Repository for Oil and Gas Energy Research (ROGER)

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Unconventional oil and gas development (UOGD) sometimes impacts water resources, including incidents of methane (CH4) migration from compromised wells and spills that degrade water with salts, organics, and metals. We hypothesized that contamination may be more common where UOGD overlaps with legacy coal, oil, and gas extraction. We tested this hypothesis on ∼7000 groundwater analyses from the largest U.S. shale gas play (Marcellus), using data mining techniques to explore UOGD contamination frequency. Corroborating the hypothesis, we discovered small, statistically significant regional correlations between groundwater chloride concentrations ([Cl]) and UOGD proximity and density where legacy extraction was extremely dense (southwestern Pennsylvania (SWPA)) but no such correlations where it was minimal (northeastern Pennsylvania). On the other hand, legacy extraction of shallow gas in SWPA may have lessened today’s gas leakage, as no regional correlation was detected for [CH4] in SWPA. We identify hotspots where [Cl] and [CH4] increase by 3.6 and 3.0 mg/L, respectively, per UOG well drilled in SWPA. If the [Cl] correlations document contamination via brines leaked from wellbores, impoundments, or spills, we calculate that thallium concentrations could exceed EPA limits in the most densely developed hotspots, thus posing a potential human health risk.

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A thorough understanding of produced water (PW) quality is critical to advance the knowledge and tools for effective PW management, treatment, risk assessment, and feasibility for beneficial reuse outside the oil and gas industry. This study provides the first step to better understand PW quality to develop beneficial reuse programs that are protective of human health and the environment. In total, 46 PW samples from unconventional operations in the Permian Basin and ten surface water samples from the Pecos River in New Mexico were collected for quantitative target analyses of more than 300 constituents. Water quality analyses of Pecos River samples could provide context and baseline information for the potential discharge and reuse of treated PW in this area. Temporal PW and river water quality changes were monitored for eight months in 2020. PW samples had total dissolved solids (TDS) concentrations ranging from 100,800–201,500 mg/L. Various mineral salts, metals, oil and grease, volatile and semi-volatile organic compounds, radionuclides, ammonia, hydraulic fracturing additives, and per- and polyfluoroalkyl substances were detected at different concentrations. Chemical characterization of organic compounds found in Pecos River water showed no evidence of PW origin. Isometric log-ratio Na-Cl-Br analysis showed the salinity in the Pecos River samples appeared to be linked to an increase in natural shallow brine inputs. This study outlines baseline analytical information to advance PW research by describing PW and surrounding surface water quality in the Permian Basin that will assist in determining management strategies, treatment methods, potential beneficial reuse applications, and potential environmental impacts specific to intended beneficial use of treated PW.

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The demand for natural gas has led to the development of techniques used to access unconventional oil and natural gas (UOG) resources, due to the novelty of UOG, the potential impacts to freshwater ecosystems are not fully understood. We used a dual pronged approach to study the effects of UOG development on microbial biodiversity and function via a laboratory microcosm experiment and a survey study of streams with and without UOG development within their watersheds. The microcosm experiment simulated stream contamination with produced water, a byproduct of UOG operations, using sediment collected from one high water-quality stream and two low water-quality streams. For the survey study, biofilm and sediment samples were collected from streams experiencing varying levels of UOG development. In the microcosm experiment, produced water decreased microbial aerobic and anaerobic CO2 production in the high water-quality stream sediment but had a positive effect on this microbial activity in the lower water-quality stream sediments, suggesting habitat degradation alters the response of microbes to contaminants. Results from the stream survey indicate UOG development alters stream water temperature, chemistry, sediment aerobic and anaerobic CO2 production, and microbial community biodiversity in both sediments and biofilms. Correlations among UOG associated land use, environmental, and microbial variables suggest increases in light availability and sediment delivery to streams, due to deforestation and land disturbance, impact stream microbial communities and their function. Consistent changes in the relative abundance of bacterial taxa suggest microorganisms may be good indicators of the environmental changes associated with UOG development. The observed impacts of UOG development on microbial community composition and carbon cycling could have cascading effects on stream health and broader ecosystem function.

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Unconventional oil and gas (UOG) extraction can augment energy supplies in countries with viable gas resources, but it risks damaging water resources. Water supply problems for fracking can also limit UOG extraction, especially in water-stressed regions. Regulations are one of the main tools used to minimize UOG extraction impacts on water resources. Many states in the US and Canada have extensive regulations to protect water resources during UOG extraction but they are often ineffective, either because they were poorly drafted or because they are not properly enforced. South Africa is a water-scarce, groundwater-dependent country that is considering UOG extraction in the future. South African groundwater experts were surveyed on what regulations are needed to protect groundwater resources and how to enforce them. This study recommends specific UOG extraction regulations to protect groundwater resources, which are not only relevant to South Africa, but also to other countries that extract UOG resources.

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Health studies report associations between metrics of residential proximity to unconventional oil and gas (UOG) development and adverse health endpoints. We investigated whether exposure through household groundwater is captured by existing metrics and a newly developed metric incorporating groundwater flow paths. We compared metrics with detection frequencies/concentrations of 64 organic and inorganic UOG-related chemicals/groups in residential groundwater from 255 homes (Pennsylvania n = 94 and Ohio n = 161). Twenty-seven chemicals were detected in ≥20% of water samples at concentrations generally below U.S. Environmental Protection Agency standards. In Pennsylvania, two organic chemicals/groups had reduced odds of detection with increasing distance to the nearest well: 1,2-dichloroethene and benzene (Odds Ratio [OR]: 0.46, 95% confidence interval [CI]: 0.23–0.93) and m- and p-xylene (OR: 0.28, 95% CI: 0.10–0.80); results were consistent across metrics. In Ohio, the odds of detecting toluene increased with increasing distance to the nearest well (OR: 1.48, 95% CI: 1.12–1.95), also consistent across metrics. Correlations between inorganic chemicals and metrics were limited (all |ρ| ≤ 0.28). Limited associations between metrics and chemicals may indicate that UOG-related water contamination occurs rarely/episodically, more complex metrics may be needed to capture drinking water exposure, and/or spatial metrics in health studies may better reflect exposure to other stressors.

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Regulatory agencies routinely assess the presence of stray gas release from unconventional gas wells by sampling for methane in nearby groundwater after the well is drilled or if citizens complain about methane in their water. We studied whether methane concentrations in groundwater naturally vary through time in a shale gas basin where unconventional development and hydraulic fracturing has not yet occurred, to test the assumption that pre-drilling observations of well water quality can be reliable measures for assessing impacts of later gas drilling. We collected groundwater samples from 11 domestic wells in New York monthly for 13 months for methane and ion concentrations in a highly gas productive part of the Appalachian basin where fracking has been banned. Changing methane concentrations correlated with changes in chloride and bromide, indicating changing mixtures of shallow freshwater and deeper formation brine extracted by the wells through time. The hydrogeologic setting of a water well can cause variability in methane concentrations that may mimic stray gas but cannot be attributable to gas drilling. For this reason, before and after testing has limited utility to distinguish impacts of gas drilling from other causes of changing methane concentrations unless that testing includes sampling a comprehensive set of ions multiple times prior to drilling.

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Advances in water treatment technologies paired with potential restrictions on oil and gas (O the sole major breakthrough has been in the development of salt-tolerant fracturing chemicals that allow for reuse of produced water for fracking operations. Guided research should assist in the development of fit-for-purpose solutions to maximize the reuse of treated produced water. This is exemplified by the case studies presented here that detail currently operating treatment facilities for reclamation and reuse of produced water.

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Quantifying impacts of unconventional oil and gas production on water resources and aquatic habitats is critical for developing management approaches for mitigation. The study objective was to evaluate impacts of oil and gas production on groundwater and surface water and assess approaches to reduce these impacts using the Permian Basin as a case study. Water demand for hydraulic fracturing (HF) was compared to water supplies. We also examined contamination from surface spills. Results show that water demand for HF peaked in 2019, representing ~28% of water use in non-mining sectors. Most HF water was sourced from aquifers with ~1100 wells drilled in the Ogallala aquifer in 2019. The State monitoring network did not show regional groundwater depletion but was not sufficiently dense to address local impacts. Groundwater depletion is more critical in the western Delaware Basin within the Permian Basin because groundwater is connected to large flowing springs (e.g. San Solomon Springs) and to the Pecos River which has total dissolved solids ranging from ~3000 to 14,000 mg/L. Most produced water (70–80%) is disposed in shallow geologic units that could result in overpressuring and potential groundwater contamination from leakage through ~70,000 abandoned oil wells, including orphaned wells. While there is little evidence of leakage from abandoned wells, the state monitoring system was not designed to assess leakage from these wells. Oil spill counts totaled ~11,000 in the Permian (2009–2018). Approaches to mitigating adverse impacts on water management include reuse of PW for HF; however, there is an excess of PW in the Delaware Basin. Treatment and reuse in other sectors outside of oil and gas are also possibilities. Data gaps include reporting of water sources for HF, PW quality data required for assessing treatment and reuse, subsurface disposal capacity for accommodating PW, and spills from PW in Texas.

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Conflicting evidence exists as to whether or not unconventional oil and gas (UOG) development has enhanced methane transport into groundwater aquifers over the past 15 years. In this study, recent groundwater samples were collected from 90 domestic wells and 4 springs in Northeastern Pennsylvania located above the Marcellus Shale after more than a decade of UOG development. No statistically significant correlations were observed between the groundwater methane level and various UOG geospatial metrics, including proximity to UOG wells and well violations, as well as the number of UOG wells and violations within particular radii. The δ13C and methane-to-higher chain hydrocarbon signatures suggested that the elevated methane levels were not attributable to UOG development nor could they be explained by using simple biogenic–thermogenic end-member mixing models. Instead, groundwater methane levels were significantly correlated with geochemical water type and topographical location. Comparing a subset of contemporary methane measurements to their co-located pre-drilling records (n = 64 at 49 distinct locations) did not indicate systematic increases in methane concentration but did reveal several cases of elevated concentration (n = 12) across a spectrum of topographies. Multiple lines of evidence suggested that the high-concentration groundwater methane could have originated from shallow thermogenic methane that migrated upward into groundwater aquifers with Appalachian Basin brine.

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Skip to Next Section A comprehensive programme of baseline groundwater hydrochemical monitoring has been carried out in connection with the proposed hydraulic fracturing of a 2 to 3 km deep Bowland Shale gas reservoir in borehole KM8 at Kirby Misperton, North Yorkshire, UK. The monitoring infrastructure encompassed: five on-site boreholes with hydraulically open intervals ranging from shallow weathered cover to a c. 200 m deep Corallian limestone aquifer, six off-site wells (hydraulically open in superficial materials and/or Kimmeridge Clay) and four surface water monitoring stations. Groundwater chemistry was high stratified with depth, ranging from slightly acidic, fresh, very hard Ca-HCO3-SO4 waters in shallow weathered cover, to brackish, calcium-depleted, highly alkaline waters in the Corallian aquifer. Dissolved methane was detected in most boreholes, with 10 µg/L being typical of shallow boreholes and around 50 mg/L in the Corallian. Low ethane concentrations and isotopic evidence suggest that the methane was predominantly microbial in origin (carboxylate fermentation at shallow depth, natural methanogenic CO2 reduction at greater depth). Elevated dissolved ethane (20-30 µg/L) was found in one well of intermediate depth, suggesting admixture of a possible thermogenic component, although this could be derived directly from the Kimmeridge Clay penetrated by the well.

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The expansion of petroleum resource development has led to growing concern regarding greenhouse gas emissions from fugitive gas migration, which occurs at some wells due to well integrity failure. In this study, we quantify methane surface expression and emissions resulting from gas migration using a number of complementary techniques, and thereby evaluate surface expression processes as well as the strengths and limitations of the monitoring techniques. Methane emissions were found to be highly localized and variable over time. Injected gas reached the surface via preferential pathways through the soils and also along an installed groundwater monitoring well. Cumulative emissions were estimated from flux chamber measurements to be 3.8–6.5% of the injected gas; whereas eddy covariance (EC) data inferred approximately 26% of the injected gas was released to the atmosphere. Together these methods provide enhanced interpretation of surface expression at the site, advance our understanding on fugitive gas migration from integrity compromised energy wells and provide insights to improve monitoring and detection strategies with a view to reducing future greenhouse gas emissions. Moreover that, up to 75% of fugitive gas released at the site remained in the subsurface, shows that capillary barriers will mitigate greenhouse gas emissions from leaky wells; however, may infer greater potential for impacts on groundwater resources, if present.

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Both unconventional and conventional oil and gas production have led to instances of brine contamination of near-surface environments from spills of saline produced waters. Strontium isotope ratios (87Sr/86Sr) have been used as a sensitive tracer of sources of brine contamination in surface waters and shallow aquifers in areas where oil and gas production are limited to only a few reservoirs and produced water sources are well-defined. Recent expansion of conventional and unconventional oil and gas production to additional tight formations within sedimentary basins has resulted in production of formation waters from multiple oil and gas reservoirs that may have similar chemical and isotopic ratios, including 87Sr/86Sr. This study evaluates the utility of 87Sr/86Sr, the most widely available tracer dataset beyond major ion chemistry and water stable isotopes, as a tracer of brine contamination related to conventional and unconventional oil and gas production in the Williston, Appalachian and Permian basins. Multiple stacked oil and gas reservoirs within each basin have overlapping formation water 87Sr/86Sr, based on a non-parametric statistical test. For example, in the Appalachian Basin, produced waters from unconventional gas production in the Middle Devonian Marcellus and Upper Ordovician Utica shales have overlapping 87Sr/86Sr. In the Permian Basin, produced waters from the unconventional Pennsylvanian-Permian Wolfcamp Shale and conventional and unconventional Pennsylvanian Cisco/Canyon/Strawn formations have similar 87Sr/86Sr. In the Williston Basin produced waters from Late Devonian to Early Mississippian Bakken Formation unconventional oil production have overlapping 87Sr/86Sr with produced waters associated with minor production of conventional oil from the Middle Devonian Winnipegosis. Improved spatial characterization of 87Sr/86Sr and other isotopic signatures of produced waters from various oil/gas reservoirs are needed to constrain geographic and depth variability of produced waters in hydrocarbon producing regions. This is particularly important, as unconventional oil and gas production expands in areas of existing conventional oil and gas production, where delineating sources of saline produced waters in cases of accidental surface spills or subsurface leakage will become a greater challenge. Sr isotopes alone may not be able to distinguish produced waters in areas with overlapping production from reservoirs with similar isotopic signatures.

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Lightly salted surface waters Hydraulic fracturing uses a water-based mixture to open up tight oil and gas formations. The process is mostly contained, but concerns remain about the potential for surface water contamination. Bonetti et al. found a small increase in certain ions associated with hydraulic fracturing across several locations in the United States (see the Perspective by Hill and Ma). These small increases appeared 90 to 180 days after new wells were put in and suggest some surface water contamination. The magnitude appears small but may require that more attention be paid to monitoring near-well surface waters. Science, aaz2185, this issue p. 896; see also abk3433, p. 853 The impact of unconventional oil and gas development on water quality is a major environmental concern. We built a large geocoded database that combines surface water measurements with horizontally drilled wells stimulated by hydraulic fracturing (HF) for several shales to examine whether temporal and spatial well variation is associated with anomalous salt concentrations in United States watersheds. We analyzed four ions that could indicate water impact from unconventional development. We found very small concentration increases associated with new HF wells for barium, chloride, and strontium but not bromide. All ions showed larger, but still small-in-magnitude, increases 91 to 180 days after well spudding. Our estimates were most pronounced for wells with larger amounts of produced water, wells located over high-salinity formations, and wells closer and likely upstream from water monitors. A small but detectable increase in salt concentration associated with hydraulic fracturing appears in surface waters. A small but detectable increase in salt concentration associated with hydraulic fracturing appears in surface waters.

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Tapping into oil and gas reserves comes at the expense of contaminating water Tapping into oil and gas reserves comes at the expense of contaminating water

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Following the large increase in unconventional hydrocarbon production in North America and elsewhere in the last 15 years, many jurisdictions have implemented groundwater monitoring programs to verify whether these subsurface industrial activities impact shallow groundwater quality. The interpretation of groundwater monitoring results typically relies mostly on dissolved alkane chemical and isotopic composition to infer the potential presence of thermogenic hydrocarbons presumed to originate from a deep source, which may indicate contamination. However, ambiguous results are frequently obtained, and post-genetic processes are often suspected to have modified the original gas composition. Here, we present a systematic approach to identify alkane origin with greater certainty, by thoroughly investigating four processes that may affect dissolved hydrocarbon gas: 1) late-stage methanogenesis, 2) oxidation (of methane or higher alkanes), 3) mixing between different gas sources, and 4) secondary methanogenesis. This is achieved by using empirical equations and fractionation factors available in the literature, combined to site-specific isotopic tracers (δ13CCH4, δ2HCH4, δ2HH2O, δ13CDIC) in groundwater samples. This approach is being tested and applied to a study area located in southern New Brunswick, Canada. The area overlies the McCully gas field from which unconventional natural gas is produced since 2003, and the nearby Elgin area, a prospective area for condensates. Results demonstrate that the presence of methane in groundwater is not related to the proximity of gas wells. In a few shallow wells located very close to producing gas wells in the McCully gas field, methane and ethane were detected, and the compositional and isotopic data sometimes seemed to point towards a thermogenic origin. However, consideration of the four processes led to the conclusion that the gas was of microbial origin, and that it had been oxidized to various levels. In contrast, thermogenic gas was detected in groundwater in the Elgin area, where no commercial production has yet taken place. In this area the natural hydrocarbon gas context is more complex, and the gas from some of the wells was affected by mixing, oxidation, and late-stage methanogenesis. Finally, the approach used in this paper has proven capable of disentangling the original isotopic signature from post-genetic modifications and, despite initial ambiguity, has shown no evidence that past hydraulic fracturing in the McCully gas field has affected shallow groundwater quality.

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Oil shale has received attention as an alternative energy source to petroleum because of its abundant reserves. Exploitation of oil shale can be divided into two types: ex situ and in situ exploitation. In situ transformation has been favoured because of its various advantages. Heating of oil shale leads to the production of oil and gas. To explore the influence of solid residue after pyrolysis of oil shale on the groundwater environment, we performed ultrapure water–rock interaction experiments. The results showed that Pb tended to accumulate in solid residues during pyrolysis. Additionally, the Pb concentration goes up in the immersion solution over time and as the pyrolysis temperature increased. In contrast, when we measured the soaking data of benzene series, the concentrations of benzene and toluene produced at temperatures over 350 ℃ were highest in the four oil shale pyrolysis samples after pyrolysis. The water–rock interaction experiment for 30 days led to benzene and toluene concentrations that were 104 and 1070-fold over the limit of China’s standards for groundwater quality. Over time, the content of benzene series was attenuated via biological actions. The results show that in situ oil shale mining can lead to continuous pollution in the groundwater environment.

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The potential contamination of shallow groundwater with inorganic constituents is a major environmental concern associated with shale gas extraction through hydraulic fracturing. However, the impact of shale gas development on groundwater quality is a highly controversial issue. The only way to reliably assess whether groundwater quality has been impacted by shale gas development is to collect pre-development baseline data against which subsequent changes in groundwater quality can be compared. The objective of this paper is to provide a conceptual and methodological framework for establishing a baseline of inorganic groundwater quality in shale gas areas, which is becoming standard practice as a prerequisite for evaluating shale gas development impacts on shallow aquifers. For this purpose, this paper first reviews the potential sources of inorganic contaminants in shallow groundwater from shale gas areas. Then, it reviews the previous baseline studies of groundwater geochemistry in shale gas areas, showing that a comprehensive baseline assessment includes documenting the natural sources of salinity, potential geogenic contamination, and potential anthropogenic influences from legacy contamination and surface land use activities that are not related to shale gas development. Based on this knowledge, best practices are identified in terms of baseline sampling, selection of inorganic baseline parameters, and definition of threshold levels.

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Oil and gas development has led to environmental hazards and community concerns, particularly in relation to water supply issues. Filing complaints with state agencies enables citizens to register concerns and seek investigations. We evaluated associations between county-level socio-economic and demographic factors, oil and gas drilling, and three outcomes in Pennsylvania between 2004 and 2016: number of oil and gas complaints filed, and both the number and proportion of state investigations of water supply complaints yielding a confirmed water supply impairment (i.e., “positive determination”). We used hierarchical Bayesian Poisson and binomial regression analyses. From 2004 to 2016, 9,404 oil and gas-related complaints were filed, of which 4,099 were water supply complaints. Of those, 3,906 received investigations, and 215 yielded positive determinations. We observed a 47% increase in complaints filed per $10,000 increase in annual median household income (MHI) (Rate Ratio [RR]: 1.47, 95% credible interval [CI]: 1.09–1.96) and an 18% increase per 1% increase in educational attainment (RR: 1.18, 95% CI: 1.11–1.26). While the number of complaints filed did not vary by race/ethnicity, the odds of a complaint yielding a positive determination were 0.81 times lower in counties with a higher proportion of marginalized populations (Odds Ratio [OR]: 0.81 per 1% increase in percent Black, Asian, and Native American populations combined, 95% CI: 0.64–0.99). The odds of positive determinations were also lower in areas with higher income (OR per $10,000 increase in MHI: 0.35, 95% CI: 0.09–0.96). Our results suggest these relationships are complex and may indicate potential environmental and procedural inequities, warranting further investigation.

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Recent natural gas development by means of hydraulic fracturing requires a detailed risk analysis to eliminate or mitigate damage to the natural environment. Such geo-energy related subsurface activities involve complex engineering processes and uncertain data, making comprehensive, quantitative risk assessments a challenge to develop. This research seeks to develop a risk framework utilising data for quantitative numerical analysis and expert knowledge for qualitative analysis in the form of fuzzy logic, focusing on hydraulically fractured wells during the well stimulation stage applied to scenarios in the UK and Canada. New fault trees are developed for assessing cement failure in the vertical and horizontal directions, resulting in probabilities of failure of 3.42% and 0.84%, respectively. An overall probability of migration to groundwater during the well injection stage was determined as 0.0006%, compared with a Canadian case study which considered 0.13% of wells failed during any stage of the wells life cycle. It incorporates various data types to represent the complexity of hydraulic fracturing, encouraging a more complete and accurate analysis of risk failures which engineers can directly apply to old and new hydraulic fracturing sites without the necessity for extensive historic and probabilistic data. This framework can be extended to assess risk across all stages of well development, which would lead to a gap in the modelled and actual probabilities narrowing. The framework developed has relevance to other geo-energy related subsurface activities such as CO2 sequestration, geothermal, and waste fluid injection disposal.

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As oil production in the Permian Basin surges, the impact of shale production on groundwater resources has become a growing concern. Most existing studies focus on the impact of shale production on shallow freshwater aquifers. There is little understanding of the shale development’s impact on other groundwater resources (e.g., deep carbonate aquifers and deep basin meteoric aquifers). The possible natural hydraulic connections between shallow aquifers and formation water suggest such an impact can be consequential. This study explores the relationship between shale production and groundwater using produced water (PW) samples from active unconventional oil wells. Focusing on the most productive portion of the Permian Basin—the four-county region in Southeast New Mexico between 2007 and 2016, a large produced water dataset allows us to analyze the conditional correlations between shale oil production and PW constituents. The results suggest that (1) expanding from primarily conventional wells to unconventional wells during the recent shale boom has led to dramatic increases of the TDS, chloride, sodium, and calcium levels in groundwater (i.e., producing formation). (2) Nearby oil well density positively correlates with the TDS, chloride, and sodium levels in the PW samples.

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Extensive development of horizontal drilling and hydraulic fracturing enhanced energy production but raised concerns about drinking-water quality in areas of shale-gas development. One particularly controversial case that has received significant public and scientific attention involves possible contamination of groundwater in the Trinity Aquifer in Parker County, Texas. Despite extensive work, the origin of natural gas in the Trinity Aquifer within this study area is an ongoing debate. Here, we present a comprehensive geochemical dataset collected across three sampling campaigns along with integration of previously published data. Data include major and trace ions, molecular gas compositions, compound-specific stable isotopes of hydrocarbons (δ13C-CH4, δ13C-C2H6, δ2H-CH4), dissolved inorganic carbon (δ13C-DIC), nitrogen (δ15N-N2), water (δ18O, δ2H, 3H), noble gases (He, Ne, Ar), boron (δ11B) and strontium (87Sr/86Sr) isotopic compositions of water samples from 20 drinking-water wells completed in the Trinity Aquifer. The compendium of data confirms mixing between a deep, naturally occurring salt- (Cl >250 mg/L) and hydrocarbon-rich groundwater with a low-salinity, shallower, and younger groundwater. Hydrocarbon gases display strong evidence for sulfate reduction-paired oxidation, in some cases followed by secondary methanogenesis. A subset of drinking-water wells contains elevated levels of hydrocarbons and depleted atmospherically-derived gas tracers, which is consistent with the introduction of fugitive thermogenic gas. We suggest that gas originating from the intermediate-depth Strawn Group (“Strawn”) is flowing within the annulus of a Barnett Shale gas well, and is subsequently entering the shallow aquifer system. This interpretation is supported by the expansion in the number of affected drinking-water wells during our study period and the persistence of hydrocarbon levels over time. Our data suggest post-genetic secondary water quality changes occur following fugitive gas contamination, including sulfate reduction paired with hydrocarbon oxidation and secondary methanogenesis. Importantly, no evidence for upward migration of brine or natural gas associated with the Barnett Shale was identified.

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The presence of methane and other hydrocarbons in domestic-use groundwater aquifers poses significant environmental and human health concerns. Isotopic measurements are often relied upon as indicators of groundwater aquifer contamination with methane. While these parameters are used to infer microbial metabolisms, there is growing evidence that isotopes present an incomplete picture of subsurface microbial processes. This study examined the relationships between microbiology and chemistry in groundwater wells located in the Denver-Julesburg Basin of Colorado, a rapidly urbanizing area with active oil and gas development. A primary goal was to determine if microbial data can reliably indicate the quantities and sources of groundwater methane. Comprehensive chemical and molecular analyses were performed on 39 groundwater well samples from five aquifers. Elevated methane concentrations were found in only one aquifer, and both isotopic and microbial data support a microbial origin. Microbial parameters had similar explanatory power as chemical parameters for predicting sample methane concentrations. Furthermore, a subset of samples with unique microbiology corresponded with unique chemical signatures that may be useful indicators of methane gas migration, potentially from nearby coal seams interacting with the aquifer. Microbial data may allow for more accurate determination of groundwater contamination and improved long-term water quality monitoring compared solely to isotopic and chemical data in areas with microbial methane.

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The interactions between old abandoned wellbores of suspect well integrity with hydraulic fracturing (HF), enhanced oil recovery (EOR), or salt water disposal (SWD) operations can result in upward leakage of deep aqueous liquids into overlying aquifers. This potential for upward fluid migration is largely unquantified as monitoring abandoned wells is rarely done, and leakage may go unnoticed especially when in deeper aquifers. This study performs a proximity analysis between old abandoned wells and HF, EOR, and SWD wells, and identifies commingled old abandoned wellbores, which are those wells where groundwater may flow from one aquifer to one or more other aquifers, to identify the locations with the greatest potential for upward aqueous fluid migration at three study sites in the Western Canadian Sedimentary Basin. Our analysis indicates that at all three study sites there are several locations where HF, EOR, or SWD operations are located in close proximity to a given old abandoned well. Much of this overlap occurs in formations above typically produced hydrocarbon reservoirs but below exploited potable aquifers, otherwise known as the intermediate zone, which is often connected between abandonment plugs in old abandoned wells. Information on the intermediate zone is often lacking, and this study suggests that unanticipated alterations to groundwater flow systems within the intermediate zone may be occurring. Results indicate the need for more field-based research on the intermediate zone.

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The rise of hydraulic fracturing and unconventional oil and gas (UOG) exploration in the United States has increased public concerns for water contamination induced from hydraulic fracturing fluids and associated wastewater spills. Herein, we collected surface and groundwater samples across Garfield County, Colorado, a drilling-dense region, and measured endocrine bioactivities, geochemical tracers of UOG wastewater, UOG-related organic contaminants in surface water, and evaluated UOG drilling production (weighted well scores, nearby well count, reported spills) surrounding sites. Elevated antagonist activities for the estrogen, androgen, progesterone, and glucocorticoid receptors were detected in surface water and associated with nearby shale gas well counts and density. The elevated endocrine activities were observed in surface water associated with medium and high UOG production (weighted UOG well score-based groups). These bioactivities were generally not associated with reported spills nearby, and often did not exhibit geochemical profiles associated with UOG wastewater from this region. Our results suggest the potential for releases of low-saline hydraulic fracturing fluids or chemicals used in other aspects of UOG production, similar to the chemistry of the local water, and dissimilar from defined spills of post-injection wastewater. Notably, water collected from certain medium and high UOG production sites exhibited bioactivities well above the levels known to impact the health of aquatic organisms, suggesting that further research to assess potential endocrine activities of UOG operations is warranted.

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The expansion of unconventional oil and gas development (UOGD) by means of horizontal drilling and high-volume hydraulic fracturing has been accompanied by concerns regarding the potential impacts to water resources and public health. The ban on UOGD in New York State (NYS) allows natural processes that control groundwater chemistry and dissolved methane to be evaluated without complications that could arise in regions impacted by prior unconventional shale gas development. We evaluated the controls on the occurrence and spatial variability of methane, chloride, bromine, and iodine, covering much of NYS and encompassing a range of underlying bedrock geologies. Groundwater samples were collected from 108 domestic and public supply wells. Methane concentrations in groundwater ranged from <0.001-84.6 mg/L. The variables most consistently associated with methane occurrence in groundwater include: 1) bedrock geology penetrated by wells; 2) groundwater chemical composition; 3) and confinement characterization of the well. The geochemical parameters iodine, chloride, and sodium/calcium suggest that elevated concentrations of methane are likely associated with deep brines. Higher methane concentrations are frequently accompanied by both high bromine and iodine concentrations in this study, indicating that the potential of halogens as tracers for dissolved methane need to be further investigated.

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Thirty water wells were sampled in 2018 to understand the geochemistry and age of groundwater in the Williston Basin and assess potential effects of shale-oil production from the Three Forks-Bakken petroleum system (TBPS) on groundwater quality. Two geochemical groups are identified using hierarchical cluster analysis. Group 1 represents the younger (median 4He=21.49×10-8 cm3 STP/g), less chemically evolved water. Group 2 represents the older (median 4He=1389×10-8 cm3 STP/g), more chemically evolved water. At least two samples from each group contain elevated Cl concentrations (>70 mg/L). Br/Cl, B/Cl, and Li/Cl ratios indicate multiple sources account for the elevated Cl concentrations: septic-system leachate/road deicing salt, lignite beds in the aquifers, Pierre Shale beneath the aquifers, and water associated with the TBPS (one sample). 3H and 14C data indicate that 10.8, 21.6, and 67.6% of the samples are modern (post-1952), mixed age, and premodern (pre-1953), respectively. Lumped-parameter modeling of 3H, SF6, 3He, and 14C concentrations indicates mean ages of the modern and premodern fractions range from ∼1 to 30 years and 1300 to >30,000 years, respectively. Group 2 contains the highest CH4 concentrations (0.0018 to 32 mg/L). δ13C-CH4 and C1/C2+C3 data in groundwater (-91.7 to -70.0‰ and 1280 to 13,600) indicate groundwater CH4 is biogenic in origin and not from thermogenic shale gas. Four volatile organic compounds (VOCs) were detected in two samples. One mixed-age sample contains chloroform (0.25 μg/L) and dichloromethane (0.05 μg/L), which are probably associated with septic leachate. One premodern sample contains butane (0.082 μg/L) and n-pentane (0.032 μg/L), which are probably associated with thermogenic gas from a nearby oil well. The data indicate hydrocarbon production activities do not currently (2018) widely affect Cl, CH4, and VOC concentrations in groundwater. The predominance of premodern recharge in the aquifers indicates the groundwater moves relatively slowly, which could inhibit widespread chemical movement in groundwater overlying the TBPS. Comparison of groundwater-age data from five major unconventional hydrocarbon-production areas indicates aquifer zones used for water supply in the TBPS area have a lower risk of widespread chemical movement in groundwater than similar aquifer zones in the Fayetteville (Arkansas) and Marcellus (Pennsylvania) Shale production areas, but have a higher risk than similar aquifer zones in the Eagle Ford (Texas) and Haynesville (Texas, Louisiana) Shale production areas.

Abstract:
Water risks are one of the key issues dominating environmental debates on shale gas development. Water withdrawals and wastewater discharges in shale gas fields of mountainous areas are more complicated than in plain areas due to different climatic, topographical and hydrological conditions, which would impact water resources. This research identifies the surface water-related risks from shale gas development in mountainous areas as water shortage and water pollution. Conceptions of accessibility for both water supply and water pollution are proposed to describe the vulnerability of water resources and the exposure to water pollution. Based on a risk probability model, a water risk assessment method for mountainous areas is constructed from the perspectives of dangers, exposures and vulnerabilities. Finally, the assessment method is applied in Chongqing, China. The results show that, from 2010 to 2020, the water consumption of shale gas development has a little impact on regional water resources in total, but more significant impacts are seen in a few areas, including the seasonal water-deficient areas in Western Chongqing, the urban and suburban areas with high pollutant loadings in Midwest Chongqing, and other areas with high pollutant accessibility and vulnerable water environments. The surface water-related risks of the shale gas development in Chongqing are principally composed of low and relatively low levels of risks, which cover 60% of the total area of Chongqing and display a spatial difference of west > northeast > southeast areas. Based on Monte Carlo method, the results of uncertainty analyses show the model is reliable. This research provides a reference for water comprehensive risk assessment of shale gas development in mountainous areas.

Abstract:
Policies surrounding energy development are frequently implemented in response to known or perceived problems. South Africa is in a unique position to develop prospective policies that build on knowledge gained from elsewhere. This paper provides a prospective analysis of hydrogeological risk pathways and vulnerability attributes in advance of anticipated shale gas operations in the Karoo Basin of South Africa. The ‘hazard-pathways-receptors’ approach is applied to define the hydrogeologic system in the context of potential sources of water resource contamination. This case study focuses on two critical hydrogeological risk pathways: regional groundwater flow and discrete structural features. Depending on the targeted area (hydro-litho-structural domain, depth of target, presence of aquitard, intrusion ratio), the capacity of deep natural pathways to enable hydraulic fracturing fluids, chemicals, or produced water to reach shallow groundwater, will be reduced or difficult. Deep artesian water could however be intercepted at different depths and, based on past groundwater exploration in the Karoo, water could flow into horizontal fractures or openings characterising the shallow aquifers: sills-ring complexes, lithological contacts, and transgressive fractures across dolerite dykes. However, above-ground water and wastewater management safeguards are needed to protect shallow groundwater from potential water quality degradation due to a) flowback or produced water b) stray gas and/or c) spills or illicit discharges that could introduce contaminants into groundwater resources. This paper describes a systematic approach to evaluate hydrogeologic risk pathways and informs adaptive management policies to protect South African groundwater resources.

Abstract:
As natural gas has grown in importance as a global energy source, leakage of methane (CH4) from wells has been noted. Leakage of this greenhouse gas is important because it affects groundwater quality and, when emitted to the atmosphere, climate. We hypothesized that streams might be most contaminated by CH4 in the northern Appalachian Basin in regions with the longest history of hydrocarbon extraction activities. To test this, we searched for CH4-contaminated streams basin. Methane concentrations ([CH4]) for 529 stream sites are reported, in New York, West Virginia and mostly Pennsylvania. Despite targeting contaminated areas, the median [CH4], 1.1 μg/L, was lower than a recently identified threshold indicating potential contamination, 4.0 μg/L. [CH4] values were higher in a few streams because they receive high-[CH4] groundwaters, often from upwelling seeps. By analogy to the more commonly observed type of groundwater seep known as abandoned mine drainage (AMD), we introduce the term, “gas leak discharge” (GLD) for these waters where they are not associated with coal mines. GLD and AMD, observed in all parts of the study area, are both CH4-rich. Surprisingly, the region of oldest and most productive oil/gas development did not show the highest median for stream [CH4]. Instead, the median was statistically highest where dense coal mining was accompanied by conventional and unconventional oil and gas development, emphasizing the importance of CH4 contamination from coal mines into streams.

Abstract:
Source-pathway-receptor analyses involving solute migration pathways through soil and shallow groundwater are typically undertaken to assess how people and the environment could come into contact with chemicals associated with coal seam gas operations. For the potential short‑term and long‑term release of coal seam gas fluids from storage ponds, solute concentration and dilution factors have been calculated using a water flow and solute transport modelling framework for an unsaturated zone-shallow groundwater system. Uncertainty about dilution factors was quantified for a range of system parameters: (i) leakage rates from storage ponds combined with recharge rates, (ii) a broad combination of soil and groundwater properties, and (iii) a series of increasing travel distances through soil and groundwater. Calculated dilution factors in the soil increased from sand to loam soil and increased with an increasing recharge rate, while dilution decreased for a decreasing leak rate and leak duration. In groundwater, dilution factors increase with increasing aquifer hydraulic conductivity and riverbed conductance. For a hypothetical leak duration of three years, the combined soil and groundwater dilution factors are larger than 6980 for more than 99.97% of bores that are likely to be farther than 100 m from the source. Dilution factors were more sensitive to uncertainty in leak rates than recharge rates. Based on this dilution factor, a comparison of groundwater predicted environmental concentrations and predicted no-effect concentrations for a subset of hydraulic fracturing chemicals used in Australia revealed that for all but two of the evaluated chemicals the estimated groundwater concentration (for a hypothetical water bore at 100 m from the solute source) is smaller than the no-effect concentration for the protection of aquatic ecosystems.

Abstract:
The purpose of this study is to evaluate the impact of hydraulic fracturing on groundwater quality in Ector, Midland, and Martin Counties located in the Permian Basin, West Texas. Chemical fluids used in hydraulic fracturing and groundwater quality parameters (chloride, fluoride, calcium carbonate, nitrate, pH, and total dissolved solids), were statistically analyzed assuming a normal probability function distribution and through a one-way analysis of variance of the parameters. Additionally, the depth of groundwater well versus water quality analysis as well as historical analysis of groundwater quality parameters of wells were performed. The result for each county was individually examined and contrasted with the other two counties, in order to make inferences about groundwater quality and oil and gas activities for the three counties. Potential risks to human health from the abnormal levels of the groundwater quality parameters studied were also discussed based on the Environmental Protection Agency’s (EPA) standards. This research provides important information on groundwater quality in the Permian Basin and contributes on understanding the response to development in hydraulic fracturing.

Abstract:
More than 1 million wells may have been completed using hydraulic fracturing techniques in the USA alone; however, there have been few case studies exploring the impacts on water resources due to methane migration. This study evaluated the results of three investigations initiated by the US Environmental Protection Agency, that were subsequently described in published studies at Dimock in Pennsylvania, Parker-Hood County in Texas, and Pavillion in Wyoming, as well as another study completed at Sugar Run in northeast Pennsylvania. In addition, earlier investigations at Shaws Corner in Pennsylvania, Jackson County in West Virginia, Garfield County in Colorado, and Bainbridge in Ohio are summarized. The most common cause of incidents was the presence of uncemented sections of production casings in wells that allowed gas migration from intermediate depths to shallow freshwater aquifers. In three cases, an inadequate depth of the primary top of cement (TOC) also contributed to impacts. Sources of methane were best identified through analyses of isotopes on samples from production casings, annular spaces, and water wells. In Dimock, some isotope signatures changed with time, after the completion of remedial actions. In Parker-Hood County, where impacts were not related to gas well activity, noble gas analyses were also needed to determine the source of gas. At Pavillion, where maximum methane concentrations in water wells were <1 mg/L, no significant impacts were documented. For all the sites, most or all of the fugitive gas incidents may have been prevented by fully cementing production casings to the land surface.

Abstract:
The rapid expansion of unconventional oil and gas development (UD), made possible by horizontal drilling and hydraulic fracturing, has triggered concerns over groundwater contamination and public health risks. To improve our understanding of the risks posed by UD, we develop a physically based, spatially explicit framework for evaluating groundwater well vulnerability to aqueous phase contaminants released from surface spills and leaks at UD well pad locations. The proposed framework utilizes the concept of capture probability and incorporates decision-relevant planning horizons and acceptable risks to support goal-oriented modeling for groundwater protection. We illustrate the approach in northeastern Pennsylvania, where a high intensity of UD activity overlaps with local dependence on domestic groundwater wells. Using two alternative models of the bedrock aquifer and a precautionary paradigm to integrate their results, we found that most domestic wells in the domain had low vulnerability as the extent of their modeled probabilistic capture zones were smaller than distances to the nearest existing UD well pad. We also found that simulated capture probability and vulnerability were most sensitive to the model parameters of matrix hydraulic conductivity, porosity, pumping rate, and the ratio of fracture to matrix conductivity. Our analysis demonstrated the potential inadequacy of current state-mandated setback distances that allow UD within the boundaries of delineated capture zones. The proposed framework, while limited to aqueous phase contamination, emphasizes the need to incorporate information on flow paths and transport timescales into policies aiming to protect groundwater from contamination by UD.

Abstract:
Potential environmental impacts on shallow groundwater from shale gas development facilitated by horizontal drilling and hydraulic fracturing is a widely debated “hot topic”. In terms of potential aqueous phase contamination (including flowback fluids and produced water), there is a large gap in knowledge of the indicators for routine monitoring and contamination tracing, which should be considered critical and should be prioritized for analysis. Since formation water from shale formations is the main source of flowback fluids and produced water, and there are significant differences in some specific inorganic geochemical and isotopic compositions between shallow groundwater and formation water, this study has provided a framework to determine sensitive monitoring and diagnostic indicators for tracing potential groundwater contamination from produced water using end-member analysis. The results from a case study of the Fuling Gasfield, Sichuan Basin, SW China as the first and largest commercial shale gas development site in China, shows that produced authentic formation water with similar Br/Cl and Na/Cl ratio with seawater and low δ2H and δ18O values compared to the evaporated seawater might originate from evaporated seawater modified by water-rock interactions and be mixed with fresh meteoric water. The inorganic geochemical and isotopic indicators, such as Ba, Li, Na, Cl, Br, 87Sr/86Sr (as εSrsw) and δ11B are sensitive to the detection of contamination of fresh shallow groundwater by produced formation water, even in very small fractions (0.05%). Meanwhile, we present a groundwater contamination case related to shale gas development in the Fuling Gasfield. The robust conservative geochemical (Cl and Br) and isotopic (δ11B and εSrsw) mass balances show that 0.2%–0.9% of formation water entered the shallow groundwater causing contamination. The case has also confirmed the effectiveness of those indicators. Findings from this study may help to improve groundwater monitoring and environmental regulations in countries with shale gas exploration and development.

Abstract:
Elevated dissolved methane (CH4) concentrations in groundwater are an environmental concern associated with hydraulic fracturing for shale gas. Therefore, determining dissolved CH4 baselines is important for detecting and understanding any potential environmental impacts. Such baselines should change in time and space to reflect ongoing environmental change and should be able to predict the probability that a change in dissolved CH4 concentration has occurred. We considered four dissolved CH4 concentration datasets of English groundwater using a Bayesian approach: two national datasets and two local datasets from shale gas exploration sites. The most sensitive national dataset (the previously published British Geological Survey CH4 baseline) was used as a strong prior for a larger (2153 measurements compared to 439) but less sensitive (detection limit 1000 times higher) Environment Agency dataset. The use of the strong prior over a weak prior improved the precision of the Environment Agency dataset by 75%. The expected mean dissolved CH4 concentration in English groundwater based on the Bayesian approach is 0.24 mg/l, with a 95% credible interval of 0.11 to 0.45 mg/l, and a Weibull distribution of W(0.35±0.01, 0.34±0.16). This indicates the amount of CH4 degassing from English groundwater to the atmosphere equates to between 0.7 to 3.1 kt CH4/year, with an expected value of 1.65 kt CH4/year and a greenhouse gas warming potential of 40.3 kt CO2eq/year. The two local monitoring datasets from shale gas exploration sites, in combination with the national datasets, show that dissolved CH4 concentrations in English groundwater are generally low, but locations with concentrations greater than or equal to the widely used risk action level of 10.0 mg/l do exist. Statistical analyses of groundwater redox conditions at these locations suggest that it may be possible to identify other locations with dissolved CH4 concentrations ≥10.0 mg/l using redox parameters such as Fe concentration.

Abstract:
Baseline mobile surveys of methane sources using vehicle-mounted instruments have been performed in the Fylde and Ryedale regions of Northern England over the 2016-19 period around proposed unconventional (shale) gas extraction sites. The aim was to identify and characterise methane sources ahead of hydraulically fractured shale gas extraction in the area around drilling sites. This allows a potential additional source of emissions to atmosphere to be readily distinguished from adjacent sources, should gas production take place. The surveys have used ethane:methane (C2:C1) ratios to separate combustion, thermogenic gas and biogenic sources. Sample collection of source plumes followed by high precision δ13C analysis of methane, to separate and isotopically characterise sources, adds additional biogenic source distinction between active and closed landfills, and ruminant eructations from manure. The surveys show that both drill sites and adjacent fixed monitoring sites have cow barns and gas network pipeline leaks as sources of methane within a 1 km range. These two sources are readily separated by isotopes (δ13C of -67 to -58 ‰ for barns, compared to -43 to -39 ‰ for gas leaks), and ethane:methane ratios (<0.001 for barns, compared to >0.05 for gas leaks). Under a well-mixed daytime atmospheric boundary layer these sources are generally detectable as above baseline elevations up to 100 m downwind for gas leaks and up to 500 m downwind for populated cow barns. It is considered that careful analysis of these proxies for unconventional production gas, if and when available, will allow any fugitive emissions from operations to be distinguished from surrounding sources.

Abstract:
This study proposes a new integrated framework to evaluate groundwater safety by characterizing the short-term spatiotemporal variations of methane migration risk attributed to shale gas development. A set of probabilistic- and conditionally probabilistic-based algorithms is used to represent the temporal and spatial distributions of reliability–resilience–vulnerability (RRV) over the study domain. Using RRV calculation and copula functions, the gas migration index (GMI) is calculated to identify the interrelationships among RRV for identifying the synergetic variation of RRV levels. The framework is demonstrated and discussed through the southwest shale of Bradford County, Pennsylvania. Results show that 1) reliability is quite high (>0.7) over the southern parts while the midland remains high risk of contamination; 2) low-level reliability spreads to the northern and southern areas from the central parts and gradually diffuses through most grids sparsely; reliability implies negative correlations with methane concentrations; 3) the spatiotemporal variation of resilience has high concordance with those of reliability except subtle discrepancies; and 4) the spatial distribution of high-level vulnerability has subtler classifications besides similar outlines to that of low-reliability. Moreover, results from the GMI analysis show that 1) the gas migration risk is consistently low in the south and the north in middle blocks and 2) high-level GMI shows an apparent rampant tendency across the blocks and spreads to the whole north ultimately. Therefore, GMI is better at characterizing groundwater contamination risk than using a single metric. The framework will contribute significantly to improve management practices taken by shale gas operators and regulators in protecting groundwater quality.

Abstract:
Abstract Unconventional oil and gas (UOG) extraction using fracking can damage groundwater resources, a crucial resource in many countries. Protecting groundwater will become more urgent as climate change and population growth increase pressure on water demand, especially in water-scarce countries. But despite the strategic importance of groundwater, it is often poorly managed during UOG extraction. This review considers three types of regulation (command-and-control, market-based and voluntary) in countries where UOG extraction is allowed, to identify the best suite of regulations to protect groundwater resources during this process. We propose a regulatory framework that includes both ?hard? command-and-control regulations and ?soft? market-based and voluntary regulations. If regulations are to protect groundwater resources effectively, public disclosure of UOG operations must be required and the information must be stored in publicly accessible databases. This would allow for independent scientific review of data by academia and the private sector, in addition to government scrutiny of the data. These parties can then make recommendations to government, allowing timeous and appropriate adaptive management and the amendment of regulations as necessary. And, most importantly, these regulations must be properly enforced to avoid (in some cases irreversible) damage to groundwater resources. This article is characterized under: Engineering Water > Sustainable Engineering of Water Human Water > Water Governance Science of Water > Water Quality

Abstract:
Current concerns and discussions regarding hydraulic fracturing and other activities of the oil and gas industry and geothermal energy sector are forcing a reassessment of formation waters as well as their impacts on the environment. In this review paper, the chemical and the most important physicochemical properties of low- to high-salinity formation waters are analysed and critically evaluated. Especially the complex interactions of the dissolved salts, the isotonicity and the relevance of the pH of virgin formation waters are discussed in this context for the first time. These “by-products” of the oil and gas industry are presented in a new light, whereby a clear distinction made between live and dead formation waters. Due to this significant differentiation, most research results of the past must be critically assessed and reclassified. With the highlighted importance of the composition of formation and injection waters, the most common causes for early termination of the production phases, the possible long-term damages to reservoirs and the origin of man-made earthquakes are described. Treatment concepts for dead formation/ process waters, as well as conclusions regarding an environmentally friendly management thereof, are mentioned.

Abstract:
Water samples from 50 domestic wells located <1 km (proximal) and >1 km (distal) from shale-gas wells in upland areas of the Marcellus Shale region were analyzed for chemical, isotopic, and groundwater-age tracers. Uplands were targeted because natural mixing with brine and hydrocarbons from deep formations is less common in those areas compared to valleys. CH4-isotope, predrill CH4-concentration, and other data indicate that one proximal sample (5% of proximal samples) contains thermogenic CH4 (2.6 mg/L) from a relatively shallow source (Catskill/Lock Haven Formations) that appears to have been mobilized by shale-gas production activities. Another proximal sample contains five other volatile hydrocarbons (0.03–0.4 μg/L), including benzene, more hydrocarbons than in any other sample. Modeled groundwater-age distributions, calibrated to 3H, SF6, and 14C concentrations, indicate that water in that sample recharged prior to shale-gas development, suggesting that land-surface releases associated with shale-gas production were not the source of those hydrocarbons, although subsurface leakage from a nearby gas well directly into the groundwater cannot be ruled out. Age distributions in the samples span ∼20 to >10000 years and have implications for relating occurrences of hydrocarbons in groundwater to land-surface releases associated with recent shale-gas production and for the time required to flush contaminants from the system.

Abstract:
Methane (CH4) enters waters in hydrocarbon-rich basins because of natural processes and problems related to oil and gas wells. As a redox-active greenhouse gas, CH4 degrades water or emits to the atmosphere and contributes to climate change. To detect if methane migrated from hydrocarbon wells (i.e., anomalous methane), we examined 20 751 methane-containing groundwaters from the Upper Appalachian Basin (AB). We looked for concentrations (mg/L) that indicated AB brine salts (chloride concentrations ([Cl]) > 30; [Ca]/[Na] < 0.52) to detect natural methane, and we looked for concentrations of redox-active species ([SO4] ≥ 6; [Fe] ≥ 0.3) to detect anomalous methane. These indicators highlight natural contamination by methane-containing brines or recent onset of microbial oxidation of methane coupled to iron- or sulfate-reduction. We hypothesized that only waters recently contaminated by methane still exhibit high iron and sulfate concentrations. Of the AB samples, 17 (0.08%) from 12 sites indicated potential contamination. All were located in areas with high densities of shale-gas or conventional oil/gas wells. In contrast, in southwestern Pennsylvania where brines are shallow and coal, oil, and gas all have been extracted extensively, no sites of recent methane migration were detectable. Such indicators may help screen for contamination in some areas even without predrill measurements.

Abstract:
With the increased development of oil and gas activities in northern Colorado, public concerns over the environmental impacts associated with well drilling and hydraulic fracturing have continued to rise. Issues such as leakages of “toxic” products from oil and gas operations to the subsurface environment (such as groundwater contamination) have led to community action and state regulations related to the establishment of groundwater quality monitoring sites in oil and gas activity areas, particularly those adjacent to urban development. Colorado Water Watch was a groundwater quality monitoring network comprised of seven monitoring wells in northern Colorado to monitor groundwater quality near oil and gas wells and give early warnings of contamination. Our study is aimed at developing a quantitative methodology to find ideal monitoring locations as well as evaluate them. We utilized hydraulic and geological data to select the most preferred sites to monitor groundwater quality, understand the temporal trends and identify unique anomaly signals in the oil and gas active area (Wattenberg field, northern Colorado). In addition to the site selection methodology, water quality data from Colorado Water Watch over 2 years is used to do evaluate the performance using entropy information and Principal Component Analysis. The analysis indicates that the earliest functional monitoring site (CHILL) is the most informative monitoring well, and the most recently installed monitoring sites (Gilcrest and LaSalle) are the least informative and least important stations due to their low data efficiency.

Abstract:
The contamination of surface water and ground water by human activities, such as fossil fuel extraction and agriculture, can be difficult to assess due to incomplete knowledge of the chemicals and chemistry involved. This is particularly true for the potential contamination of drinking water by nearby extraction of oil and/or gas from wells completed by hydraulic fracturing. A case that has attracted considerable attention is unconventional natural gas extraction in Susquehanna County, Pennsylvania, particularly around Dimock, Pennsylvania. We analyzed surface water and groundwater samples collected throughout Susquehanna County with complementary biological assays and high-resolution mass spectrometry. We found that Ah receptor activity was associated with proximity to impaired gas wells. We also identified certain chemicals, including disclosed hydraulic fracturing fluid additives, in samples that were either in close proximity to impaired gas wells or that exhibited a biological effect. In addition to correlations with drilling activity, the biological assays and high-resolution mass spectrometry detected substances that arose from other anthropogenic sources. Our complementary approach provides a more comprehensive picture of water quality by considering both biological effects and a broad screening for chemical contaminants.

Abstract:
Concerns over possible impacts from the rapid expansion of unconventional oil and natural gas (ONG) resource development prompted a regional domestic well sampling program focusing on the Carboniferous Maritimes Basin bedrock in southeastern New Brunswick, Canada. This work applies recent developments in robust multivariate statistical methods to overcome issues with highly non-Gaussian data and support the development of a conceptual model for the regional groundwater chemistry and the occurrence of methane. Principal component analysis reveals that the redox-sensitive species, DO, NO3, Fe, Mn, methane, As and U are the most important parameters that differentiate the samples. Permutation-based MANOVA and ANOVA testing revealed that geology was more important than geographic location and topography in influencing groundwater composition. The statistical inferences are supported by chemistry trends observed in relation to road de-icing salt and other saline sources. However, source differentiation between Carboniferous brines, entrapped post-glacial marine water and modern seawater cannot be made. Furthermore, Cl:Br ratios lower than those of seawater or regional brines suggest an origin related to the diagenesis of organic-rich sediment and that the groundwater may be influenced by local low permeability units. Combined spatial, statistical and chemical analysis shows that, while trace or low levels of methane, <1 mg/L, are found ubiquitously throughout the Maritimes Basin, elevated concentrations, >1 mg/L, are associated with the Horton Group, consistent with it being the host and inferred source of ONG resources in the province. The highest methane concentrations (14–29 mg/L) were detected in the region with a complex history of cycles of uplift and erosion which, in some locations, resulted in the juxtaposition at the surface of the Horton Group with several other groups of the Maritimes Basin. It is thought that proximity to the Horton Group can lead to naturally high methane concentrations in non-ONG-bearing units.

Abstract:
There is a need for the development of effective baselines against which the water quality impacts of industry in general, and shale gas extraction specifically, can be assessed. The salinity, and hence the specific conductance, of fluids associated with shale gas extraction is typically many times higher that of river water. The contrast between these two water types means that testing for salinity (specific conductance) could provide an ideal sentinel for detecting environmental impact of shale gas extraction. Here, Bayesian generalised linear modelling was used to predict specific conductance across English surface waters. The modelling used existing, spot-sampled data from 2005 to 2015 from 123 sites to assess whether this approach could predict variation for subsequent years or for a new site (data from 2002 to 2015). We show that the results were readily projected in to subsequent years for sites included in the initial analysis. The use of covariates (land-use, hydroclimatic and soil descriptors) did not prove useful in predicting specific conductance at further sites not previously included in the analysis. The extension of the approach to 6833 English river monitoring sites with 10 or more observations from more than one year over the period 2005–2015 showed that it was possible to reproduce the seasonal variation in river water specific conductance. The approach taken here shows that it is possible to use low-frequency but widespread monitoring data to predict natural variation at monitoring sites to give a probabilistic assessment of whether or not a pollution incident has occurred and the seasonal variation, expressed as uncertainty bounds around the observations, at a specific site has been exceeded.

Abstract:
Unconventional oil and gas (UOG) development has increased dramatically in the Marcellus Shale region over the past decade, and there is widespread public concern about the potential effects that UOG development may have on water quality. The goal of this study was to assess whether a suite of stream water quality constituents was related to the intensity of UOG development in corresponding catchments. Nineteen streams in southwestern Pennsylvania, where UOG development is prevalent, and 10 streams in western Maryland, where no UOG development has occurred, were sampled in summer 2013. Dissolved metals, radium isotopes, radon, specific conductance, stream discharge, and pH were measured. Principal component analysis revealed that samples tended to cluster by state, but some overlap in water quality existed between Maryland and Pennsylvania. Linear models were used to assess how response variables were related to UOG, other extractive activities, and landscape characteristics. These models showed that an index of oil and gas development had significant explanatory power for specific conductance, As, Ca, K, Mg, Na, and Sr. Other land use and land cover variables, such as forest, urban development, and coal mining, as well as stream discharge and pH, also were significantly associated with response variables. These results suggest that, in the Marcellus Shale region, UOG may elevate specific conductance and dissolved element concentrations in streams, but it should be considered in the context of broader patterns of land use and human activity.

Abstract:
The prospect of unconventional shale gas development in the semi-arid Karoo Basin (South Africa) has created the prerequisite to temporally characterise the natural radioactivity in associated groundwater which is solely depended on for drinking and agriculture purposes. Radon (222Rn) was the primary natural radionuclide of interest in this study; however, supplementary radium (226Ra and 228Ra) in-water measurements were also conducted. A total of 53 aquifers spanning three provinces were studied during three separate measurement campaigns from 2014 to 2016. The Karoo Basin's natural radon-in-water levels can be characterised by a minimum of 1 ± 1 Bq/L (consistent with zero or below LLD), a maximum of 183 ± 18 Bq/L and mean of 41 ± 5 Bq/L. The mean radon-in-water levels for shallow aquifers were systematically higher (55 ± 10 Bq/L) compared to deep (14 ± 3 Bq/L) or mixed aquifers (20 ± 6 Bq/L). Radon-in-water activity concentration fluctuations were predominantly observed from shallow aquifers compared to the generally steady levels of deep aquifers. A collective seasonal mean radon-in-water levels increase from the winter of 2014 (44 ± 8 Bq/L) to winter of 2016 (61 ± 16 Bq/L) was noticed which could be related to the extreme national drought experienced in 2015. Radium-in-water (228Ra and 226Ra) levels ranged from below detection level to a maximum of 0.008 Bq/L (226Ra) and 0.015 Bq/L (228Ra). The 228Ra/226Ra ratio was characterized by a minimum of 0.93, a maximum of 6.5 and a mean value of 3.3 ± 1.3. Developing and improving baseline naturally occurring radionuclide groundwater databases is vital to study potential radiological environmental impacts attributed to industrial processes such as hydraulic fracturing or mining.

Abstract:
The objective of this study is to evaluate the public water contamination in the cities of Midland and Odessa, West Texas. Even though both cities are geographically close, their sources of water for public use are different. For this study, the copper-, lead-, arsenic-, nitrate-, and chromium-level reports in drinking water, provided by the cities from 2008 to 2017, were organized and analyzed using Cubic Hermite Interpolation. The results for each contamination per city were compared and contrasted with the Environmental Protection Agency (EPA) standards. Also, this study proposed possible risks to human health, as well as potential origins of the pollutants. Finally, conclusions about the quality of water for human consumption and possible reasons behind the difference of results between the 2 cities were made.