Isotope Approach to Assess Hydrologic Connections During Marcellus Shale Drilling

Water and gas samples were collected from (1) nine shallow groundwater aquifers overlying Marcellus Shale in north‐central West Virginia before active shale gas drilling, (2) wells producing gas from Upper Devonian sands and Middle Devonian Marcellus Shale in southwestern Pennsylvania, (3) coal‐mine water discharges in southwestern Pennsylvania, and (4) streams in southwestern Pennsylvania and north‐central West Virginia. Our preliminary results demonstrate that the oxygen and hydrogen isotope composition of water, carbon isotope composition of dissolved inorganic carbon, and carbon and hydrogen isotope compositions of methane in Upper Devonian sands and Marcellus Shale are very different compared with shallow groundwater aquifers, coal‐mine waters, and stream waters of the region. Therefore, spatiotemporal stable isotope monitoring of the different sources of water before, during, and after hydraulic fracturing can be used to identify migrations of fluids and gas from deep formations that are coincident with shale gas drilling.     

Effect of Different Sampling Methodologies on Measured Methane Concentrations in Groundwater Samples

Analysis of dissolved light hydrocarbon gas concentrations (primarily methane and ethane) in water supply wells is commonly used to establish conditions before and after drilling in areas of shale gas and oil extraction. Several methods are currently used to collect samples for dissolved gas analysis from water supply wells; however, the reliability of results obtained from these methods has not been quantified. This study compares dissolved methane and ethane concentrations measured in groundwater samples collected using three sampling methods employed in pre‐ and post‐drill sampling programs in the Appalachian Basin. These include an open‐system collection method where 40 mL volatile organic analysis (VOA) vials are filled directly while in contact with the atmosphere (Direct‐Fill VOA) and two alternative methods: (1) a semi‐closed system method whereby 40 mL VOA vials are filled while inverted under a head of water (Inverted VOA) and (2) a relatively new (2013) closed system method in which the sample is collected without direct contact with purge water or the atmosphere (IsoFlask^®). This study reveals that, in the absence of effervescence, the difference in methane concentrations between the three sampling methods was relatively small. However, when methane concentrations equaled or exceeded 20 mg/L (the approximate concentration at which effervescence occurs in the study area), IsoFlask^® (closed system) samples yielded significantly higher methane concentrations than Direct‐Fill VOA (open system) samples, and Inverted VOA (semi‐closed system) samples yielded lower concentrations. These results suggest that open and semi‐closed system sample collection methods are adequate for non‐effervescing samples. However, the use of a closed system collection method provides the most accurate means for the measurement of dissolved hydrocarbon gases under all conditions.     

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

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

Environmental Factors Associated With Natural Methane Occurrence in the Appalachian Basin

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; [SO₄^2?] < 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^? & SO₄^2?” 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.     

Modeling of Methane Migration in Shallow Aquifers from Shale Gas Well Drilling

The vertical portion of a shale gas well, known as the “tophole” is often drilled using an air‐hammer bit that may introduce pressures as high as 2400 kPa (350 psi) into groundwater while penetrating shallow aquifers. A 3‐D TOUGH2 model was used to simulate the flow of groundwater under the high hydraulic heads that may be imposed by such trapped compressed air, based on an observed case in West Virginia (USA) in 2012. The model realizations show that high‐pressure air trapped in aquifers may cause groundwater to surge away from the drill site at observable velocities. If dissolved methane is present within the aquifer, the methane can be entrained and transported to a maximum distance of 10.6 m per day. Results from this study suggest that one cause of the reported increase in methane concentrations in groundwater near shale gas production wells may be the transport of pre‐existing methane via groundwater surges induced by air drilling, not necessarily direct natural gas leakage from the unconventional gas reservoir. The primary transport mechanisms are advective transport of dissolved methane with water flow, and diffusive transport of dissolved methane.     

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

Horizontal drilling and hydraulic fracturing have enhanced unconventional hydrocarbon recovery but raised environmental concerns related to water quality. Because most basins targeted for shale‐gas development in the USA have histories of both active and legacy petroleum extraction, confusion about the hydrogeological context of naturally occurring methane in shallow aquifers overlying shales remains. The Karoo Basin, located in South Africa, provides a near‐pristine setting to evaluate these processes, without a history of conventional or unconventional energy extraction. We conducted a comprehensive pre‐industrial evaluation of water quality and gas geochemistry in 22 groundwater samples across the Karoo Basin, including dissolved ions, water isotopes, hydrocarbon molecular and isotopic composition, and noble gases. Methane‐rich samples were associated with high‐salinity, NaCl‐type groundwater and elevated levels of ethane, ⁴He, and other noble gases produced by radioactive decay. This endmember displayed less negative δ¹³C‐CH₄ and evidence of mixing between thermogenic natural gases and hydrogenotrophic methane. Atmospheric noble gases in the methane‐rich samples record a history of fractionation during gas‐phase migration from source rocks to shallow aquifers. Conversely, methane‐poor samples have a paucity of ethane and ⁴He, near saturation levels of atmospheric noble gases, and more negative δ¹³C‐CH₄; methane in these samples is biogenic and produced by a mixture of hydrogenotrophic and acetoclastic sources. These geochemical observations are consistent with other basins targeted for unconventional energy extraction in the USA and contribute to a growing data base of naturally occurring methane in shallow aquifers globally, which provide a framework for evaluating environmental concerns related to unconventional energy development (e.g., stray gas).     

Oxidation of fugitive methane in ground water linked to bacterial sulfate reduction

When fugitive methane migrates upward along boreholes of oil and gas wells, it may migrate into shallow ground water or pass through overlying soil to the atmosphere. Prior to this study, there was little information on the fate of fugitive methane that migrates into ground water. In a field study near Lloydminster, Alberta, Canada, we found hydrogeochemical evidence that fugitive methane from an oil well migrated into a shallow aquifer but has been attenuated by dissimilatory bacterial sulfate reduction at low temperature ( approximately 5 degrees C) under anaerobic conditions. Evidence includes spatial and temporal trends in concentrations of methane and sulfate in ground water and associated trends in concentrations of bicarbonate and sulfide. Within 10 m of the oil well, sulfate concentrations were low, and sulfate was enriched in both 34S and 18O. Sulfate concentrations had a strong positive correlation with delta13C values of bicarbonate, and sulfide was depleted in 34S compared to sulfate. These data indicate that bacterial sulfate reduction occurred near the production well. Near the oil well, elevated concentrations of bicarbonate were observed, and the bicarbonate was depleted in 13C. Modeling indicates that the main source of this excess 13C-depleted bicarbonate is oxidized methane. In concert with the sulfate concentration and isotope data, these results support an interpretation that in situ bacterial oxidation of methane has occurred, linked to bacterial sulfate reduction. Bacterial sulfate reduction may play a major role in bioattenuation of fugitive natural gas in ground water in western Canada.     

Controls on Methane Occurrences in Aquifers Overlying the Eagle Ford Shale Play,South Texas

Assessing natural vs. anthropogenic sources of methane in drinking water aquifers is a critical issue in areas of shale oil and gas production. The objective of this study was to determine controls on methane occurrences in aquifers in the Eagle Ford Shale play footprint. A total of 110 water wells were tested for dissolved light alkanes, isotopes of methane, and major ions, mostly in the eastern section of the play. Multiple aquifers were sampled with approximately 47 samples from the Carrizo‐Wilcox Aquifer (250‐1200 m depth range) and Queen City‐Sparta Aquifer (150‐900 m depth range) and 63 samples from other shallow aquifers but mostly from the Catahoula Formation (depth <150 m). Besides three shallow wells with unambiguously microbial methane, only deeper wells show significant dissolved methane (22 samples >1 mg/L, 10 samples >10 mg/L). No dissolved methane samples exhibit thermogenic characteristics that would link them unequivocally to oil and gas sourced from the Eagle Ford Shale. In particular, the well water samples contain very little or no ethane and propane (C1/C2+C3 molar ratio >453), unlike what would be expected in an oil province, but they also display relatively heavier δ¹³C_methane (>?55‰) and δD_methane (>?180‰). Samples from the deeper Carrizo and Queen City aquifers are consistent with microbial methane sourced from syndepositional organic matter mixed with thermogenic methane input, most likely originating from deeper oil reservoirs and migrating through fault zones. Active oxidation of methane pushes δ¹³C_methane and δD_methane toward heavier values, whereas the thermogenic gas component is enriched with methane owing to a long migration path resulting in a higher C1/C2+C3 ratio than in the local reservoirs.     

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas,Eastern Kentucky

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ¹³C‐CH₄ and δ²H‐CH₄) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ¹³C‐CH₄ and δ²H‐CH₄ ranged from ?84.0‰ to ?58.3‰ and from ?246.5‰ to ?146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO₂ reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region.     

Potential Contaminant Pathways from Hydraulically Fractured Shale to Aquifers

Hydraulic fracturing of deep shale beds to develop natural gas has caused concern regarding the potential for various forms of water pollution. Two potential pathways—advective transport through bulk media and preferential flow through fractures—could allow the transport of contaminants from the fractured shale to aquifers. There is substantial geologic evidence that natural vertical flow drives contaminants, mostly brine, to near the surface from deep evaporite sources. Interpretative modeling shows that advective transport could require up to tens of thousands of years to move contaminants to the surface, but also that fracking the shale could reduce that transport time to tens or hundreds of years. Conductive faults or fracture zones, as found throughout the Marcellus shale region, could reduce the travel time further. Injection of up to 15,000,000 L of fluid into the shale generates high pressure at the well, which decreases with distance from the well and with time after injection as the fluid advects through the shale. The advection displaces native fluids, mostly brine, and fractures the bulk media widening existing fractures. Simulated pressure returns to pre‐injection levels in about 300 d. The overall system requires from 3 to 6 years to reach a new equilibrium reflecting the significant changes caused by fracking the shale, which could allow advective transport to aquifers in less than 10 years. The rapid expansion of hydraulic fracturing requires that monitoring systems be employed to track the movement of contaminants and that gas wells have a reasonable offset from faults.     

Trace Element Behavior in Methane‐Rich and Methane‐Free Groundwater in North and East Texas

There is concern about adverse impacts of natural gas (primarily methane) production on groundwater quality; however, data on trace element concentrations are limited. The objective of this study was to compare the distribution of trace elements in groundwater samples with and without dissolved methane in aquifers overlying the Barnett Shale (Hood and Parker counties, 207 samples) and the Haynesville Shale (Panola County, 42 samples). Both shales have been subjected to intensive hydraulic fracturing for gas production. Well clusters with high dissolved methane were previously found in these counties and are thought to be of natural origin. Overall, groundwater in these counties is of excellent quality with typically low elemental concentrations. Several statistical analyses strongly suggest that most trace element concentrations, generally at low background levels, are no higher and even reduced when dissolved methane is present. In addition, trace element concentrations are not correlated with distance to gas wells. The reduction in trace element concentrations is attributed to anaerobic microbial degradation of methane, is associated with a higher pH (>8.5), and, likely, with precipitation of carbonates and pyrite and formation of clays. Trace and other elements are likely incorporated within the precipitating mineral crystalline network or sorbed. High pH values are found throughout these high‐methane clusters (e.g., Parker‐Hood cluster), even in subregions where methane is not present, which is consistent with a pervasive natural origin of dissolved methane rather than a limited gas well source.     

Controls on Methane Occurrences in Shallow Aquifers Overlying the Haynesville Shale Gas Field,East Texas

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.     

Noble gas anomalies related to high-intensity methane gas seeps in the Black Sea

Dissolved noble gases and tritium were analyzed at a series of high-intensity methane gas seeps in the Black Sea to study the transport and gas exchange induced by bubble-streams in the water column. These processes affect marine methane emissions to the atmosphere and are therefore relevant to climate warming. The seep areas investigated are located in the Dnepr paleo-delta, west of Crimea, and in the Sorokin Trough mud volcano area, south-east of Crimea. Noble gas concentration profiles at active seep sites revealed prominent anomalies compared to reference profiles that are unaffected by outgassing. Supersaturations of the light noble gases helium and neon observed relatively close to the sea floor are interpreted as effects of gas exchange between the water and the rising bubbles. Depletions of the heavy noble gases argon, krypton and xenon that were detected above an active, bubble-releasing mud volcano appear to be related to the injection of fluids depleted in noble gases that undergo vertical transport in the water column due to small density differences. In both cases, the noble gas anomalies clearly document seep-specific processes which are difficult to detect by other methods. Helium is generally enriched in the deep water of the Black Sea due to terrigenic input. Although exceptionally high helium concentrations observed in one seep area indicate a locally elevated helium flux, most of the seeps studied seem to be negligible sources of terrigenic helium. Noble gas analyses of sediment pore waters from the vicinity of a mud volcano showed large vertical gradients in helium concentrations. The helium isotope signature of the pore waters points to a crustal origin for helium, whereas the deep water of the Black Sea also contains a small mantle-type component.     

Methane Occurrences in Aquifers Overlying the Barnett Shale Play with a Focus on Parker County,Texas

Clusters of elevated methane concentrations in aquifers overlying the Barnett Shale play have been the focus of recent national attention as they relate to impacts of hydraulic fracturing. The objective of this study was to assess the spatial extent of high dissolved methane previously observed on the western edge of the play (Parker County) and to evaluate its most likely source. A total of 509 well water samples from 12 counties (14,500 km²) were analyzed for methane, major ions, and carbon isotopes. Most samples were collected from the regional Trinity Aquifer and show only low levels of dissolved methane (85% of 457 unique locations <0.1 mg/L). Methane, when present is primarily thermogenic (δ¹³C 10th and 90th percentiles of ?57.54 and ?39.00‰ and C1/C2+C3 ratio 10th, 50th, and 90th percentiles of 5, 15, and 42). High methane concentrations (>20 mg/L) are limited to a few spatial clusters. The Parker County cluster area includes historical vertical oil and gas wells producing from relatively shallow formations and recent horizontal wells producing from the Barnett Shale (depth of ～1500 m). Lack of correlation with distance to Barnett Shale horizontal wells, with distance to conventional wells, and with well density suggests a natural origin of the dissolved methane. Known commercial very shallow gas accumulations (<200 m in places) and historical instances of water wells reaching gas pockets point to the underlying Strawn Group of Paleozoic age as the main natural source of the dissolved gas.     

Some Challenges Posed by Coal Bed Methane Regional Assessment Modeling

Coal measures (coal bearing rock strata) can contain large reserves of methane. These reserves are being exploited at a rapidly increasing rate in many parts of the world. To extract coal seam gas, thousands of wells are drilled at relatively small spacing to depressurize coal seams to induce desorption and allow subsequent capture of the gas. To manage this process effectively, the effect of coal bed methane (CBM) extraction on regional aquifer systems must be properly understood and managed. Groundwater modeling is an integral part of this management process. However, modeling of CBM impacts presents some unique challenges, as processes that are operative at two very different scales must be adequately represented in the models. The impacts of large‐scale gas extraction may be felt over a large area, yet despite the significant upscaling that accompanies construction of a regional model, near‐well conditions and processes cannot be ignored. These include the highly heterogeneous nature of many coal measures, and the dual‐phase flow of water and gas that is induced by coal seam depressurization. To understand these challenges, a fine‐scale model was constructed incorporating a detailed representation of lithological heterogeneity to ensure that near‐well processes and conditions could be examined. The detail of this heterogeneity was at a level not previously employed in models built to assess groundwater impacts arising from CBM extraction. A dual‐phase reservoir simulator was used to examine depressurization and water desaturation processes in the vicinity of an extractive wellfield within this fine‐scale model. A single‐phase simulator was then employed so that depressurization errors incurred by neglecting near‐well, dual‐phase flow could be explored. Two models with fewer lithological details were then constructed in order to examine the nature of depressurization errors incurred by upscaling and to assess the interaction of the upscaling process with the requirement for adequate representation of near‐source, dual‐phase processes.     

Applications of a total dissolved gas pressure probe in ground water studies

Measurements of dissolved gases have numerous applications in ground water hydrology, and it is now possible to measure the total dissolved gas pressure in situ using a probe. Dissolved gas pressure is measured by submerging a headspace volume with a gas-permeable membrane, allowing dissolved gases in the water to equilibrate with gases in the headspace, then measuring the pressure in the headspace with a pressure transducer. Total dissolved gas pressure (TGP) probes have many potential uses in ground water studies employing dissolved gases, including: (1) determining approximate excess air levels, which may provide information about the time and location of recharge; (2) screening wells for air contamination, which can compromise the accuracy of dissolved gas tracer techniques: (3) detecting a trapped gas phase, which can significantly reduce hydraulic conductivity and impede the transport of dissolved solutes and gases; (4) enabling the use of gas-filled passive diffusion samplers for determining accurate dissolved gas concentrations; and (5) determining relative concentrations of CH4 and CO2 when they are known to be highly abundant. Although TGP probes designed for surface water have been available for several years, TGP probes suitable for ground water applications have only recently become available. Herein we present what are, to our knowledge, the first reported ground water dissolved gas data collected using a TGP probe. We also explain the basic operating principles of these probes and discuss the potential applications listed.     

Low-Cost Apparatus for On-Site Monitoring of Methane in Ground Water

An upsurge in oil- and gas-well drilling in northwestern Pennsylvania and western New York has been accompanied by several incidents of contamination of ground water by methane. Determining which well is causing the contamination is extremely difficult if more than one gas or oil well is present in the area.
The fact that the solubility of methane decreases as the pressure on ground water decreases provides a quantitative basis for monitoring changes in the amount of methane in the ground water. Quantitative measurements of the volume of methane given off by ground water pumped from a well as the water enters atmospheric pressure permit detection of temporal changes in the gas content which are too subtle to be detected visually. These gas volume changes may, in some cases, be correlated with variations in the pressure of methane in the annulus of nearby individual gas/oil wells and thus may provide a means of pinpointing the gas/oil well that is causing the methane contamination.
The basic principle of the gas-volume monitoring apparatus (GVMA) described in this paper is that as a measured amount of ground water enters atmospheric pressure the gas which comes out of solution is trapped and measured. The GVMA can be constructed of materials costing less than $100 and requires no special skills to assemble or operate. In a recent study conducted in a western New York village, four homeowners were able to collect quantitative gas-volume data from their household water wells daily in about one-half hour. Unlike laboratory analyses for dissolved methane, there is no cost involved in monitoring with the GVMA beyond the initial instrument cost and operator time. Another advantage is that the data are available immediately.     

Life cycle greenhouse gas footprint of shale gas: a probabilistic approach

With the increase in natural gas (NG) production in recent years, primarily from shale gas, some sources, including the US Environmental Protection Agency (EPA), have suggested that upstream methane emissions are increasing. Much of the recent controversy has centered on emissions during well drilling, testing, and completion even though emissions downstream of the wellhead are also of concern. The study critically assessed the current state of knowledge about the life cycle GHG footprint of NG, analyzed the assumptions, data and analysis methodologies used in the existing literature. This study comprehensively analyzed the emission of methane from different stage of the life of well for conventional and unconventional NG using the EPA’s revised 2011 estimates as well as other existing literature and publicly available government data. The study proposed a probabilistic model to estimate the range of total GHG footprint of NG with varying probabilities. Through the bottom up approach starting from the well construction to the delivery of NG to the small user and using Monte Carlo simulation, the study identified the critical sources of fugitive emissions from the NG. As expected, emissions from well completion and periodic emissions (e.g. liquid unloading in the case of onshore conventional wells and workovers in the case of unconventional wells) are significant contributors to the overall GHG footprint of NG, and possess large opportunity for reduction. Finally the application of probabilistic model is demonstrated through a case study using the data from the Montney and Horn River shale gas basins in the Northern British Columbia to estimate the range of total GHG footprint of shale gas with varying probabilities. The study found that the GHG footprint of Montney and Horn River wells are much smaller than that of Barnett shale (which is representative of US shale gas) due to strict flaring regulations followed in BC. The study also undercuts the outcome of Howarth et al. (Clim Chang Lett 106:679–690, 2011), which states that the GHG footprint of shale gas is at least 20 % greater than coal.     

Geochemistry of the Springfield Plateau aquifer of the Ozark Plateaus Province in Arkansas,Kansas, Missouri and Oklahoma,USA

Geochemical data indicate that the Springfield Plateau aquifer, a carbonate aquifer of the Ozark Plateaus Province in central USA, has two distinct hydrochemical zones. Within each hydrochemical zone, water from springs is geochemically and isotopically different than water from wells. Geochemical data indicate that spring water generally interacts less with the surrounding rock and has a shorter residence time, probably as a result of flowing along discrete fractures and solution openings, than water from wells. Water type throughout most of the aquifer was calcium bicarbonate, indicating that carbonate‐rock dissolution is the primary geochemical process occurring in the aquifer. Concentrations of calcium, bicarbonate, dissolved oxygen and tritium indicate that most ground water in the aquifer recharged rapidly and is relatively young (less than 40 years). In general, field‐measured properties, concentrations of many chemical constituents, and calcite saturation indices were greater in samples from the northern part of the aquifer (hydrochemical zone A) than in samples from the southern part of the aquifer (hydrochemical zone B). Factors affecting differences in the geochemical composition of ground water between the two zones are difficult to identify, but could be related to differences in chert content and possibly primary porosity, solubility of the limestone, and amount and type of cementation between zone A than in zone B. In addition, specific conductance, pH, alkalinity, concentrations of many chemical constituents and calcite saturation indices were greater in samples from wells than in samples from springs in each hydrochemical zone. In contrast, concentrations of dissolved oxygen, nitrite plus nitrate, and chloride generally were greater in samples from springs than in samples from wells. Water from springs generally flows rapidly through large conduits with minimum water–rock interactions. Water from wells flow through small fractures, which restrict flow and increase water–rock interactions. As a result, springs tend to be more susceptible to surface contamination than wells. The results of this study have important implications for the geochemical and hydrogeological processes of similar carbonate aquifers in other geographical locations. Copyright © 2000 John Wiley & Sons, Ltd.     

Groundwater Protection and Unconventional Gas Extraction: The Critical Need for Field‐Based Hydrogeological Research

Unconventional natural gas extraction from tight sandstones, shales, and some coal‐beds is typically accomplished by horizontal drilling and hydraulic fracturing that is necessary for economic development of these new hydrocarbon resources. Concerns have been raised regarding the potential for contamination of shallow groundwater by stray gases, formation waters, and fracturing chemicals associated with unconventional gas exploration. A lack of sound scientific hydrogeological field observations and a scarcity of published peer‐reviewed articles on the effects of both conventional and unconventional oil and gas activities on shallow groundwater make it difficult to address these issues. Here, we discuss several case studies related to both conventional and unconventional oil and gas activities illustrating how under some circumstances stray or fugitive gas from deep gas‐rich formations has migrated from the subsurface into shallow aquifers and how it has affected groundwater quality. Examples include impacts of uncemented well annuli in areas of historic drilling operations, effects related to poor cement bonding in both new and old hydrocarbon wells, and ineffective cementing practices. We also summarize studies describing how structural features influence the role of natural and induced fractures as contaminant fluid migration pathways. On the basis of these studies, we identify two areas where field‐focused research is urgently needed to fill current science gaps related to unconventional gas extraction: (1) baseline geochemical mapping (with time series sampling from a sufficient network of groundwater monitoring wells) and (2) field testing of potential mechanisms and pathways by which hydrocarbon gases, reservoir fluids, and fracturing chemicals might potentially invade and contaminate useable groundwater.