbon recovery but raised environmental concerns related to water quality. Because most basins targeted for shale-gas development in the USA have histories of both active and legacy petroleum extraction, confusion about the hydrogeological context of naturally occurring methane in shallow aquifers overlying shales remains. The Karoo Basin, located in South Africa, provides a near-pristine setting to evaluate these processes, without a history of conventional or unconventional energy extraction. We conducted a comprehensive pre-industrial evaluation of water quality and gas geochemistry in 22 groundwater samples across the Karoo Basin, including dissolved ions, water isotopes, hydrocarbon molecular and isotopic composition, and noble gases. Methane-rich samples were associated with high-salinity, NaCl-type groundwater and elevated levels of ethane, 4 He, and other noble gases produced by radioactive decay. This endmember displayed less negative δ13 C-CH4 and evidence of mixing between thermogenic natural gases and hydrogenotrophic methane. Atmospheric noble gases in the methane-rich samples record a history of fractionation during gas-phase migration from source rocks to shallow aquifers. Conversely, methane-poor samples have a paucity of ethane and 4 He, near saturation levels of atmospheric noble gases, and more negative δ13 C-CH4 ; methane in these samples is biogenic and produced by a mixture of hydrogenotrophic and acetoclastic sources. These geochemical observations are consistent with other basins targeted for unconventional energy extraction in the USA and contribute to a growing data base of naturally occurring methane in shallow aquifers globally, which provide a framework for evaluating environmental concerns related to unconventional energy development (e.g., stray gas).