Repository for Oil and Gas Energy Research (ROGER)

Abstract:
A holistic risk assessment of surface water (SW) contamination due to lead-210 (Pb-210) in oil produced water (PW) from the Bakken Shale in North Dakota (ND) was conducted. Pb-210 is a relatively long-lived radionuclide and very mobile in water. Because of limited data on Pb-210, a simulation model was developed to determine its concentration based on its parent radium-226 and historical total dissolved solids levels in PW. Scenarios where PW spills could reach SW were analyzed by applying the four steps of the risk assessment process. These scenarios are: (1) storage tank overflow, (2) leakage in equipment, and (3) spills related to trucks used to transport PW. Furthermore, a survey was conducted in ND to quantify the risk perception of PW from different stakeholders. Findings from the study include a low probability of a PW spill reaching SW and simulated concentration of Pb-210 in drinking water higher than the recommended value established by the World Health Organization. Also, after including the results from the risk perception survey, the assessment indicates that the risk of contamination of the three scenarios evaluated is between medium-high to high.

Abstract:
Modern drilling techniques, notably horizontal drilling and hydraulic fracturing, have enabled unconventional oil production (UOP) from the previously inaccessible Bakken Shale Formation located throughout Montana, North Dakota (ND) and the Canadian province of Saskatchewan. The majority of UOP from the Bakken shale occurs in ND, strengthening its oil industry and businesses, job market, and its gross domestic product. However, similar to UOP from other low-permeability shales, UOP from the Bakken shale can result in environmental and human health effects. For example, UOP from the ND Bakken shale generates a voluminous amount of saline wastewater including produced and flowback water that are characterized by unusual levels of total dissolved solids (350 g/L) and elevated levels of toxic and radioactive substances. Currently, 95% of the saline wastewater is piped or trucked onsite prior to disposal into Class II injection wells. Oil and gas wastewater (OGW) spills that occur during transport to injection sites can potentially result in drinking water resource contamination. This study presents a critical review of potential water resource impacts due to deterministic (freshwater withdrawals and produced water management) and probabilistic events (spills due to leaking pipelines and truck accidents) related to UOP from the Bakken shale in ND.

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Understanding the source of dissolved methane in drinking-water aquifers is critical for assessing potential contributions from hydraulic fracturing in shale plays. Shallow groundwater in the Texas portion of the Haynesville Shale area (13,000 km2) was sampled (70 samples) for methane and other dissolved light alkanes. Most samples were derived from the fresh water bearing Wilcox formations and show little methane except in a localized cluster of 12 water wells (17% of total) in a approximately 30 × 30 km2 area in Southern Panola County with dissolved methane concentrations less than 10 mg/L. This zone of elevated methane is spatially associated with the termination of an active fault system affecting the entire sedimentary section, including the Haynesville Shale at a depth more than 3.5 km, and with shallow lignite seams of Lower Wilcox age at a depth of 100 to 230 m. The lignite spatial extension overlaps with the cluster. Gas wetness and methane isotope compositions suggest a mixed microbial and thermogenic origin with contribution from lignite beds and from deep thermogenic reservoirs that produce condensate in most of the cluster area. The pathway for methane from the lignite and deeper reservoirs is then provided by the fault system.

Abstract:
The development of shale gas resources was made possible by the combination of horizontal drilling and high-volume hydraulic fracturing (fracking). Environmental concerns have been raised relative to shale gas production, especially potential impacts on groundwater. Fluids related to unconventional oil and gas (O&G) operations contain chemical compounds that can impact groundwater quality. Such impacts can occur due to (1) the infiltration of surface contaminant releases, (2) failures of the integrity of O&G wells, and (3) upward fluid migration from a shale/tight reservoir along preferential paths that can be natural (faults or fracture zone) or man-made (O&G wells). Surface releases represent the most probable mechanism leading to groundwater contamination. Improvements in O&G drilling operations under stringent regulations can minimize this risk. Experts identify O&G well integrity as the most challenging issue that may lead to groundwater contamination. Failure of casing and cement can lead to upward fluid flow within or outside O&G wells, especially of methane. Integrity failures leading to fluid migration to shallow fresh water aquifers or to the surface are well understood and can be detected and repaired, but this can be complex and costly. A few regulators now impose groundwater monitoring to detect impacts from integrity failures. Occurrences of communication with existing O&G wells from fracking operations have also led some regulators to impose rules aiming to avoid such potential fluid migration paths. There is an ongoing scientific debate regarding the potential for fluids to migrate upward from exploited shale gas units to aquifers through natural preferential paths. WIREs Water 2017, 4:e1188. doi: 10.1002/wat2.1188 For further resources related to this article, please visit the WIREs website.

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The shale slip, cement failure and micro annulus caused by hydraulic fracturing in shale gas well may generate local loads which have significant effects on the stress status and yield of the casing. Local loads are considered in the well integrity analysis based on the Mechanics of Materials. A mechanical model is established for the casing behavior under local loads. The accuracy of the model is verified by numerical simulation, Nesrter's method and field data. The effects of local loads and casing dimension on the casing failure are illustrated by the sensitivity analysis. The analysis results show that the casing collapse is more likely to occur under the radial local loads than under parallel ones. Increasing casing thickness and decreasing casing outer diameter are in favor of reducing the casing failure in shale gas wells. The local loads region has the greatest effect on anti-collapse strength of the casing when φ = 90°. Through decreasing the wellbore diameter of shale gas wells and intersecting the natural fractures of shale gas reservoir reasonably, the directional drilling safety, cementing quality and well integrity can be effectively improved, and the casing deformation can be much reduced.

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The proposed drilling for shale gas resources in the Eastern Cape Karoo region of South Africa has triggered much debate over the potential effects of hydraulic fracturing on water resources. Herein we present results on some limnological aspects of surface waterbodies in this water-scarce region before shale gas exploration. Thirty-three waterbodies (nine dams, 13 depression wetlands and 11 rivers) were sampled in November 2014 and April 2015. Principal component analysis revealed that depression wetlands and rivers had distinct physicochemical signatures, whereas dams were highly variable in their physicochemical attributes and exhibited characteristics similar to those of either rivers or depression wetlands. Non-parametric multivariate regressions and permutational multivariate analysis of variance (MANOVA) indicated that landscape variables such as underlying geology, altitude and land use poorly explained the physicochemical characteristics of the sampled waterbodies. Waterbody type was the only factor that explained a significant amount of the variation in physicochemistry during both sampling events. These data need to be supplemented by water quality information from additional sites and over longer time periods, as well as supporting data relating to other aspects, such as algae and invertebrates, before they can be used as a baseline for the long-term monitoring of freshwater ecosystems in the region.

Abstract:
Since the early 2000s, oil and natural gas production in the United States have been transformed through technological innovation. Hydraulic fracturing, combined with advanced directional drilling techniques, made it possible to economically extract oil and gas resources previously inaccessible. The resulting surge in production increased domestic energy supplies and brought economic benefits to many areas of the United States. The growth in domestic oil and gas production also raised concerns about potential impacts to human health and the environment, including potential effects on the quality and quantity of drinking water resources. Some residents living close to oil and gas production wells have investigated changes in the quality of drinking water and assert that hydraulic fracturing is responsible for these changes. Other concerns include competition for water between hydraulic fracturing activities and other water users, especially in areas of the country experiencing drought, and the disposal of wastewater generated from hydraulic fracturing. This investigation synthesizes available scientific literature and data to assess the potential for hydraulic fracturing for oil and gas to change the quality or quantity of drinking water resources, and identifies factors affecting the frequency or severity of potential changes. This investigation can be used by federal, tribal, state, and local officials; industry; and the public to better understand and address any vulnerabilities of drinking water resources to hydraulic fracturing activities.

Abstract:
A dramatic increase in unconventional drilling that utilizes hydraulic fracturing to extract oil/gas over the past decade has led to concern over handling and management of produced/ flowback water (PFW; hydraulic-fracturing wastewater) because the potential exists for its accidental release into the environment. This PFW contains high amounts of total dissolved solids acquired from interaction with the reservoir formation. Development and testing of geochemical methods, such as strontium (Sr) isotope ratio (87Sr/86Sr) analysis, to determine the origin of dissolved solids in an environment would be valuable. Samples acquired from different sources in Texas overlying and within the Barnett Shale, such as surface/ground water and PFW, contain unique Sr concentrations and 87Sr/86Sr values, with the potential to be used as a geochemical fingerprint. This study shows that because of the very high concentration of Sr in PFW and its high 87Sr/86Sr value, when as little as 1% of a sample is PFW, the sample experiences a measurable change in 87Sr/86Sr. To determine which phase within the reservoir rock imparts its 87Sr/86Sr to the PFW, sequential extractions were performed on powdered Barnett Shale core samples. Results of the extractions show varying geochemical affinities and distinct 87Sr/86Sr values by leaching solution. However, a direct link to the PFW sample was not conclusive, likely because of the unknown location of the PFW sample and the spatially variable 87Sr/86Sr of the Barnett Shale. Future work requires further cooperation with industry or federal agencies that could provide a more complete set of samples.

Abstract:
The process of hydraulic fracturing for recovery of oil and natural gas uses large amounts of fresh water and produces a comparable amount of wastewater, much of which is typically transported by truck. Truck transport of water is an expensive and energy-intensive process with significant external costs including roads damages, and pollution. The integrated development plan (IDP) is the industry nomenclature for an integrated oil and gas infrastructure system incorporating pipeline-based transport of water and wastewater, centralized water treatment, and high rates of wastewater recycling. These IDP have been proposed as an alternative to truck transport systems so as to mitigate many of the economic and environmental problems associated with natural gas production, but the economic and environmental performance of these systems have not been analyzed to date. This study presents a quantification of lifecycle greenhouse gas (GHG) emissions and road damages of a generic oil and gas field, and of an oil and gas development sited in the Denver-Julesburg basin in the northern Colorado region of the US. Results demonstrate that a reduction in economic and environmental externalities can be derived from the development of these IDP-based pipeline water transportation systems. IDPs have marginal utility in reducing GHG emissions and road damage when they are used to replace in-field water transport, but can reduce GHG emissions and road damage by factors of as much as 6 and 7 respectively, when used to replace fresh water transport and waste-disposal routes for exemplar Northern Colorado oil and gas fields.

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Abstract:
Poland, due to the estimated shale gas deposits amounting to 346-768 billion m3 has become one of the most attractive regions for shale gas exploration in Europe. Throughout the period 2010-2015, 72 exploratory drillings have been made (as of 4.01.2016) while hydraulic fracturing was carried out...

Abstract:
Hydraulic fracturing for shale gas exploration is not free from environmental risk. The environmental concerns related to hydraulic fracturing has been greatly attracted. One of most important environmental concerns is regional water quality which may be contaminated by produced waters through induced and natural fractures and wastewater discharge. At present, the baseline water quality must be firstly obtained to identify potential pollution of the activity and monitoring indicators should be studied for better environmental monitoring. We sampled shallow groundwater, produced waters, shale rock and soil in the Jiaoshiba shale-gas region, SW China and measurements have included water chemistry and isotopes. Preliminary results show that the present shallow karst groundwater quality is pretty good with the total dissolved solids (TDS) ranging from 129 to 343mg/L and with water chemistry type of HCO3-Ca, However, some groundwaters have been polluted by agricultural activities. Produced waters have relatively high salinity with TDS ranging from 2 to 14g/L. Laboratory experiment of fracturing liquid and shale rock interaction at simulated reservoir conditions shows that TDS in the flowback fluid increases 10 times and Ca2+, Na+, Cl− and SO42− make dominant contributions. The main geochemical reactions are inferred to be pyrite oxidation and the dissolution of calcite, dolomite and plagioclase, resulting in increases of major ions in the flowback fluid. The inorganic geochemical monitoring indicators for shale gas exploration of the Silurian Longmaxi formation has been determined.

Abstract:
Since naturally occurring methane and saline groundwater are nearly ubiquitous in many sedimentary basins, delineating the effects of anthropogenic contamination sources is a major challenge for evaluating the impact of unconventional shale gas development on water quality. This study investigates the geochemical variations of groundwater and surface water before, during, and after hydraulic fracturing and in relation to various geospatial parameters in an area of shale gas development in northwestern West Virginia, United States. To our knowledge, we are the first to report a broadly integrated study of various geochemical techniques designed to apportion natural and anthropogenic sources of natural gas and salt contaminants both before and after drilling. These measurements include inorganic geochemistry (major cations and anions), stable isotopes of select inorganic constituents including strontium (87Sr/86Sr), boron (δ11B), lithium (δ7Li), and carbon (δ13C-DIC), select hydrocarbon molecular (methane, ethane, propane, butane, and pentane) and isotopic tracers (δ13C-CH4, δ13C-C2H6), tritium (3H), and noble gas elemental and isotopic composition (He, Ne, Ar) in 112 drinking-water wells, with repeat testing in 33 of the wells (total samples=145). In a subset of wells (n=20), we investigated the variations in water quality before and after the installation of nearby (<1 km) shale-gas wells. Methane occurred above 1 ccSTP/L in 37% of the groundwater samples and in 79% of the samples with elevated salinity (chloride >50 mg/L). The integrated geochemical data indicate that the saline groundwater originated via naturally occurring processes, presumably from the migration of deeper methane-rich brines that have interacted extensively with coal lithologies. These observations were consistent with the lack of changes in water quality observed in drinking-water wells following the installation of nearby shale-gas wells. In contrast to groundwater samples that showed no evidence of anthropogenic contamination, the chemistry and isotope ratios of surface waters near known spills or leaks occurring at disposal sites (n=8) mimicked the composition of the Marcellus flowback fluids, and show direct evidence for impact on surface water by fluids accidentally released from nearby shale-gas well pads and oil and gas wastewater disposal sites. Overall this study presents a comprehensive geochemical framework that can be used as a template for assessing the sources of elevated hydrocarbons and salts to water resources in areas potentially impacted by oil and gas development.

Abstract:
The large volume of wastewater produced during unconventional oil and gas (UOG) extraction is a significant challenge for the energy industry and of environmental concern, as the risks due to leaks, spills, and migration of these fluids into natural waters are unknown. UOG wastewater is often hypersaline, and contains myriad organic and inorganic substances added for production purposes and derived from the source rock or formation water. In this study, we examined the organic composition and toxicology of water and sediments in a stream adjacent to an underground injection disposal facility that handles UOG wastewaters. We sampled water and streambed sediments from an unnamed tributary of Wolf Creek upstream from the disposal facility, near the injection well, and downstream. Two sites downstream from the disposal facility contained organic compounds in both water and sediments that were consistent with a source from UOG wastewater. These compounds included: 2-(2-butoxyethoxy)-ethanol, tris(1-chloro-2-propyl)phosphate, α, α-dimethyl-benzenemethanol, 3-ethyl-4-methyl-1H-pyrrole-2,5-dione, and tetrahydro-thiophene-1,1-dioxide in water, diesel fuel hydrocarbons (e.g. pentacosane, Z-14-nonacosane), and halogenated hydrocarbons (e.g., 1-iodo-octadecane, octatriacontyl trifluoroacetate, dotriacontyl pentafluoropropionate) in sediments. Concentrations of UOG-derived organic compounds at these sites were generally low, typically 4 to <1 μg/L in the water, and <70 μg/g (dry wt.) in the sediment. In addition, water and sediment at a site immediately downstream from the facility contained many chromatographically unresolved and unidentified hydrocarbons. In contrast, sites upstream from the facility or in nearby watersheds not influenced by the disposal well facility contained primarily natural (biologically produced) organic substances from the local environment. Toxicological assays of human cell line exposures to water and sediment showed minimal effects. Results indicate that UOG wastewater has entered the stream and that UOG-derived organic substances are present. The contamination level, however, is low and appears to be restricted to sites immediately downstream from the disposal facility at this time.

Abstract:
Unconventional natural gas (UNG) extraction (fracking) is ongoing in 29 North American shale basins (20 states), with ~6000 wells found within the Fayetteville shale (north-central Arkansas). If the chemical signature of fracking is detectable in streams, it can be employed to bookmark potential impacts. We evaluated benthic biofilm community composition as a proxy for stream chemistry so as to segregate anthropogenic signatures in eight Arkansas River catchments. In doing so, we tested the hypothesis that fracking characteristics in study streams are statistically distinguishable from those produced by agriculture or urbanization.

Abstract:
Water-quality and isotopic data were collected in central Nevada, USA in an exploration hydraulic fracturing area with no previous oil or gas production. The target shales of the Elko Formation are unique fresh-water hydrocarbon reservoirs with relatively dilute source water (8.5 g/L total dissolved solids [TDS]). Additionally, the Elko Formation is underlain by a fresh-water carbonate aquifer (0.2-0.3 g/L TDS) that outcrops downgradient of the exploration area. The water quality and isotopic data were used to evaluate pre-hydraulic fracturing conditions in this undeveloped area. The same data were also collected for groundwater and surface-water sites about two months and one year after exploration hydraulic fracturing. No systematic differences in water chemistry were observed between pre- and post-hydraulic fracturing samples. Based on water chemistry of shallow groundwater, surface water, and from the production zone, the most useful constituents identified for monitoring for potential future incursion of reservoir-associated fluids into the near-surface environment are TDS (or electrical conductivity), chloride, propane, methanol, ethanol, and 2-butoxyethanol. Groundwater flow and transport models were developed to evaluate the potential movement of hydrocarbons and hydraulic fracturing fluids from the targeted zones, which are about 1800 to 3600 m beneath the land surface, to shallow groundwater (<300 m below land surface). Model simulations indicate that hydraulic fracturing fluid remains contained within the target shales for at least 1,000 years for most development scenarios.

Abstract:
The baseline chemistry of groundwater from two aquifers in the Vale of Pickering, North Yorkshire, has been investigated ahead of a proposal to explore for shale gas, planning permission for which has recently been granted. Groundwater in a shallow aquifer including Quaternary and/or Jurassic Kimmeridge Clay deposits shows compositions distinct from a Corallian (Jurassic) Limestone aquifer, reflecting different lithologies and hydrogeological conditions. Corallian groundwaters along the margins of the vale are controlled by reaction with carbonate, with redox conditions varying according to degree of aquifer confinement. Superficial aquifer groundwaters are confined and strongly reducing, with some observed high concentrations of dissolved CH4 (up to 37 mg/L; Feb 2016 data). This appears to be of mixed biogenic-thermogenic origin but further work is needed to determine whether the source includes a deeper hydrocarbon reservoir contributing via fractures, or a shallower source in the Quaternary or Kimmeridge sediments. The data show a shallow aquifer with a high-CH4 baseline which pre-dates any shale-gas activity.

Abstract:
Extraction of oil and gas from unconventional sources, such as shale, has dramatically increased over the past ten years, raising the potential for spills or releases of chemicals, waste materials, and oil and gas. We analyzed spill data associated with unconventional wells from Colorado, New Mexico, North Dakota and Pennsylvania from 2005 to 2014, where we defined unconventional wells as horizontally drilled into an unconventional formation. We identified materials spilled by state and for each material we summarized frequency, volumes and spill rates. We evaluated the environmental risk of spills by calculating distance to the nearest stream and compared these distances to existing setback regulations. Finally, we summarized relative importance to drinking water in watersheds where spills occurred. Across all four states, we identified 21,300 unconventional wells and 6622 reported spills. The number of horizontal well bores increased sharply beginning in the late 2000s; spill rates also increased for all states except PA where the rate initially increased, reached a maximum in 2009 and then decreased. Wastewater, crude oil, drilling waste, and hydraulic fracturing fluid were the materials most often spilled; spilled volumes of these materials largely ranged from 100 to 10,000L. Across all states, the average distance of spills to a stream was highest in New Mexico (1379m), followed by Colorado (747m), North Dakota (598m) and then Pennsylvania (268m), and 7.0, 13.3, and 20.4% of spills occurred within existing surface water setback regulations of 30.5, 61.0, and 91.4m, respectively. Pennsylvania spills occurred in watersheds with a higher relative importance to drinking water than the other three states. Results from this study can inform risk assessments by providing improved input parameters on volume and rates of materials spilled, and guide regulations and the management policy of spills.

Abstract:
The rapid expansion in unconventional gas development over the past two decades has led to concerns over the potential impacts on groundwater resources. Although numerical models are invaluable for assessing likelihood of impacts at particular sites, simpler analytical models are also useful because they help develop hydrological understanding. Analytical approaches are also valuable for preliminary assessments and to determine where more complex models are warranted. In this article, we present simple analytical solutions that can be used to predict: (1) the spatial extent of drawdown from horizontal wells drilled into the gas-bearing formation, and rate of recovery after gas production ceases; (2) the potential for upward transport of contaminants from the gas-bearing formation to shallow aquifers during hydraulic fracturing operations when pressures in the gas-bearing formation are greatly increased; and (3) the potential downward leakage of water from shallow aquifers during depressurization of gas-bearing formations. In particular, we show that the recovery of pressure after production ceases from gas-bearing shale formations may take several hundred years, and we present critical hydraulic conductivity values for intervening aquitards, below which the impact on shallow aquifers will be negligible. The simplifying assumptions inherent in these solutions will limit their predictive accuracy for site-specific assessments, compared to numerical models that incorporate knowledge of spatial variations in formation properties and which may include processes not considered in the simpler solutions.

Abstract:
Natural gas production from the Marcellus Shale formation has significantly changed energy landscape in recent years. Accidental release, including spills, leakage, and seepage of the Marcellus Shale flow back and produced waters can impose risks on natural water resources. With many competing processes during the reactive transport of chemical species, it is not clear what processes are dominant and govern the impacts of accidental release of Marcellus Shale waters (MSW) into natural waters. Here we carry out numerical experiments to explore this largely unexploited aspect using cations from MSW as tracers with a focus on abiotic interactions between cations released from MSW and natural water systems. Reactive transport models were set up using characteristics of natural water systems (aquifers and rivers) in Bradford County, Pennsylvania. Results show that in clay-rich sandstone aquifers, ion exchange plays a key role in determining the maximum concentration and the time scale of released cations in receiving natural waters. In contrast, mineral dissolution and precipitation play a relatively minor role. The relative time scales of recovery τrr, a dimensionless number defined as the ratio of the time needed to return to background concentrations over the residence time of natural waters, vary between 5 and 10 for Na, Ca, and Mg, and between 10 and 20 for Sr and Ba. In rivers and sand and gravel aquifers with negligible clay, τrr values are close to 1 because cations are flushed out at approximately one residence time. These values can be used as first order estimates of time scales of released MSW in natural water systems. This work emphasizes the importance of clay content and suggests that it is more likely to detect contamination in clay-rich geological formations. This work highlights the use of reactive transport modeling in understanding natural attenuation, guiding monitoring, and predicting impacts of contamination for risk assessment.

Abstract:
Since the 1800s, natural gas has been extracted from wells drilled into conventional reservoirs. Today, gas is also extracted from shale using high-volume hydraulic fracturing (HVHF). These wells sometimes leak methane and must be re-sealed with cement. Some researchers argue that methane concentrations, C, increase in groundwater near shale-gas wells and that “fracked” wells leak more than conventional wells. We developed techniques to mine datasets of groundwater chemistry in Pennsylvania townships where contamination had been reported. Values of C measured in shallow private water wells were discovered to increase with proximity to faults and to conventional, but not shale-gas, wells in the entire area. However, in small subareas, C increased with proximity to some shale-gas wells. Data mining was used to map a few hotspots where C significantly correlates with distance to faults and gas wells. Near the hotspots, 3 out of 132 shale-gas wells (~ 2%) and 4 out of 15 conventional wells (27%) intersect faults at depths where they are reported to be uncased or uncemented. These results demonstrate that even though these data techniques do not establish causation, they can elucidate the controls on natural methane emission along faults and may have implications for gas well construction.

Abstract:
In recent years, concerns have been raised about the potential environmental impacts of oil and gas (O&G) exploitation, especially regarding groundwater resources. However, there have been few studies carried out to assess the actual risk of O&G exploitation based on specific local conditions. This paper reports on a study aiming to assess the potential risk to groundwater quality related to the development of a tight sandstone petroleum reservoir underlying a shallow fractured rock aquifer system in the Haldimand sector of Gaspé, Québec, Canada. In this generally rural setting, the drilling of a provincially permitted horizontal O&G exploration well was halted by new municipal regulations. Draft provincial environmental regulations were subsequently issued to define environmental requirements for hydrocarbon exploration wells. Our study thus also aimed to provide an example of how to comply with the new hydrogeological characterization requirements. This paper reports on the process followed to qualitatively assess the risk of O&G operations and natural oil seeps to groundwater quality. The assessment focused on indicators of potential preferential fluid migration paths between the reservoir level and shallow aquifers. Field work and data analysis were used to define geological, hydrogeological and geochemical contexts on which a numerical model was developed to represent groundwater flow, mass transport and groundwater residence time. The risk for groundwater quality was qualitatively assessed from the implications of the study area context relative to 1) the new provincial regulatory requirements; 2) potential contaminant release mechanisms related to O&G exploration drilling operations; and 3) the expected effects that contaminant releases could have on groundwater.

Abstract:
The geochemical characteristics of shallow groundwater are essential for environmental impact studies in the shale gas production area. Jiaoshiba in the Sichuan basin is the first commercial-scale shale gas production area in China. This paper studied the geochemical and isotopic characteristics of the shallow groundwater of the area for future environmental concerns. Results show that the average pH of the shallow groundwater is 7.5 and the total dissolved solids (TDS) vary from 150 mg/L to 350 mg/L. The main water types are HCO3-Ca and HCO3-Ca·Mg due to the carbonates dissolution equilibrium in karst aquifers. The concentrations of major ions and typical toxic elements including Mn, Cr, Cu, Zn, Ba, and Pb are below the drinking water standard of China and are safe for use as drinking water. The high nitrate content is inferred to be caused by agricultural pollution. The shallow groundwater is recharged by local precipitation and flows in the vertical circulation zone. Evidences from low TDS, water isotopes, and high 3H and 14C indicate that the circulation rate of shallow groundwater is rapid, and the lateral groundwater has strong renewability. Once groundwater pollution from deep shale gas production occurs, it will be recovered soon by enough precipitation.

Abstract:
As shale and tight gas basins are increasingly used to extract natural gas, understanding how gas migrates is important. Wood and Sanei find that secondary migration in a tight-gas basin leads to up-dip transmission of enriched methane into surficial strata which may leak into groundwater and the atmosphere.

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Recently we reported an association of certain diseases with unconventional gas development (UGD). The purpose of this study is to examine UGD's possible impacts on groundwater quality in northeastern Pennsylvania. In this study, we compared our groundwater data (Columbia 58 samples) with those published data from Cabot (1701 samples) and Duke University (150 samples). For each dataset, proportions of samples with elevated levels of dissolved constituents were compared among four groups, identified as upland far (i.e. ≥1km to the nearest UGD gas well), upland near (<1km), valley far (≥1km), and valley near (<1km) groups. The Columbia data do not show statistically significant differences among the 4 groups, probably due to the limited number of samples. In Duke samples, Ca and CI levels are significantly higher in the valley near group than in the valley far group. In the Cabot dataset, methane, Na, and Mn levels are significantly higher in valley far samples than in upland far samples. In valley samples, Ca, Cl, SO4, and Fe are significantly higher in the near group (i.e. <1km) than in the far group. The association of these constituents in valley groundwater with distance is observed for the first time using a large industry dataset. The increase may be caused by enhanced mixing of shallow and deep groundwater in valley, possibly triggered by UGD process. If persistent, these changes indicate potential for further impact on groundwater quality. Therefore, there is an urgent need to conduct more studies to investigate effects of UGD on water quality and possible health outcomes.

Abstract:
Regulatory inspection and violation reports provide insight into the impact of natural gas extraction on the surrounding environment, human health, and public safety. Inspection reports for natural gas wells in Pennsylvania were collected from the Pennsylvania DEP Compliance Report from 2000 to 2014. Analysis of 215,444 inspection records for 70,043 conventional and unconventional wells was conducted in order to compare the odds of violations occurring under different circumstances. Logistic regression models were used to estimate the probability of violations occurring for both conventional and unconventional wells. When inspected, conventional wells had 40% higher odds of having a violation. However, unconventional wells had higher odds for environmental violations related to waste discharge as well as cementing and casing failures. Large operators had 40% lower odds of having any violation than smaller operators. While larger operators had fewer violations, a few of the largest companies had rates of violation much higher than the average for all operators, with some reaching violation rates as high as 1 in 4 active wells. A well also has a higher chance of being in violation if it is in the first year (85%) or second year (109%) since its spud date.

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This study places constraints on the source and transport mechanisms of methane found in groundwater within the Barnett Shale footprint in Texas using dissolved noble gases, with particular emphasis on 84Kr and 132Xe. Dissolved methane concentrations are positively correlated with crustal 4He, 21Ne and 40Ar and suggest that noble gases and methane originate from common sedimentary strata, likely the Strawn Group. In contrast to most samples, four water wells with the highest dissolved methane concentrations unequivocally show strong depletion of all atmospheric noble gases (20Ne, 36Ar, 84Kr, 132Xe) with respect to air-saturated water (ASW). This is consistent with predicted noble gas concentrations in a water phase in contact with a gas phase with initial ASW composition at 18°C-25°C and it suggests an in-situ, highly localized gas source. All of these four wells tap into the Strawn Group and it is likely that small gas accumulations known to be present in the shallow subsurface were reached. Additionally, lack of correlation of 84Kr/36Ar and 132Xe/36Ar fractionation levels along with 4He/20Ne with distance to the nearest gas production wells does not support the notion that methane present in these groundwaters migrated from nearby production wells either conventional or using hydraulic fracturing techniques.

Abstract:
Interaction between hydraulically generated fractures and existing wells (frac hits) could represent a potential risk to groundwater. In particular, frac hits on abandoned oil and gas wells could lead to upward leakage into overlying aquifers, provided migration pathways are present along the abandoned well. However, potential risk to groundwater is relatively unknown because few studies have investigated the probability of frac hits on abandoned wells. In this study, actual numbers of frac hits were not determined. Rather, the probability for abandoned wells to intersect hypothetical stimulated reservoir sizes of horizontal wells was investigated. Well data were compiled and analyzed for location and reservoir information, and sensitivity analyses were conducted by varying assumed sizes of stimulated reservoirs. This study used public and industry data for the Eagle Ford Shale play in south Texas, with specific attention paid to abandoned oil and gas wells converted into water wells (converted wells). In counties with Eagle Ford Shale activity, well-data analysis identified 55,720 abandoned wells with a median age of 1983, and 2400 converted wells with a median age of 1954. The most aggressive scenario resulted in 823 abandoned wells and 184 converted wells intersecting the largest assumed stimulated reservoir size. Analysis showed abandoned wells have the potential to be intersected by multiple stimulated reservoirs, and risks for intersection would increase if currently permitted horizontal wells in the Eagle Ford Shale are actually completed. Results underscore the need to evaluate historical oil and gas activities in areas with modern unconventional oil and gas activities.

Abstract:
The extraction of oil and natural gas from unconventional shale formations has prompted a series of investigations to examine the quality of the groundwater in the overlying aquifers. Here we present a reconnaissance analysis of groundwater quality in the Eagle Ford region of southern Texas. These data reveal two distinct sample populations that are differentiable by bromide/chloride ratios. Elevated levels of fluoride, nitrate, sulfate, various metal ions, and the detection of exotic volatile organic compounds highlight a high bromide group of samples, which is geographically clustered, while encompassing multiple hydrogeological strata. Samples with bromide/chloride ratios representative of connate water displayed elevated levels of total organic carbon, while revealing the detection of alcohols and chlorinated compounds. These findings suggest that groundwater quality in the Western Gulf Basin is, for the most part, controlled by a series of natural processes; however, there is also evidence of episodic contamination events potentially attributed to unconventional oil and gas development or other anthropogenic activities. Collectively, this characterization of natural groundwater constituents and exogenous compounds will guide targeted remediation efforts and provides insight for agricultural entities, industrial operators, and rural communities that rely on groundwater in southern Texas.

Abstract:
Environmental monitoring of shale gas production and geological carbon dioxide (CO2) storage requires identification of subsurface gas sources. Noble gases provide a powerful tool to distinguish different sources if the modifications of the gas composition during transport can be accounted for. Despite the recognition of compositional changes due to gas migration in the subsurface, the interpretation of geochemical data relies largely on zero-dimensional mixing and fractionation models. Here we present two-phase flow column experiments that demonstrate these changes. Water containing a dissolved noble gas is displaced by gas comprised of CO2 and argon. We observe a characteristic pattern of initial co-enrichment of noble gases from both phases in banks at the gas front, followed by a depletion of the dissolved noble gas. The enrichment of the co-injected noble gas is due to the dissolution of the more soluble major gas component, while the enrichment of the dissolved noble gas is due to stripping from the groundwater. These processes amount to chromatographic separations that occur during two-phase flow and can be predicted by the theory of gas injection. This theory provides a mechanistic basis for noble gas fractionation during gas migration and improves our ability to identify subsurface gas sources after post-genetic modification. Finally, we show that compositional changes due to two-phase flow can qualitatively explain the spatial compositional trends observed within the Bravo Dome natural CO2 reservoir and some regional compositional trends observed in drinking water wells overlying the Marcellus and Barnett shale regions. In both cases, only the migration of a gas with constant source composition is required, rather than multi-stage mixing and fractionation models previously proposed.

Abstract:
The recent boom in shale gas development in the Marcellus Shale has increased interest in the methods to distinguish between naturally occurring methane in groundwater and stray methane associated with drilling and production operations. This study evaluates the relationship between natural methane occurrence and three principal environmental factors (groundwater redox state, water type, and topography) using two pre-drill datasets of 132 samples from western Pennsylvania, Ohio, and West Virginia and 1417 samples from northeastern Pennsylvania. Higher natural methane concentrations in residential wells are strongly associated with reducing conditions characterized by low nitrate and low sulfate ([NO3−] < 0.5 mg/L; [SO42−] < 2.5 mg/L). However, no significant relationship exists between methane and iron [Fe(II)], which is traditionally considered an indicator of conditions that have progressed through iron reduction. As shown in previous studies, water type is significantly correlated with natural methane concentrations, where sodium (Na) -rich waters exhibit significantly higher (p<0.001) natural methane concentrations than calcium (Ca)-rich waters. For water wells exhibiting Na-rich waters and/or low nitrate and low sulfate conditions, valley locations are associated with higher methane concentrations than upland topography. Consequently, we identify three factors (“Low NO3− & SO42−” redox condition, Na-rich water type, and valley location), which, in combination, offer strong predictive power regarding the natural occurrence of high methane concentrations. Samples exhibiting these three factors have a median methane concentration of 10,000 µg/L. These heuristic relationships may facilitate the design of pre-drill monitoring programs and the subsequent evaluation of post-drill monitoring results to help distinguish between naturally occurring methane and methane originating from anthropogenic sources or migration pathways.

Abstract:
The recent expansion of natural gas and oil extraction using unconventional oil and gas development (UD) practices such as horizontal drilling and hydraulic fracturing has raised questions about the potential for environmental impacts. Prior research has focused on evaluations of air and water quality in particular regions without explicitly considering temporal variation; thus, little is known about the potential effects of UD activity on the environment over longer periods of time. Here, we present an assessment of private well water quality in an area of increasing UD activity over a period of 13 months. We analyzed samples from 42 private water wells located in three contiguous counties on the Eastern Shelf of the Permian Basin in Texas. This area has experienced a rise in UD activity in the last few years, and we analyzed samples in four separate time points to assess variation in groundwater quality over time as UD activities increased. We monitored general water quality parameters as well as several compounds used in UD activities. We found that some constituents remained stable over time, but others experienced significant variation over the period of study. Notable findings include significant changes in total organic carbon and pH along with ephemeral detections of ethanol, bromide, and dichloromethane after the initial sampling phase. These data provide insight into the potentially transient nature of compounds associated with groundwater contamination in areas experiencing UD activity.

Abstract:
Recent expansion of shale and coal seam gas production worldwide has increased the need for geochemical studies in aquifers near gas deposits, to determine processes impacting groundwater quality and better understand the origins and behavior of dissolved hydrocarbons. We determined dissolved methane concentrations (n = 36) and δ(13)C and δ(2)H values (n = 31) in methane and groundwater from the 46,000-km(2) Gippsland Basin in southeast Australia. The basin contains important water supply aquifers and is a potential target for future unconventional gas development. Dissolved methane concentrations ranged from 0.0035 to 30 mg/L (median = 8.3 mg/L) and were significantly higher in the deep Lower Tertiary Aquifer (median = 19 mg/L) than the shallower Upper Tertiary Aquifer (median = 3.45 mg/L). Groundwater δ(13)CDIC values ranged from -26.4 to -0.4 ‰ and were generally higher in groundwater with high methane concentrations (mean δ(13)CDIC = -9.5 ‰ for samples with >3 mg/L CH4 vs. -16.2 ‰ in all others), which is consistent with bacterial methanogenesis. Methane had δ(13)CCH4 values of -97.5 to -31.8 ‰ and δ(2)HCH4 values of -391 to -204 ‰ that were also consistent with bacterial methane, excluding one site with δ(13)CCH4 values of -31.8 to -37.9 ‰, where methane may have been thermogenic. Methane from different regions and aquifers had distinctive stable isotope values, indicating differences in the substrate and/or methanogenesis mechanism. Methane in the Upper Tertiary Aquifer in Central Gippsland had lower δ(13)CCH4 (-83.7 to -97.5 ‰) and δ(2)HCH4 (-236 to -391 ‰) values than in the deeper Lower Tertiary Aquifer (δ(13)CCH4 = -45.8 to -66.2 ‰ and δ(2)HCH4 = -204 to -311 ‰). The particularly low δ(13)CCH4 values in the former group may indicate methanogenesis at least partly through carbonate reduction. In deeper groundwater, isotopic values were more consistent with acetate fermentation. Not all methane at a given depth and location is interpreted as being necessarily produced in situ. We propose that high dissolved sulphate concentrations in combination with high methane concentrations can indicate gas resulting from contamination and/or rapid migration as opposed to in situ bacterial production or long-term migration. Isotopes of methane and dissolved inorganic carbon (DIC) serve as further lines of evidence to distinguish methane sources. The study demonstrates the value of isotopic characterisation of groundwater including dissolved gases in basins containing hydrocarbons.

Abstract:
Baseline characterization of concentrations and isotopic values of dissolved natural gases is needed to identify contamination caused by the leakage of fugitive gases from oil and gas activities. Methods to collect and analyze baseline concentration-depth profiles of dissolved CH4 and C2H6 and δ13C-CH4 in shales and Quaternary clayey tills were assessed at two sites in the Williston Basin, Canada. Core and cuttings samples were stored in Isojars® in a low O2 headspace prior to analysis. Measurements and multiphase diffusion modeling show that the gas concentrations in core samples yield well-defined and reproducible depth profiles after 31-d equilibration. No measurable oxidative loss or production during core sample storage was observed. Concentrations from cuttings and mud gas logging (including IsoTubes®) were much lower than from cores, but correlated well. Simulations suggest the lower concentrations from cuttings can be attributed to drilling time, and therefore their use to define gas concentration profiles may have inherent limitations. Calculations based on mud gas logging show the method can provide estimates of core concentrations if operational parameters for the mud gas capture cylinder are quantified. The δ13C-CH4 measured from mud gas, IsoTubes®, cuttings, and core samples are consistent, exhibiting slight variations that should not alter the implications of the results in identifying the sources of the gases. This study shows core and mud gas techniques and, to a lesser extent, cuttings, can generate high-resolution depth profiles of dissolved hydrocarbon gas concentrations and their isotopes.

Abstract:
Hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH4) from deeper formations. This study compares concentrations and isotopic compositions of CH4 sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH4 ranging from 0.05 mg/L to 10 mg/L, thus, no immediate remediation is required. The δ13C values of CH4 ranged from −66‰ to −16‰, and δ2H values ranged from −286‰ to −86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH4 was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH4 occurrence corresponded with groundwater abundant in Na+, Cl−, and HCO3−, and with low concentrations of SO42−. The CH4 and SO42−concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH4 was abundant in more reducing waters, and SO42− was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH4 oxidation in shallow groundwater.

Abstract:
Underground injection (UI) is an effective and efficient means of disposing of wastewater from shale gas production. However, the influence of UI on groundwater systems should be examined carefully to protect drinking groundwater sources. A regional hydrogeological model based on TOUGH2-MP/EOS7R of part of the Sichuan Basin is established to simulate pressure changes and solute transport in response to wastewater injection into deep aquifers. Wastewater is assumed to be injected through a well at a rate of 5.45 kg s−1 for 5 years and a post-injection period of 45 years. The simulation results indicate that UI will cause significant pressure buildup during the injection period, after which pressure will dissipate during the post-injection period. The mass fraction of solute increased over the entire simulation period. The draft regulation under the Safe Drinking Water Act and the level III groundwater quality standards regulated by the Chinese government is referenced as the criteria for evaluating the influence of UI on groundwater systems. It is found that maximum pressure levels caused by UI may exceed safe levels. Uncertainties with respect to permeability are analyzed from previous studies and injection test results. Lower levels of permeability incur higher degrees of pressure buildup when UI is implemented. Different injection schemes are discussed, and we verify that pressure buildup from time-variant injection schemes is less than that from constant injection schemes for the same total injection volume. Injection schemes should be carefully evaluated before implementing UI in a shale gas reservoir.

Abstract:
Unconventional oil and gas development has generated intense public concerns about potential impacts to groundwater quality. Specific pathways of contamination have been identified; however, overall rates of contamination remain ambiguous. We used an archive of geochemical data collected from 1988 to 2014 to determine the sources and occurrence of groundwater methane in the Denver-Julesburg Basin of northeastern Colorado. This 60,000-km2 region has a 60-y-long history of hydraulic fracturing, with horizontal drilling and high-volume hydraulic fracturing beginning in 2010. Of 924 sampled water wells in the basin, dissolved methane was detected in 593 wells at depths of 20–190 m. Based on carbon and hydrogen stable isotopes and gas molecular ratios, most of this methane was microbially generated, likely within shallow coal seams. A total of 42 water wells contained thermogenic stray gas originating from underlying oil and gas producing formations. Inadequate surface casing and leaks in production casing and wellhead seals in older, vertical oil and gas wells were identified as stray gas migration pathways. The rate of oil and gas wellbore failure was estimated as 0.06% of the 54,000 oil and gas wells in the basin (lower estimate) to 0.15% of the 20,700 wells in the area where stray gas contamination occurred (upper estimate) and has remained steady at about two cases per year since 2001. These results show that wellbore barrier failure, not high-volume hydraulic fracturing in horizontal wells, is the main cause of thermogenic stray gas migration in this oil- and gas-producing basin.

Abstract:
High volume, hydraulic fracturing (HVHF) processes, used to extract natural gas and oil from underground shale deposits, pose many potential hazards to the environment and human health. HVHF can negatively affect the environment by contaminating soil, water, and air matrices with potential pollutants. Due to the relatively novel nature of the process, hazards to surface waters and human health are not well known. The purpose of this article is to link the impacts of HVHF operations on surface water integrity, with human health consequences. Surface water contamination risks include: increased structural failure rates of unconventional wells, issues with wastewater treatment, and accidental discharge of contaminated fluids. Human health risks associated with exposure to surface water contaminated with HVHF chemicals include increased cancer risk and turbidity of water, leading to increased pathogen survival time. Future research should focus on modeling contamination spread throughout the environment, and minimizing occupational exposure to harmful chemicals.

Abstract:
A system approach is used to investigate the potential risk of groundwater contamination from a failure associated with hydraulic fracturing. The focus is on the role of permeability anisotropy, initial saturation of the medium, leakage depth and leakage rate in controlling the contamination risk at environmentally sensitive locations. We numerically simulate the fluid flow and chemical transport in the geological formations, and use the Monte Carlo algorithm to quantify uncertainty. Geological and operational parameters are selected as random variables. We develop a risk framework to assess three environmental performance metrics: the solute concentration, the arrival times from source to receptor, and the ingestion hazard of the contaminated aquifer. We define risk as the probability of exceeding a certain threshold level for each metric. The effect of parametric uncertainty in risk is also analyzed. The results show that risk strongly depends on water saturation and the anisotropy of the permeability distribution. Furthermore, the measured risk value is more sensitive to leakage depth and leakage rate when compared to the hydrogeological properties. Findings of this study may be applied to situations with more stringent well integrity requirements to ensure that hydraulic fracturing is practiced in an environmentally safe and sound manner, with minimal risk to water contamination.

Abstract:
Shale gas production in the US, predominantly from the Marcellus shale, has been accused of methane emissions and contaminating drinking water under the suspicion that this is caused by hydraulic fracturing in combination with leaking wells. Misunderstandings of the risks of shale gas production are widespread and are causing communication problems. This paper discusses recent preliminary results from the US Environmental Protection Agency (EPA) draft study, which is revealing fact-based issues: EPA did not find evidence that these mechanisms have led to widespread, systemic impacts on drinking water resources in the United States, which contrasts many broad-brushed statements in media and public. The complex geological situation and extraction history of oil, gas and water in the Marcellus area in Pennsylvania is a good case for learnings and demonstrating the need for proper analysis and taking the right actions to avoid problems. State-of-the-art technology and regulations of proper well integrity are available, and their application will provide a sound basis for shale gas extraction.

Abstract:

Abstract:
The development of unconventional oil and gas (UOG) resources has rapidly increased in recent years; however, the environmental impacts and risks are poorly understood. A single well can generate millions of liters of wastewater, representing a mixture of formation brine and injected hydraulic fracturing fluids. One of the most common methods for wastewater disposal is underground injection; we are assessing potential risks of this method through an intensive, interdisciplinary study at an injection disposal facility in West Virginia. In June 2014, waters collected downstream from the site had elevated specific conductance (416 µS/cm) and Na, Cl, Ba, Br, Sr and Li concentrations, compared to upstream, background waters (conductivity, 74 µS/cm). Elevated TDS, a marker of UOG wastewater, provided an early indication of impacts in the stream. Wastewater inputs are also evident by changes in 87Sr/86Sr in stream water adjacent to the disposal facility. Sediments downstream from the facility were enriched in Ra and had high bioavailable Fe(III) concentrations relative to upstream sediments. Microbial communities in downstream sediments had lower diversity and shifts in composition. Although the hydrologic pathways were not able to be assessed, these data provide evidence demonstrating that activities at the disposal facility are impacting a nearby stream and altering the biogeochemistry of nearby ecosystems.

Abstract:
The association between hydrocarbon-rich reservoirs and organic-rich source rocks means unconventional oil and gas plays usually occur in mature sedimentary basins—where large-scale conventional development has already taken place. Abandoned wells in proximity to hydraulic fracturing could be affected by increased fluid pressures and corresponding newly generated fractures that directly connect (frac hit) to an abandoned well or to existing fractures intersecting an abandoned well. If contaminants migrate to a pathway hydraulically connected to an abandoned well, upward leakage may occur. Potential effects of hydraulic fracturing on upward flow through a particular type of leaky abandoned well—abandoned oil and gas wells converted into water wells were investigated using numerical modeling. Several factors that affect flow to leaky wells were considered including proximity of a leaky well to hydraulic fracturing, flowback, production, and leaky well abandonment methods. The numerical model used historical records and available industry data for the Eagle Ford Shale play in south Texas. Numerical simulations indicate that upward contaminant migration could occur through leaky converted wells if certain spatial and hydraulic conditions exist. Upward flow through leaky converted wells increased with proximity to hydraulic fracturing, but decreased when flowback and production occurred. Volumetric flow rates ranged between 0 and 0.086 m3/d for hydraulic-fracturing scenarios. Potential groundwater impacts should be paired with plausible transport mechanisms, and upward flow through leaky abandoned wells could be unrelated to hydraulic fracturing. The results also underscore the need to evaluate historical activities.

Abstract:
Concern over potential impact of shale gas development on shallow groundwater systems requires greater understanding of crustal scale fluid movement. We examined natural deeply circulating groundwater systems in northeastern British Columbia adjacent to a region of shale gas development, in order to elucidate origin of waters, depths of circulation, and controls on fluid flow. These systems are expressed as thermal springs that occur in the deformed sedimentary rocks of the Liard Basin. Stable isotope data from these springs show that they originate as meteoric water. Although there are no thermal anomalies in the region, outlet temperatures range from 30 to 56 °C, reflecting depth of circulation. Based on aqueous geothermometry and geothermal gradients, circulation depths up to 3.8 km are estimated, demonstrating connection of deep groundwater systems to the surface. Springs are also characterised by leakage of thermogenic gas from deep strata that is partly attenuated by methanotrophic microbial communities in the spring waters. Springs are restricted to anomalous structural features, cross cutting faults, and crests of fault-cored anticlines. On a regional scale they are aligned with the major tectonic features of the Liard Line and Larsen Fault. This suggests that while connection of surface to deep reservoirs is possible, it is rare and restricted to highly deformed geologic units that produce permeable pathways from depth through otherwise thick intervening shale units. Results allow a better understanding of potential for communication between deep shale gas units and shallow aquifer systems.

Abstract:
Gas production from shale formations by hydraulic fracturing has raised concerns about the effects on the quality of fresh groundwater. The migration of injected fracking fluids towards the surface was investigated in the North German Basin, based on the known standard lithology. This included cases with natural preferential pathways such as permeable fault zones and fracture networks. Conservative assumptions were applied in the simulation of flow and mass transport triggered by a high pressure boundary of up to 50 MPa excess pressure. The results show no significant fluid migration for a case with undisturbed cap rocks and a maximum of 41 m vertical transport within a permeable fault zone during the pressurization. Open fractures, if present, strongly control the flow field and migration; here vertical transport of fracking fluids reaches up to 200 m during hydraulic fracturing simulation. Long-term transport of the injected water was simulated for 300 years. The fracking fluid rises vertically within the fault zone up to 485 m due to buoyancy. Progressively, it is transported horizontally into sandstone layers, following the natural groundwater flow direction. In the long-term, the injected fluids are diluted to minor concentrations. Despite the presence of permeable pathways, the injected fracking fluids in the reported model did not reach near-surface aquifers, either during the hydraulic fracturing or in the long term. Therefore, the probability of impacts on shallow groundwater by the rise of fracking fluids from a deep shale-gas formation through the geological underground to the surface is small.

Abstract:
The development of unconventional oil and gas resources, controversial in many countries, is currently being pursued by the South African government. This activity can have large impacts on the socio-economic and biophysical environments, especially water resources. In South Africa, little consideration has been given to water-related impacts from the perspective of the interrelated people–ecosystem linkages that are necessary for sustainable social and economic development. This article explores specific water-related linkages between facets of the natural and social environments pertaining to unconventional oil and gas extraction, with the objective of achieving more effective water resources management and water policy development.

Abstract:
More than 90% of Germany's domestic natural gas production and reserves are located in Lower Saxony, North Germany. Recently, research has been intensified with respect to unconventional shale gas, revealing a large additional resource potential in northern Germany. However, many concerns arise within the general public and government/political institutions over potential groundwater contamination from additional gas wells through hydraulic fracturing operations. In order to determine the naturally occurring background methane concentrations, ∼1000 groundwater wells, covering ∼48 000 km2, have been sampled and subsequently analyzed for dissolved methane, ethane and propane and the isotopic composition of methane (δ13C). Dissolved methane concentrations cover a range of ∼7 orders of magnitude between the limit of quantification at ∼20 nl/l and 60 ml/l. The majority of groundwater wells exhibit low concentrations (<1 μl/l), a small number of samples (65) reveal concentration in the range >10 ml/l. In 27% of all samples ethane and in 8% ethane and propane was detected. The median concentration of both components is generally very low (ethane 50 nl/l, propane 23 nl/l). Concentrations reveal a bimodal distribution of the dissolved gas, which might mirror a regional trend due to different hydrogeological settings. The isotopic composition of methane is normally distributed (mean ∼ −70‰ vs PDB), but shows a large variation between −110‰ and +20‰. Samples with δ13C values lower than −55‰ vs PDB (66%) are indicative for methanogenic biogenic processes. 5% of the samples are unusually enriched in 13C (≥25‰ vs PDB) and can best be explained by microbial methane oxidation. According to a standard diagnostic diagram based on methane δ13C values and the ratio of methane over the sum over ethane plus propane (“Bernard”-diagram) less than 4% of the samples plot into the diagnostic field of typical thermogenic natural gases. However, in most cases only ethane has been detected and the remaining less than 15 samples demonstrate an uncommon ratio of ethane to propane compared to typical thermogenic hydrocarbons. These data do not suggest a migration of deeper sourced gases, but a thermogenic source cannot be excluded entirely for some samples. However, ethane and propane can also be generated by microbial processes and might therefore represent ubiquitous background groundwater abundances of these gases. Nevertheless, our data suggest that due to the exceedingly low concentration of ethane and propane, respective concentration changes might prove to be a more sensitive parameter than methane to detect possible migration of deeper sourced (thermally generated) hydrocarbons into a groundwater aquifer.

Abstract:
A comprehensive analysis of all publicly available data and reports was conducted to evaluate impact to Underground Sources of Drinking Water (USDWs) as a result of acid stimulation and hydraulic fracturing in the Pavillion, WY, Field. Although injection of stimulation fluids into USDWs in the Pavillion Field was documented by EPA, potential impact to USDWs at the depths of stimulation as a result of this activity was not previously evaluated. Concentrations of major ions in produced water samples outside expected levels in the Wind River Formation, leakoff of stimulation fluids into formation media, and likely loss of zonal isolation during stimulation at several production wells, indicates that impact to USDWs has occurred. Detection of organic compounds used for well stimulation in samples from two monitoring wells installed by EPA, plus anomalies in major ion concentrations in water from one of these monitoring wells, provide additional evidence of impact to USDWs and indicate upward solute migration to depths of current groundwater use. Detections of diesel range organics and other organic compounds in domestic wells <600 m from unlined pits used prior to the mid-1990s to dispose diesel-fuel based drilling mud and production fluids suggest impact to domestic wells as a result of legacy pit disposal practices.

Abstract:
Development of unconventional energy resources such as shale gas and coalbed methane has generated some public concern with regard to the protection of groundwater and surface water resources from leakage of stray gas from the deep subsurface. In terms of environmental impact to and risk assessment of shallow groundwater resources, the ultimate challenge is to distinguish (a) natural in situ production of biogenic methane, (b) biogenic or thermogenic methane migration into shallow aquifers due to natural causes, and (c) thermogenic methane migration from deep sources due to human activities associated with the exploitation of conventional or unconventional oil and gas resources. This study combines aqueous and gas (dissolved and free) geochemical and isotope data from 372 groundwater samples obtained from 186 monitoring wells of the provincial Groundwater Observation Well Network (GOWN) in Alberta (Canada), a province with a long record of conventional and unconventional hydrocarbon exploration. We investigated whether methane occurring in shallow groundwater formed in situ, or whether it migrated into the shallow aquifers from elsewhere in the stratigraphic column. It was found that methane is ubiquitous in groundwater in Alberta and is predominantly of biogenic origin. The highest concentrations of biogenic methane (> 0.01 mM or >0.2 mg L-1), characterized by delta C-13(CH4) values < -55 parts per thousand, occurred in anoxic Na-Cl, Na-HCO3, and Na-HCO3-Cl type groundwaters with negligible concentrations of nitrate and sulfate suggesting that methane was formed in situ under methanogenic conditions for 39.1% of the samples. In only a few cases (3.7%) was methane of biogenic origin found in more oxidizing shallow aquifer portions suggesting limited upward migration from deeper methanogenic aquifers. Of the samples, 14.1% contained methane with delta C-13(CH4) values >-54 parts per thousand, potentially suggesting a thermogenic origin, but aqueous and isotope geochemistry data revealed that the elevated delta C-13(CH4) values were caused by microbial oxidation of biogenic methane or post-sampling degradation of low CH4 content samples rather than migration of deep thermogenic gas. A significant number of samples (39.2%) contained methane with predominantly biogenic C isotope ratios (delta C-13(CH4) < -55 parts per thousand) accompanied by elevated concentrations of ethane and sometimes trace concentrations of propane. These gases, observed in 28.1% of the samples, bearing both biogenic (delta C-13) and thermogenic (presence of C-3) characteristics, are most likely derived from shallow coal seams that are prevalent in the Cretaceous Horseshoe Canyon and neighboring formations in which some of the groundwater wells are completed. The remaining 3.7% of samples were not assigned because of conflicting parameters in the data sets or between replicates samples. Hence, despite quite variable gas concentrations and a wide range of delta C-13(CH4) values in baseline groundwater samples, we found no conclusive evidence for deep thermogenic gas migration into shallow aquifers either naturally or via anthropogenically induced pathways in this baseline groundwater survey. This study shows that the combined interpretation of aqueous geochemistry data in concert with chemical and isotopic compositions of dissolved and/or free gas can yield unprecedented insights into formation and potential migration of methane in shallow groundwater. This enables the assessment of cross-formational methane migration and provides an understanding of alkane gas sources and pathways necessary for a stringent baseline definition in the context of current and future unconventional hydrocarbon exploration and exploitation.

Abstract:
Shale gas exploration in the St. Lawrence Platform of southern Quebec (eastern Canada) focussed on the Upper Ordovician Utica Shale from 2006 to 2010 during which 28 wells were drilled, 18 of which were fracked. The St. Lawrence Platform is thus considered as a pristine geological domain where potential environmental effects of fracking can be evaluated relative to the natural baseline conditions of the shallow aquifers. In the Saint-Édouard area southwest of Quebec City, it has been shown that groundwater carries variable and locally high levels of naturally occurring dissolved hydrocarbons in which thermogenic ethane and propane can be found. Fifteen shallow (30–147 m) wells were drilled into bedrock and sampled (cores and cuttings) with the purpose of characterizing the shallow bedrock in a shale gas pre-development context. The shallow bedrock geology is made of three Upper Ordovician clastic formations. The Lotbinière and Les Fonds formations are time- and facies-correlative with the Utica Shale present at a depth of 1.5 to 2 km in this area. They are dominated by calcareous black shales with minor siltstone and micrite beds. The Nicolet Formation is the youngest unit of the area and consists of gray to dark gray shales with locally abundant thick siltstone and fine-grained sandstone beds. The organic matter in the Lotbinière and Les Fonds formations is represented by solid bitumen with subordinate liptinite algae, graptolites and chitinozoans representing normal marine Type II kerogen. Both formations are at the post-peak hydrocarbon generation as indicated by the equivalent random vitrinite reflectance of 0.94 to 1.04%. Rock Eval data support the Type II nature of the kerogen and the late oil window maturation level. Hydrocarbon extracts from the three formations have yielded high to low concentrations of C1 to C6. For all units, an upward decrease in total volatiles (C1 + C2 + C3) together with an increase in the gas dryness ratio (C1/C2 + C3) is recorded, the transitions occurring at depths shallower than 50 m where the shales are more fractured. The upward increase in the gas dryness ratio results from the more significant reduction of ethane and propane concentrations compared to that of methane. Consistent with the dryness ratio trend, the δ13CVPDB values of methane change from thermogenic values (≈− 50‰) for deeper samples, to more biogenic (negative) values (<− 60‰) at shallow depths. A similar δ2HVSMOW trend of more negative values at shallower depths is noted. The δ13CVPDB and δ2HVSMOW values of rock-hosted methane indicate that samples at shallow depth recorded a microbial influence. It is proposed that diffusion and some microbial degradation of hydrocarbons are responsible for the decrease of rock volatiles and the in situ generation of biogenic methane in the shales at shallow depths to mix with the in situ thermogenic methane. The Utica Shale is a very good source rock with high generation potential. However, thermogenic volatiles can also originate from shallower units with much shorter migration pathways. The mixed thermogenic and biogenic methane in the groundwater results from fracture-enhanced diffusion and biodegradation of volatiles at shallow depths.