skip to main content

Title: 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 ( 226 Ra + 228 Ra) and higher 228 Ra/ 226 Ra ratios. As with the Marcellus Shale, elemental ratios (Sr/Ca) and isotope ratios ( 87 Sr/ 86 Sr) can distinguish UPP produced waters from many conventional oil and gas formations. Sr/Ca and 87 Sr/ 86 Sr 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 87 Sr/ 86 Sr, 228 Ra/ 226 Ra ratios may be the more » best tracer to distinguish these waters. « less
; ;
Award ID(s):
Publication Date:
Journal Name:
Environmental Science: Processes & Impacts
Page Range or eLocation-ID:
1224 to 1232
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    The resurgence of oil and gas extraction in the Appalachian Basin has resulted in an excess of oil and gas brines in Pennsylvania, West Virginia, and Ohio. Primarily driven by unconventional development, this expansion has also impacted conventional wells and consequently, created economic pressure to develop effective and cheap disposal options. Using brine as a road treatment, directly or as a processed deicer, however, creates substantial concern that naturally occurring radioactive material in the brines can contaminate roads and road-side areas. Current decision making is based on risk exposure scenarios developed by regulatory agencies based on recreational users in rural areas and exposures to drivers during a typical commute. These scenarios are not appropriate for evaluating exposures to residential deicer users or people living near treated streets. More appropriate exposure scenarios were developed in this work and exposures predicted with these models based on laboratory measurements and literature data. Exposure scenarios currently used for regulatory assessment of brine road treatment result in predicted exposures of 0.4–0.6 mrem/year. Residential exposures predicted by the scenarios developed in this work are 4.6 mrem/year. If the maximum range of near-road soil radium concentrations observed in the region is used in this residential scenariomore »(60 pCi/g226Ra, 50 pCi/g228Ra), residents living near these roads would be exposed to an estimated 296 mrems/year, above regulatory exposure thresholds used in nuclear facility siting assessments. These results underline the urgent need to clarify exposure risks from the use of oil and gas brines as a road treatment, particularly given the existing disparities in the distribution of road impacts across socioeconomic status.

    « less
  2. Hydraulic fracturing of deep shale formations generates large volumes of wastewater that must be managed through treatment, reuse, or disposal. Produced wastewater liberates formation-derived radionuclides and contains previously uncharacterized organohalides thought to be generated within the shale well, both posing unknown toxicity to human and ecological health. Here, we assess the toxicity of 42 input media and produced fluid samples collected from four wells in the Utica formation and Marcellus Shale using two distinct endpoint screening assays. Broad spectrum acute toxicity was assessed using a bioluminescence inhibition assay employing the halotolerant bacterium Aliivibrio fischeri , while predictive mammalian cytotoxicity was evaluated using a N -acetylcysteine (NAC) thiol reactivity assay. The acute toxicity and thiol reactivity of early-stage flowback was higher than later produced fluids, with levels diminishing through time as the natural gas wells matured. Acute toxicity of early stage flowback and drilling muds were on par with the positive control, 3,5-dichlorophenol (6.8 mg L −1 ). Differences in both acute toxicity and thiol reactivity between paired natural gas well samples were associated with specific chemical additives. Samples from wells containing a larger diversity and concentration of organic additives resulted in higher acute toxicity, while samples from a well applyingmore »a higher composition of ammonium persulfate, a strong oxidizer, showed greater thiol reactivity, predictive of higher mammalian toxicity. Both acute toxicity and thiol reactivity are consistently detected in produced waters, in some cases present up to nine months after hydraulic fracturing. These results support that specific chemical additives, the reactions generated by the additives, or the constituents liberated from the formation by the additives contribute to the toxicity of hydraulic fracturing produced waters and reinforces the need for careful consideration of early produced fluid management.« less
  3. Abstract

    Recent advances in shale gas development have largely outpaced efforts to manage associated waste streams that pose significant environmental risks. Wastewater management presents significant challenges in the Marcellus shale, where increasing fluid volumes concomitant with expanding development will threaten to overwhelm existing infrastructure over the next decade. In this work, we forecast growth in drilling, flowback, and produced fluid volumes through 2025 based on historic data and consider conventional and alternative disposal options to meet future demands. The results indicate that nearly 12 million m3(74 MMbbl) of wastewater will be generated annually by 2025. Even assuming wastewater recycling rates in the region rebound, meeting increased demands for wastewater that cannot be reused due to poor quality or logistics would require significant capital investment to expand existing disposal pathways, namely treatment and discharge at centralized facilities or dedicated brine injection in Ohio. Here, we demonstrate the logistical and environmental advantages of an alternative strategy: repurposing depleted oil and gas wells for dedicated injection of wastewater that cannot otherwise be reused or recycled. Hubs of depleted wells could accommodate projected increases in wastewater volumes more efficiently than existing disposal options, primarily because the proximity of depleted wells to active production sitesmore »would substantially reduce wastewater transport distances and associated costs. This study highlights the need to reevaluate regional-scale shale wastewater management practices in the context of evolving wastewater qualities and quantities, as strategic planning will result in more socially and economically favorable options while avoiding adverse environmental impacts that have overshadowed the environmental benefits of natural gas expansion in the energy sector.

    « less
  4. Oil and gas (O&G) extraction generates large volumes of produced water (PW) in regions that are often water-stressed. In Wyoming, generators are permitted under the National Pollutant Discharge Elimination System (NPDES) program to discharge O&G PW for beneficial use. In one Wyoming study region, downstream of the NPDES facilities exist naturally occurring wetlands referred to herein as produced water retention ponds (PWRPs). Previously, it was found that dissolved radium (Ra) and organic contaminants are removed within 30 km of the discharges and higher-resolution sampling was required to understand contaminant attenuation mechanisms. In this study, we sampled three NPDES discharge facilities, five PWRPs, and a reference background wetland not impacted by O&G PW disposal. Water samples, grab sediments, sediment cores and vegetation were collected. No inorganic PW constituents were abated through the PWRP series but Ra was shown to accumulate within PWRP grab sediments, upwards of 2721 Bq kg −1 , compared to downstream sites. Ra mineral association with depth in the sediment profile is likely controlled by the S cycle under varying microbial communities and redox conditions. Under anoxic conditions, common in wetlands, Ra was available as an exchangeable ion, similar to Ca, Ba and Sr, and S was mostlymore »water-soluble. 226 Ra concentration ratios in vegetation samples, normalizing vegetation Ra to sediment Ra, indicated that ratios were highest in sediments containing less exchangeable 226 Ra. Sequential leaching data paired with redox potentials suggest that oxic conditions are necessary to contain Ra in recalcitrant sediment minerals and prevent mobility and bioavailability.« less
  5. Hydraulic fracturing requires the injection of large volumes of fluid to extract oil and gas from low permeability unconventional resources ( e.g. , shale, coalbed methane), resulting in the production of large volumes of highly complex and variable waste fluids. Shale gas fluid samples were collected from two hydraulically fractured wells in Morgantown, WV, USA at the Marcellus Shale Energy and Environment Laboratory (MSEEL) and analyzed using ultrahigh resolution mass spectrometry to investigate the dissolved organic sulfur (DOS) pool. Using a non-targeted approach, ions assigned DOS formulas were analyzed to identify dominant DOS classes, describe their temporal trends and their implications, and describe the molecular characteristics of the larger DOS pool. The average molecular weight of organic sulfur compounds in flowback decreased and was lowest in produced waters. The dominant DOS classes were putatively assigned to alcohol sulfate and alcohol ethoxysulfate surfactants, likely injected as fracturing fluid additives, on the basis of exact mass and homolog distribution matching. This DOS signature was identifiable 10 months after the initial injection of hydraulic fracturing fluid, and an absence of genes that code for alcohol ethoxysulfate degrading proteins ( e.g. , sulfatases) in the shale well genomes and metagenomes support that these additivesmore »are not readily degraded biologically and may continue to act as a chemical signature of the injected fluid. Understanding the diversity, lability, and fate of organic sulfur compounds in shale wells is important for engineering productive wells and preventing gas souring as well as understanding the consequences of unintended fluid release to the environment. The diversity of DOS, particularly more polar compounds, needs further investigation to determine if the identified characteristics and temporal patterns are unique to the analyzed wells or represent broader patterns found in other formations and under other operating conditions.« less