Geochemical and isotope analysis of produced water from the Utica/Point Pleasant Shale, Appalachian Basin.

While development of the Utica/Point Pleasant Shale (UPP) is extensive in Ohio (U.S.) and increasing in Pennsylvania and West Virginia, few studies report the chemistry of produced waters from UPP wells. These data have important implications for developing best management practices for handling and waste disposal, or identifying the fluid in the event of accidental spill events. Here, we evaluated the elemental and isotope chemistry of UPP produced waters from 26 wells throughout Ohio, Pennsylvania, and West Virginia to determine any unique fluid chemistries that could be used for forensic studies. Compared to the Marcellus, UPP produced waters contain higher activities of total radium (226Ra + 228Ra) and higher 228Ra/226Ra ratios. As with the Marcellus Shale, elemental ratios (Sr/Ca) and isotope ratios (87Sr/86Sr) can distinguish UPP produced waters from many conventional oil and gas formations. Sr/Ca and 87Sr/86Sr ratios can fingerprint small fractions (∼0.1%) of UPP produced water in freshwater. However, because Marcellus and UPP produced waters display similar major elemental chemistry (i.e., Na, Ca, and Cl) and overlapping ratios of Sr/Ca and 87Sr/86Sr, 228Ra/226Ra ratios may be the best tracer to distinguish these waters.

Accuracy of methods for reporting inorganic element concentrations and radioactivity in oil and gas wastewaters from the Appalachian Basin, U.S. based on an inter-laboratory comparison.

Accurate and precise analyses of oil and gas (O&G) wastewaters and solids (e.g., sediments and sludge) are important for the regulatory monitoring of O&G development and tracing potential O&G contamination in the environment. In this study, 15 laboratories participated in an inter-laboratory comparison on the chemical characterization of three O&G wastewaters from the Appalachian Basin and four solids impacted by O&G development, with the goal of evaluating the quality of data and the accuracy of measurements for various analytes of concern. Using a variety of different methods, analytes in the wastewaters with high concentrations (i.e., >5 mg L-1) were easily detectable with relatively high accuracy, often within ±10% of the most probable value (MPV). In contrast, often less than 7 of the 15 labs were able to report detectable trace metal(loid) concentrations (i.e., Cr, Ni, Cu, Zn, As, and Pb) with accuracies of approximately ±40%. Despite most labs using inductively coupled plasma mass spectrometry (ICP-MS) with low instrument detection capabilities for trace metal analyses, large dilution factors during sample preparation and low trace metal concentrations in the wastewaters limited the number of quantifiable determinations and likely influenced analytical accuracy. In contrast, all the labs measuring Ra in the wastewaters were able to report detectable concentrations using a variety of methods including gamma spectroscopy and wet chemical approaches following Environmental Protection Agency (EPA) standard methods. However, the reported radium activities were often greater than ±30% different to the MPV possibly due to calibration inconsistencies among labs, radon leakage, or failing to correct for self-attenuation. Reported radium activities in solid materials had less variability (±20% from MPV) but accuracy could likely be improved by using certified radium standards and accounting for self-attenuation that results from matrix interferences or a density difference between the calibration standard and the unknown sample. This inter-laboratory comparison illustrates that numerous methods can be used to measure major cation, minor cation, and anion concentrations in O&G wastewaters with relatively high accuracy while trace metal(loid) and radioactivity analyses in liquids may often be over ±20% different from the MPV.

Environmental and Human Health Impacts of Spreading Oil and Gas Wastewater on Roads.

Thirteen states in the United States allow the spreading of O&G wastewaters on roads for deicing or dust suppression. In this study, the potential environmental and human health impacts of this practice are evaluated. Analyses of O&G wastewaters spread on roads in the northeastern, U.S. show that these wastewaters have salt, radioactivity, and organic contaminant concentrations often many times above drinking water standards. Bioassays also indicated that these wastewaters contain organic micropollutants that affected signaling pathways consistent with xenobiotic metabolism and caused toxicity to aquatic organisms like Daphnia magna. The potential toxicity of these wastewaters is a concern as lab experiments demonstrated that nearly all of the metals from these wastewaters leach from roads after rain events, likely reaching ground and surface water. Release of a known carcinogen (e.g., radium) from roads treated with O&G wastewaters has been largely ignored. In Pennsylvania from 2008 to 2014, spreading O&G wastewater on roads released over 4 times more radium to the environment (320 millicuries) than O&G wastewater treatment facilities and 200 times more radium than spill events. Currently, state-by-state regulations do not require radium analyses prior to treating roads with O&G wastewaters. Methods for reducing the potential impacts of spreading O&G wastewaters on roads are discussed.