Repository for Oil and Gas Energy Research (ROGER)

Abstract:
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.

Abstract:
Hydraulic fracturing operations have been viewed as the cause of certain environmental issues including groundwater contamination. The potential for hydraulic fracturing to induce contaminant pathways in groundwater is not well understood since gas wells are completed while isolating the water table and the gas-bearing reservoirs lay thousands of feet below the water table. Recent studies have attributed ground water contamination to poor well construction and leaks in the wellbore annulus due to ruptured wellbore casings. In this paper, a geospatial model of the Barnett Shale region was created using ArcGIS. The model was used for spatial analysis of groundwater quality data in order to determine if regional variations in groundwater quality, as indicated by various groundwater constituent concentrations, may be associated with the presence of hydraulically fractured gas wells in the region. The Barnett Shale reservoir pressure, completions data, and fracture treatment data were evaluated as predictors of groundwater quality change. Results indicated that elevated concentrations of certain groundwater constituents are likely related to natural gas production in the study area and that beryllium, in this formation, could be used as an indicator variable for evaluating fracturing impacts on regional groundwater quality. Results also indicated that gas well density and formation pressures correlate to change in regional water quality whereas proximity to gas wells, by itself, does not. The results also provided indirect evidence supporting the possibility that micro annular fissures serve as a pathway transporting fluids and chemicals from the fractured wellbore to the overlying groundwater aquifers.

Abstract:
In 2010, a dramatic increase in the levels of total trihalomethane (THM) and the relative proportion of brominated species was observed in finished water at several Pennsylvania water utilities (PDW) using the Allegheny River as their raw water supply. An increase in bromide (Br−) concentrations in the Allegheny River was implicated to be the cause of the elevated water disinfection byproducts. This study focused on quantifying the contribution of Br− from a commercial wastewater treatment facility (CWTF) that solely treats wastes from oil and gas producers and discharges into the upper reaches of the Allegheny River, and impacts on two downstream PDWs. In 2012, automated daily integrated samples were collected on the Allegheny River at six sites during three seasonal two-week sampling campaigns to characterize Br− concentrations and river dispersion characteristics during periods of high and low river discharges. The CWTF discharges resulted in significant increases in Br− compared to upstream baseline values in PDW raw drinking water intakes during periods of low river discharge. During high river discharge, the assimilative dilution capacity of the river resulted in lower absolute halide concentrations, but significant elevations Br− concentrations were still observed at the nearest downstream PDW intake over baseline river levels. On days with active CWTF effluent discharge the magnitude of bromide impact increased by 39 ppb (53%) and 7 ppb (22%) for low and high river discharge campaigns, respectively. Despite a declining trend in Allegheny River Br− (2009–2014), significant impacts from CWTF and coal-fired power plant discharges to Br− concentrations during the low river discharge regime at downstream PDW intakes was observed, resulting in small modeled increases in total THM (3%), and estimated positive shifts (41–47%) to more toxic brominated THM analogs. The lack of available coincident measurements of THM, precursors, and physical parameters limited the interpretation of historical trends.

Abstract:
To assess potential future impacts on shallow aquifers by leakage of natural gas from unconventional energy resource development it is essential to establish a reliable baseline. Occurrence of methane in shallow groundwater in Alberta between 2006 and 2014 was assessed and was ubiquitous in 186 sampled monitoring wells. Free and dissolved gas sampling and measurement approaches yielded comparable results with low methane concentrations in shallow groundwater, but in 28 samples from 21 wells methane exceeded 10 mg/L in dissolved gas and 300,000 ppmv in free gas. Methane concentrations in free and dissolved gas samples were found to increase with well depth and were especially elevated in groundwater obtained from aquifers containing coal seams and shale units. Carbon isotope ratios of methane averaged − 69.7 ± 11.1‰ (n = 63) in free gas and − 65.6 ± 8.9‰ (n = 26) in dissolved gas. δ13C values were not found to vary with well depth or lithology indicating that methane in Alberta groundwater was derived from a similar source. The low δ13C values in concert with average δ2HCH4 values of − 289 ± 44‰ (n = 45) suggest that most methane was of biogenic origin predominantly generated via CO2 reduction. This interpretation is confirmed by dryness parameters typically > 500 due to only small amounts of ethane and a lack of propane in most samples. Comparison with mud gas profile carbon isotope data revealed that methane in the investigated shallow groundwater in Alberta is isotopically similar to hydrocarbon gases found in 100–250 meter depths in the WCSB and is currently not sourced from thermogenic hydrocarbon occurrences in deeper portions of the basin. The chemical and isotopic data for methane gas samples obtained from Alberta groundwater provide an excellent baseline against which potential future impact of deeper stray gases on shallow aquifers can be assessed.

Abstract:
Real and potential environmental effects of drill cuttings deposition in open-mining pit were studied. An analysis of selected parameters of deposited drilling waste, groundwater taken from piezometers and eluates obtained during batch leaching tests of drill cuttings was the basis for the estimation. The high concentrations of barium, lead, and zinc in drilling waste (maximum measured values equal to 54; 152; and 438 mg/kg dry weight, respectively) do not allow to classify the examined materials as inert waste from the extractive industries. The groundwater taken from the piezometers located around the drilling waste landfill contained high concentrations of total organic carbon (up to 21.9 mgC/L) boron, calcium, magnesium, manganese, aluminum, and potassium (up to 2.12; 455; 148; 1.75; 5.11; and 25 mg/L, respectively). In contrast to this observation, concentrations of barium and chlorides were the most exceeded in the batch leaching tests. It suggests that pollution of groundwater was not caused by drilling waste deposition.

Abstract:
As a prelude to potential development of South Africa’s shale gas resources, it is critical to develop and implement effective groundwater governance arrangements. Existing policies and plans were analysed to determine whether critical gaps or barriers exist that could potentially lead to impacts on groundwater systems. Ten high-priority governance challenges were identified: (a) defining relevant metrics for baseline groundwater quality and availability; (b) developing guidelines for shale gas resource licensing, exploration, drilling, extraction, production, and completion; (c) defining and enforcing compliance monitoring systems; (d) dealing punitively with non-compliant operators; (e) mitigating and managing risks to prevent impairment of groundwater resources; (f) implementing a goal-based regulatory framework; g) enforcing strict chemical disclosure requirements; (h) coordinating across government departments and regulatory bodies meaningfully and productively; (i) implementing a framework for subsidiarity and support to local water management; and (j) providing an incentive framework that supports strong groundwater management and environmental protection. To overcome these challenges, it is recommended that a decentralised, polycentric, bottom-up approach involving multiple institutions is developed to adaptively manage shale gas development. This transition from the current rigid regulatory structure can foster cooperation and collaboration among key stakeholders. The use of a pro-active groundwater governance structure that can accommodate current, near-term, and long-term shale gas development is important for ensuring that future energy development in South Africa incorporates the influence of other simultaneous stressors such as climate (e.g. drought), landuse changes, population growth, industry, and competing demands for water.

Abstract:
Prior work suggests spatial parameters (e.g., landscape position, distance to nearest gas well) can be used to estimate the amount of dissolved methane in domestic drinking water wells overlying the deep Marcellus Shale. New York (NY) provides an opportunity to investigate methane occurrence prior to expansion of high-volume hydraulic fracturing because unconventional gas production is currently banned in the state. We sampled domestic groundwater wells for methane in 2013 (n = 137) across five counties of NY bordering Pennsylvania, and then resampled a subset of those wells in 2014 for methane concentrations and δ13C-CH4 and δD-CH4. The majority of waters from wells sampled (77%) had low concentrations of methane (<0.1 mg/L), and only 5% (n = 7) had actionable levels of methane (>10 mg/L). Dissolved methane concentrations did not change as a function of proximity to existing vertical gas wells, nor other parameters indicating subsurface planes of weakness (i.e., faults or lineaments). Methane levels were significantly higher in wells closer to hydrography flow lines, and most strongly correlated to Na-HCO3 water type. The distribution of methane between Ca-HCO3 (n = 76) and Na-HCO3 (n = 23) water types significantly differed (p < 0.01), with median methane concentrations of 0.002 and 0.78 mg/L, respectively. Combined classification of sampled waters based on the dominant water cation, well topographic position, and geologic unit of well completion effectively identified wells with a greater than 50% probability of having methane concentrations exceeding 1 mg/L. Such classification schemes may be useful as a screening tool to assess natural versus gas production-related sources of methane in domestic wells.

Abstract:
The objective of this paper is to review different risk assessment techniques applicable to onshore unconventional oil and gas production to determine the risks to water quantity and quality associated with hydraulic fracturing and produced water management. Water resources could be at risk without proper management of water, chemicals, and produced water. Previous risk assessments in the oil and gas industry were performed from an engineering perspective leaving aside important social factors. Different risk assessment methods and techniques are reviewed and summarized to select the most appropriate one to perform a holistic and integrated analysis of risks at every stage of the water life cycle. Constraints to performing risk assessment are identified including gaps in databases, which require more advanced techniques such as modeling. Discussions on each risk associated with water and produced water management, mitigation strategies, and future research direction are presented. Further research on risks in onshore unconventional oil and gas will benefit not only the U.S. but also other countries with shale oil and gas resources.

Abstract:
The potential impact of rapid development of unconventional oil and natural gas resources using hydraulic fracturing and horizontal drilling on regional groundwater quality has received significant attention. Major concerns are methane or oil/gas related hydrocarbon (such as TPHs, BTEX including benzene, toluene, ethybenzene and xylene) leaks into the aquifer due to the failure of casing and/or stray gas migration. Previously, we investigated the relationship between oil and gas activity and dissolved methane concentration in a drinking water aquifer with the major finding being the presence of thermogenic methane contamination, but did not find detectable concentrations of TPHs or BTEX. To understand if aqueous and gas phases from the producing formation were transported concurrently to drinking water aquifers without the presence of oil/gas related hydrocarbons, the ionic composition of three water groups was studied: (1) uncontaminated deep confined aquifer, (2) suspected contaminated groundwater - deep confined aquifer containing thermogenic methane, and (3) produced water from nearby oil and gas wells that would represent aqueous phase contaminants. On the basis of quantitative and spatial analysis, we identified that the “thermogenic methane contaminated” groundwater did not have similarities to produced water in terms of ionic character (e.g. Cl/TDS ratio), but rather to the “uncontaminated” groundwater. The analysis indicates that aquifer wells with demonstrated gas phase contamination have not been contacted by an aqueous phase from oil and gas operations according to the methodology we use in this study and the current groundwater quality data from COGCC. However, the research does not prove conclusively that this the case. The results may provide insight on contamination mechanisms since improperly sealed well casing may result in stray gas but not aqueous phase transport.

Abstract:
Unconventional oil and gas (UOG) production produces large quantities of wastewater with complex geochemistry and largely uncharacterized impacts on surface waters. In this study, we assessed shifts in microbial community structure and function in sediments and waters upstream and downstream from a UOG wastewater disposal facility. To do this, quantitative PCR for 16S rRNA and antibiotic resistance genes along with metagenomic sequencing were performed. Elevated conductivity and markers of UOG wastewater characterized sites sampled downstream from the disposal facility compared to background sites. Shifts in overall high level functions and microbial community structure were observed between background sites and downstream sediments. Increases in Deltaproteobacteria and Methanomicrobia and decreases in Thaumarchaeota were observed at downstream sites. Genes related to dormancy and sporulation and methanogenic respiration were 18–86 times higher at downstream, impacted sites. The potential for these sediments to serve as reservoirs of antimicrobial resistance was investigated given frequent reports of the use of biocides to control the growth of nuisance bacteria in UOG operations. A shift in resistance profiles downstream of the UOG facility was observed including increases in acrB and mexB genes encoding for multidrug efflux pumps, but not overall abundance of resistance genes. The observed shifts in microbial community structure and potential function indicate changes in respiration, nutrient cycling, and markers of stress in a stream impacted by UOG waste disposal operations.

Abstract:
Spatial gaps in environmental monitoring have important consequences for public policy and regulation of new industrial developments. In the case of Marcellus Shale gas extraction, a water-intensive new form of energy production that is taking place in the state of Pennsylvania (USA), the perception of large gaps in government water monitoring efforts have motivated numerous civil society organizations (CSOs) to initiate their own monitoring programs. Using geospatial mapping, this study reveals that nearly half of the watersheds in the region lack government water monitoring, and CSOs are the sole source of continuous or frequent monitoring data in 22% of the watersheds. While many watersheds remain unmonitored, the gaps do not map on to demographic characteristics typically associated with environmental injustice. This study probes both the reasons for and the implications of the gaps in watershed monitoring, drawing conclusions about the promise and limitations of citizen science.

Abstract:

Abstract:
The last decade has seen a dramatic increase in domestic energy production from unconventional reservoirs. This energy boom has generated marked economic benefits, but simultaneously evoked significant concerns regarding the potential for drinking-water contamination in shallow aquifers. Presently, efforts to evaluate the environmental impacts of shale gas development in the northern Appalachian Basin (NAB), located in the northeastern US, are limited by: (1) a lack of comprehensive “pre-drill” data for groundwater composition (water and gas); (2) uncertainty in the hydrogeological factors that control the occurrence of naturally present CH4 and brines in shallow Upper Devonian (UD) aquifers; and (3) limited geochemical techniques to quantify the sources and migration of crustal fluids (specifically methane) at various time scales. To address these questions, we analyzed the noble gas, dissolved ion, and hydrocarbon gas geochemistry of 72 drinking-water wells and one natural methane seep all located ≫1 km from shale gas drill sites in the NAB. In the present study, we consciously avoided groundwater wells from areas near active or recent drilling to ensure shale gas development would not bias the results. We also intentionally targeted areas with naturally occurring CH4 to characterize the geochemical signature and geological context of gas-phase hydrocarbons in shallow aquifers of the NAB. Our data display a positive relationship between elevated [CH4], [C2H6], [Cl], and [Ba] that co-occur with high [4He]. Although four groundwater samples show mantle contributions ranging from 1.2% to 11.6%, the majority of samples have [He] ranging from solubility levels (∼45 × 10−6 cm3 STP/L) with below-detectable [CH4] and minor amounts of tritiogenic 3He in low [Cl] and [Ba] waters, up to high [4He] = 0.4 cm3 STP/L with a purely crustal helium isotopic end-member (3He/4He = ∼0.02 times the atmospheric ratio (R/Ra)) in samples with CH4 near saturation for shallow groundwater (P(CH4) = ∼1 atmosphere) and elevated [Cl] and [Ba]. These data suggest that 4He is dominated by an exogenous (i.e., migrated) crustal source for these hydrocarbon gas- and salt-rich fluids. In combination with published inorganic geochemistry (e.g., 87Sr/86Sr, Sr/Ba, Br−/Cl−), new noble gas and hydrocarbon isotopic data (e.g., 20Ne/36Ar, C2+/C1, δ13C-CH4) suggest that a hydrocarbon-rich brine likely migrated from the Marcellus Formation (via primary hydrocarbon migration) as a dual-phase fluid (gas + liquid) and was fractionated by solubility partitioning during fluid migration and emplacement into conventional UD traps (via secondary hydrocarbon migration). Based on the highly fractionated 4He/CH4 data relative to Marcellus and UD production gases, we propose an additional phase of hydrocarbon gas migration where natural gas previously emplaced in UD hydrocarbon traps actively diffuses out into and equilibrates with modern shallow groundwater (via tertiary hydrocarbon migration) following uplift, denudation, and neotectonic fracturing. These data suggest that by integrating noble gas geochemistry with hydrocarbon and dissolved ion chemistry, one can better determine the source and migration processes of natural gas in the Earth’s crust, which are two critical factors for understanding the presence of hydrocarbon gases in shallow aquifers.

Abstract:
Unconventional natural gas production in the Marcellus and Utica formations of the Northeastern United States raises concerns about potential impacts to shallow groundwater. We examined and interpreted 13,040 analyses from pre-drilling groundwater samples from domestic water wells in northeastern (NE) Pennsylvania and 8004 samples from water wells in the “Western Area” which includes southwest Pennsylvania, eastern Ohio, and north-central West Virginia. These samples were acquired on behalf of Chesapeake Energy Corporation as part of its local pre-drilling water supply monitoring program. We evaluated concentrations of major ions and metals relative to federal drinking-water-quality standards upon which regulatory decisions are often based. Chesapeake’s dataset, the most comprehensive for these areas, shows that exceedance of at least one water-quality standard occurs in 63% of water well samples in NE Pennsylvania and 87% in the Western Area. In NE Pennsylvania, 10% of the samples exceeded one or more of the United States Environmental Protection Agency’s (USEPA) primary maximum contaminant levels (MCLs) for drinking-water supplies, 46.1% of the samples exceeded one or more of USEPA secondary maximum contaminant levels (SMCLs), and another 7% exceeded one or more of USEPA health advisory or regional screening levels for tap water. In the Western Area 8% of samples exceeded one or more MCLs, 65% exceeded one or more SMCLs, and 15% exceeded one or more health advisory or regional screening levels for tap water. Chesapeake’s dataset, orders of magnitude larger than any in previously published literature, shows that water-quality exceedances relate to factors such: as where the sample occurs within the groundwater flow system, the natural groundwater chemical type (hydrochemical facies), the geologic unit producing the water, and/or the topographic position (valley versus upland). Our comparison of these results to historical groundwater data from NE Pennsylvania, which pre-dates most unconventional shale gas development, shows that the recent pre-drilling geochemical data is similar to historical data. We see no broad changes in variability of chemical quality in this large dataset to suggest any unusual salinization caused by possible release of produced waters from oil and gas operations, even after thousands of gas wells have been drilled among tens of thousands of domestic wells within the two areas studied. Our evaluation also agrees with early researchers such as Piper (1933) and Lohman (1939, 1937) who found that the saline waters in both areas underlie fresher groundwater. The saline water is naturally-occurring connate brine or salt water which has not been flushed by circulating meteoric water; rather than vertical migration of salt water from deep strata such as the Marcellus shale as suggested by Warner et al. (2012). Elevated metals concentrations, particularly iron and manganese, partly relate to sample turbidity; dissolved metals would provide a more accurate measurement of metals in shallow groundwater than does the total metals analysis typically required by regulations.

Abstract:
A review of available literature and current governance approaches related to the potential impacts of hydraulic fracturing on water quality (including drinking water) was developed. The paper identifies gaps in literature and (or) current governance approaches that should be addressed to guide decision-makers in the development of appropriate regulatory regimes that will enable assessment of the impacts of hydraulic fracturing on water quality. The lack of credible and comprehensive data are shown to have been a major setback to properly investigate and monitor hydraulic fracturing activities and their potential risks on the environment and water quality. A review of current governance approaches demonstrates that some jurisdictions have implemented baseline and post-operation water quality monitoring requirements; however, there are large variations in site-specific monitoring requirements across Canada and the United States. In light of recent information, a targeted approach is suggested based on risk..., Les auteurs ont conduit une revue incluant la littérature disponible et les approches courantes de gouvernance reliées aux impacts potentiels de la fracturation hydraulique sur la qualité de l’eau, incluant l’eau potable. On identifie des failles dans la littérature et (ou) les approches courantes de gouvernance qui devraient être considérées afin de guider les preneurs de décisions dans le développement de régimes règlementaires appropriés, rendant possible l’évaluation des impacts de la fracturation hydraulique sur la qualité de l’eau. On démontre que le manque de données crédibles et intégratives a constitué un empêchement majeur pour examiner correctement et faire le suivi des activités de fracturation hydraulique et de leur potentiel de risques pour l’environnement et la qualité de l’eau. Cette revue des approches actuelles de gouvernance démontre que certaines juridictions on mis sur pied une ligne de base et l’exigence de faire le suivi de la qualité de l’eau après les opérations; cependant on obse...

Abstract:
Migration of stray methane gas near the town of Dimock, Pennsylvania, has been at the center of the debate on the safety of shale gas drilling and hydraulic fracturing in the United States. The presented study relates temporal variations in molecular concentrations and stable isotope compositions of methane and ethane to shale-gas well activity (i.e., vertical/horizontal drilling, hydraulic fracturing and remedial actions). This was accomplished by analyzing data collected, between 2008 and 2012, by state and federal agencies and the gas well operator. In some cases, methane migration started prior to hydraulic fracturing. Methane levels of contaminated water wells sampled were one to several orders of magnitude greater than the concentrations due to natural variation in water wells of the local area. Isotope analyses indicate that all samples had a thermogenic origin at varying maturity levels, but from formations above the hydraulically fractured Marcellus Shale. The results from the initial water well samples were similar to annular gas values, but not those of production gases. This indicates that leakage by casing cement seals most likely caused the impacts, not breaks in the production casing walls. Remediation by squeeze cementing was partially effective in mitigating impacts of gas migration. In several cases where remediation caused a substantial reduction in methane levels, there were also substantial changes in the isotope values, providing evidence of two sources, one natural and the other man-induced. Sampling water wells while venting gas wells appears to be a cost-effective method for determining if methane migration has occurred.

Abstract:
Detailed research on the content of heavy metals in ground and surface waters in the upper Sanna River catchment was initiated in 2013. The investigations were conducted in one of the most promising areas of potential shale gas extraction, in which the Frampol 1 test wellbore was drilled in 2012 (SE Poland, Roztocze Region). In the area of the wellbore, hydrochemical analyses of the waters of the river drainage zone were performed. Water was sampled from six objects representing soil water, porous groundwater, fissure-layer groundwater, and river water. The hydrological regime of groundwater and surface water was analysed based on data obtained from automatic recorders of water levels and results of periodic measurements of water flow. In 2013, water was sampled on a monthly basis for determination of the levels of Ba, Sr, Al, Fe, Mn, Zn, Cu, Cd, Co, Cr, Ni, As, V, Rb, Pb, Th, and U. The analysis results showed that the concentration of Sr was usually in the range of 100-400 A mu g/L, Fe 10-100 A mu g/L, Ba 10-40 A mu g/L, and Mn, Al, and Zn 1-10 A mu g/L. The concentration of the other metals generally did not exceed 1 A mu g/L. The concentrations of the elements analysed in the zone of drinking water intake were within the range specified by Polish and WHO standards. Significant differences were found in the metal content in the analysed waters; they were related to the water intake site, form of land management, and hydrometeorological conditions. The highest metal content was recorded in soil and river waters and the lowest in the spring waters of the main water-bearing horizon. At the current stage of the research, no impact of the Frampol 1 shale gas exploration wellbore on the metal content in the upper Sanna River catchment was found.

Abstract:
One of the critical environmental questions about hydraulic fracturing in shales is the potential for contamination of ground and surface water. There are two specific concerns arising from hydraulic treatments: 1) whether hydraulic fractures extend upward through overlying strata to reach overlying aquifers containing drinking water, and 2) whether injected fluids push native fluids upward into these overlying aquifers. In this work, the extent of likely fracture growth through overlying layers during hydraulic treatment of the Marcellus shale was estimated using a hydraulic fracture model. A wide range of material and fluid flow properties in a multi-layered geologic model was considered. The model was based on conditions and characteristics applicable to the Marcellus shale in that part of the Appalachian basin within southwestern Pennsylvania. Predictions of vertical termination frequencies for hydraulic fractures were used in a multi-layer model of the strata and natural fractures for studying brine migration through the natural and induced fracture network. NFFLOW, the software for explicitly modeling flow within networks of fractures, was utilized to compute transient flow rates according to the schedule of injected fluid during hydraulic fracturing. To aid our analysis, the modeled sequence of geologic strata was capped with a fictitious unfractured, but moderately-permeable layer, which serves as a monitoring zone. The analysis assumes one well lateral was placed in the middle of the Marcellus shale with hydraulic fractures penetrating layers in the model. The newly-developed geomechanical module within NFFLOW was used to represent stress-sensitivity of the fractures. This allows the opening and closing of fracture apertures with changes in fluid pressures within fracture segments. Pressure increases in the formations overlying the Tully limestone, indicating fluid flow, was observed due to the hydraulic stimulation; and the impact of these increased pressures on brine migration towards the surface was considered.

Abstract:
Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency’s maximum contaminant levels, and low levels of both gasoline range (0–8 ppb) and diesel range organic compounds (DRO; 0–157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.

Abstract:
Construction of unconventional natural gas (UNG) infrastructure (e.g., well pads, pipelines) is an increasingly common anthropogenic stressor that increases potential sediment erosion. Increased sediment inputs into nearby streams may decrease autotrophic processes through burial and scour, or sediment bound nutrients could have a positive effect through alleviating potential nutrient limitations. Ten streams with varying catchment UNG well densities (0–3.6 wells/km2) were sampled during winter and spring of 2010 and 2011 to examine relationships between landscape scale disturbances associated with UNG activity and stream periphyton [chlorophyll a (Chl a)] and gross primary production (GPP). Local scale variables including light availability and water column physicochemical variables were measured for each study site. Correlation analyses examined the relationships of autotrophic processes and local scale variables with the landscape scale variables percent pasture land use and UNG metrics (well density and well pad inverse flow path length). Both GPP and Chl a were primarily positively associated with the UNG activity metrics during most sample periods; however, neither landscape variables nor response variables correlated well with local scale factors. These positive correlations do not confirm causation, but they do suggest that it is possible that UNG development can alleviate one or more limiting factors on autotrophic production within these streams. A secondary manipulative study was used to examine the link between nutrient limitation and algal growth across a gradient of streams impacted by natural gas activity. Nitrogen limitation was common among minimally impacted stream reaches and was alleviated in streams with high UNG activity. These data provide evidence that UNG may stimulate the primary production of Fayetteville shale streams via alleviation of N-limitation. Restricting UNG activities from the riparian zone along with better enforcement of best management practices should help reduce these possible impacts of UNG activities on stream autotrophic processes.

Abstract:
Oil and gas extraction and coal-fired electrical power generating stations produce wastewaters that are treated and discharged to rivers in Western Pennsylvania with public drinking water system (PDWS) intakes. Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used to quantify inorganic species in wastewater and river samples using a method based on EPA Method 200.7 rev4.4. A total of 53 emission lines from 30 elements (Al, As, B, Ba, Ca, Cd, Ce, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, Tl, V, and Zn) were investigated. Samples were prepared by microwave-assisted acid digestion using a mixture of 2% HNO3 and 0.5% HCl. Lower interferences and better detection characteristics resulted in selection of alternative wavelengths for Al, As, Sb, Mg, Mo, and Na. Radial view measurements offered accurate determinations of Al, Ba, K, Li, Na, and Sr in high-brine samples. Spike recovery studies and analyses of reference materials showed 80–105% recoveries for most analytes. This method was used to quantify species in samples with high to low brine concentrations with method detection limits a factor of 2 below the maximum contaminant limit concentrations of national drinking water standards. Elements B, Ca, K, Li, Mg, Na, and Sr were identified as potential tracers for the sources impacting PDWS intakes. Usability of the ICP-OES derived data for factor analytic model applications was also demonstrated.

Abstract:
Multiple stressors threaten stream physical and biological quality, including elevated nutrients and other contaminants, riparian and in-stream habitat degradation and altered natural flow regime. Unconventional oil and gas (UOG) development is one emerging stressor that spans the U.S. UOG development could alter stream sedimentation, riparian extent and composition, in-stream flow, and water quality. We developed indices to describe the watershed sensitivity and exposure to natural and anthropogenic disturbances and computed a vulnerability index from these two scores across stream catchments in six productive shale plays. We predicted that catchment vulnerability scores would vary across plays due to climatic, geologic and anthropogenic differences. Across-shale averages supported this prediction revealing differences in catchment sensitivity, exposure, and vulnerability scores that resulted from different natural and anthropogenic environmental conditions. For example, semi-arid Western shale play catchments (Mowry, Hilliard, and Bakken) tended to be more sensitive to stressors due to low annual average precipitation and extensive grassland. Catchments in the Barnett and Marcellus-Utica were naturally sensitive from more erosive soils and steeper catchment slopes, but these catchments also experienced areas with greater UOG densities and urbanization. Our analysis suggested Fayetteville and Barnett catchments were vulnerable due to existing anthropogenic exposure. However, all shale plays had catchments that spanned a wide vulnerability gradient. Our results identify vulnerable catchments that can help prioritize stream protection and monitoring efforts. Resource managers can also use these findings to guide local development activities to help reduce possible environmental effects.

Abstract:
Understanding the transport of hydraulic fracturing (HF) fluid that is injected into the deep subsurface for shale gas extraction is important to ensure that shallow drinking water aquifers are not contaminated. Topographically driven flow, overpressured shale reservoirs, permeable pathways such as faults or leaky wellbores, the increased formation pressure due to HF fluid injection, and the density contrast of the HF fluid to the surrounding brine can encourage upward HF fluid migration. In contrast, the very low shale permeability and capillary imbibition of water into partially saturated shale may sequester much of the HF fluid, and well production will remove HF fluid from the subsurface. We review the literature on important aspects of HF fluid migration. Single-phase flow and transport simulations are performed to quantify how much HF fluid is removed via the wellbore with flowback and produced water, how much reaches overlying aquifers, and how much is permanently sequestered by capillary imbibition, which is treated as a sink term based on a semianalytical, one-dimensional solution for two-phase flow. These simulations include all of the important aspects of HF fluid migration identified in the literature review and are performed in five stages to faithfully represent the typical operation of a hydraulically fractured well. No fracturing fluid reaches the aquifer without a permeable pathway. In the presence of a permeable pathway, 10 times more fracturing fluid reaches the aquifer if well production and capillary imbibition are not included in the model.

Abstract:
Flowback fluids associated with hydraulic fracturing shale gas extraction are a potential source of contamination for shallow aquifers. In the Marcellus Shale region of northeastern Pennsylvania, certified water tests have been used to establish baseline water chemistry of private drinking water wells. This study investigates whether a single, certified multiparameter water test is sufficient for establishing baseline water chemistry from which possible future contamination by flowback waters could be reliably recognized. We analyzed the water chemistry (major and minor inorganic elements and stable isotopic composition) of multiple samples collected from lake, spring, and well water from 35 houses around Fiddle Lake, Susquehanna County, PA that were collected over approximately a two-year period. Statistical models estimated variance of results within and between households and tested for significant differences between means of our repeated measurements and prior certified water tests. Overall, groundwater chemistry varies more spatially due to heterogeneity of minerals within the bedrock aquifer and due to varying inputs of road salt runoff from paved roads than it does temporally at a single location. For wells located within road salt-runoff zones, Na+ and Cl− concentrations, although elevated, are generally consistent through repeated measurements. High acid neutralizing capacity (ANC) and base cation concentrations in well water sourced from mineral weathering reactions, and a uniform stable isotopic composition for well water, suggests long flowpaths for groundwater that dampen seasonal variability of most elements. Exceptions occur for two wells within road salt runoff zones that show the greatest range of concentrations for Na+ and Cl−, suggesting that these wells have a faster pathway to surficial recharge. Additionally, sampling protocols can induce variability for Fe, Mn, and Pb, making other elements identified in flowback fluids (Ba, Br, Ca, Cl, Mg, Na, Sr) more dependable indicators of contamination. Although there is general concordance between our repeated measurements and the certified test results, characterizing baseline chemistry is strengthened when results from multiple households are combined to establish regional upper baseline limits that will have a low probability of being exceeded by future samples unless conditions have changed.

Abstract:
Public and regulatory agencies are concerned over the potential for drinking water contamination related to high-volume hydraulic fracturing (hydrofracking) of the Marcellus shale in Pennsylvania and in New York State (NYS), where exploitation of Marcellus gas has not yet begun. Unique natural tracers are helpful for distinguishing the influence of formation water and/or flow-back water. Here we use halogen concentrations, particularly bromine and iodine, to characterize natural variability of baseline water chemistry in the southern tier of NYS. Majority of streams and drinking water wells have Br and I concentrations below 1 and 0.1 μM, respectively, a range typical for relatively pristine surface water and shallow groundwater. Wells that have higher Br and I concentrations are likely affected by formation waters. Br/I ratios indicate two different sources of formation waters in these wells, possibly controlled by geologic settings. Our results suggest that iodine, combined with other halogens, may be a novel and sensitive tool for fingerprinting trace levels of formation water signal in drinking water sources.

Abstract:
The ecologically sensitive Susquehanna River Basin (SRB) is an important recharge area and drinking water source for a large population in the northeastern United States. Seasonal road salt application, the presence of regional brines at shallow depths, and produced waters associated with active and legacy conventional Upper Devonian oil and gas wells could increase total dissolved solids (TDS) in groundwater and streams. This study focused on SRB watersheds along the New York/Pennsylvania border, in order to assess current water quality and to establish baseline geochemistry for ground and surface water in a region with potential for increased development of the Marcellus Shale and other unconventional shale gas units. Geochemical composition was determined for 300 stream samples collected from ten sites in four watersheds over variable seasonal flow conditions, and for groundwater from over 500 drinking water wells in this region. Results indicate that many streams and groundwater wells in the study area have elevated TDS levels that indicate pre-existing contributions from saline sources. Dilution of these inputs with fresh water, and the lack of low-level trace element concentrations and isotopic composition in many water quality analyses, highlight the need for alternate robust and sensitive chemical signatures. Comparison with Cl/Br anion ratios and 87Sr/86Sr isotope ratios indicate that the (Ba + Sr)/Mg ratio can be used to discriminate between road salt and regional brine in these cases, and mixing models show that even small additions (0.1–0.01%) of these contaminants can be detected with this cation ratio. The (Ba + Sr)/Mg ratio may be even more sensitive (by an order of magnitude) to incursions of Marcellus Shale produced water, depending on the composition of Marcellus produced waters in this region. This study highlights the need for baseline sampling of freshwater reservoirs and the characterization of potential high TDS sources at a local and regional scale.

Abstract:
Unconventional natural gas development via horizontal drilling and hydraulic fracturing has greatly increased the supply of natural gas in the United States. However, the practice presents concerns about the possibility for impacts on shallow groundwater aquifers. The Deep River Triassic Basin in central North Carolina is likely to contain natural gas that could be extracted via hydraulic fracturing in the future. Unlike other states where hydraulic fracturing has been employed, North Carolina has no history of commercial oil and gas extraction. In this study, we measured water chemistry, dissolved gases, and volatile organic compounds in 51 private drinking water well samples over the Deep River Triassic Basin. Our data document the background water quality of shallow aquifers in the Deep River Basin, which could provide an important baseline dataset if hydraulic fracturing occurs here in the future. We found only two of the 51 water wells sampled had dissolved CH4 concentrations >0.1 mg/L, and no well had a methane concentration >0.5 mg/L. The δ 13C–CH4 of the two highest CH4 concentration water wells (−69.5‰ and −61‰) suggest a biogenic CH4 source and are distinct from the δ 13C–CH4 of two test gas wells drilled in the area (−54.41‰ and −45.11‰). Unlike other basins overlying shale gas formations in the US, we find no evidence for CH4 migration into shallow groundwater in the Triassic basin. In addition, we found only seven VOCs in five water samples, with all levels below the US EPA’s maximum contaminant levels. Ion and trace metal concentrations in most samples were also below US EPA primary drinking water standards, with the exception of two samples that exceed the standards for As. We modeled the depth of the upper surface of the Cumnock Shale formation in the Deep River Basin using a kriging algorithm and found that its depth below the surface is shallow (0–∼1500 m) relative to other shale formations that have been drilled commercially in the US, including the Marcellus in Pennsylvania and the Fayetteville in Arkansas. The relatively shallow shale, combined with the presence of multiple faults and diabase intrusions that characterize the geology of the area, may make the Deep River Triassic Basin more vulnerable to deep fluid connectivity to shallow aquifers.

Abstract:
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.

Abstract:
Reports highlight the safety of hydraulic fracturing for drinking water if it occurs ?many hundreds of meters to kilometers underground?. To our knowledge, however, no comprehensive analysis of hydraulic fracturing depths exists. Based on fracturing depths and water use for ?44?000 wells reported between 2010 and 2013, the average fracturing depth across the United States was 8300 ft (?2500 m). Many wells (6900; 16%) were fractured less than a mile from the surface, and 2600 wells (6%) were fractured above 3000 ft (900 m), particularly in Texas (850 wells), California (720), Arkansas (310), and Wyoming (300). Average water use per well nationally was 2?400?000 gallons (9?200?000 L), led by Arkansas (5?200?000 gallons), Louisiana (5?100?000 gallons), West Virginia (5?000?000 gallons), and Pennsylvania (4?500?000 gallons). Two thousand wells (?5%) shallower than one mile and 350 wells (?1%) shallower than 3000 ft were hydraulically fractured with >1 million gallons of water, particularly in Arkansas, New Mexico, Texas, Pennsylvania, and California. Because hydraulic fractures can propagate 2000 ft upward, shallow wells may warrant special safeguards, including a mandatory registry of locations, full chemical disclosure, and, where horizontal drilling is used, predrilling water testing to a radius 1000 ft beyond the greatest lateral extent.

Abstract:
Due to the rapid expansion in hydraulic fracturing (fracking), there is a need for robust, portable and specific water analysis techniques. Early detection of contamination is crucial for the prevention of lasting environmental damage. Bromide can potentially function as an early indicator of water contamination by fracking waste, because there is a high concentration of bromide ions in fracking wastewaters. To facilitate this, a microfluidic paper-based analytical device (μPAD) has been developed and optimized for the quantitative colorimetric detection of bromide in water using a smartphone. A paper microfluidic platform offers the advantages of inexpensive fabrication, elimination of unstable wet reagents, portability and high adaptability for widespread distribution. These features make this assay an attractive option for a new field test for on-site determination of bromide.

Abstract:
Development of shale gas entails environmental risk, particularly with respect to water resources, and stakeholders are keen to assess such risks before making development decisions. We focus on Pennsylvania, USA and the Marcellus Shale, the most productive shale play in the country. We examine compliance data recorded by the state regulatory agency in order to assess environmental risks and their trends and drivers over time. Overall, we track 3267 shale gas violations, noting that environmental violation rates increase from 2007 to 2009, remain high through 2010, and then drop in 2011 and thereafter. Violations related to spills and erosion were most commonly issued. A single change in policy resulted in a 45% decrease in environmental violation rates. Furthermore, for every 1% increase in wells drilled per inspections conducted, there was a 0.56% decrease in environmental violation rates. Similar effects were not found for administrative violations. Operator identity, price of gas, and other major policies were not significantly correlated with violation rates. In comparing conventional and shale gas extraction compliance we found that shale gas development entails more risk related to spills and solid waste management, while conventional development entails more risk associated with cementing and casing issues, and site restoration.

Abstract:
The exploration of unconventional shale energy reserves and the extensive use of hydraulic fracturing during well stimulation have raised concerns about the potential effects of unconventional oil and gas extraction (UOG) on the environment. Most accounts of groundwater contamination have focused primarily on the compositional analysis of dissolved gases to address whether UOG activities have had deleterious effects on overlying aquifers. Here, we present an analysis of 550 groundwater samples collected from private and public supply water wells drawing from aquifers overlying the Barnett shale formation of Texas. We detected multiple volatile organic carbon compounds throughout the region, including various alcohols, the BTEX family of compounds, and several chlorinated compounds. These data do not necessarily identify UOG activities as the source of contamination; however, they do provide a strong impetus for further monitoring and analysis of groundwater quality in this region as many of the compounds we detected are known to be associated with UOG techniques.

Abstract:
Oil and gas extraction in shale plays expanded rapidly in the U.S. and is projected to expand globally in the coming decades. Arkansas has doubled the number of gas wells in the state since 2005 mostly by extracting gas from the Fayetteville Shale with activity concentrated in mixed pasture-deciduous forests. Concentrated well pads in close proximity to streams could have adverse effects on stream water quality and biota if sedimentation associated with developing infrastructure or contamination from fracturing fluid and waste occurs. Cumulative effects of gas activity and local habitat conditions on macroinvertebrate communities were investigated across a gradient of gas well activity (0.2-3.6wells per km(2)) in ten stream catchments in spring 2010 and 2011. In 2010, macroinvertebrate density was positively related to well pad inverse flowpath distance from streams (r=0.84, p<0.001). Relatively tolerant mayflies Baetis and Caenis (r=0.64, p=0.04), filtering hydropsychid caddisflies (r=0.73, p=0.01), and chironomid midge densities (r=0.79, p=0.008) also increased in streams where more well pads were closer to stream channels. Macroinvertebrate trophic structure reflected environmental conditions with greater sediment and primary production in streams with more gas activity close to streams. However, stream water turbidity (r=0.69, p=0.02) and chlorophyll a (r=0.89, p<0.001) were the only in-stream variables correlated with gas well activities. In 2011, a year with record spring flooding, a different pattern emerged where mayfly density (p=0.74, p=0.01) and mayfly, stonefly, and caddisfly richness (r=0.78, p=0.008) increased in streams with greater well density and less silt cover. Hydrology and well pad placement in a catchment may interact to result in different relationships between biota and catchment activity between the two sample years. Our data show evidence of different macroinvertebrate communities expressed in catchments with different levels of gas activity that reinforce the need for more quantitative analyses of cumulative freshwater-effects from oil and gas development.

Abstract:
Methane and brine leakage rates and associated time scales along the cemented casing of a hypothetical decommissioned shale gas well have been assessed with a multiphase flow and multicomponent numerical model. The conceptual model used for the simulations assumes that the target shale formation is 200 m thick, overlain by a 750 m thick caprock, which is in turn overlain by a 50 m thick surficial sand aquifer, the 1000 m geological sequence being intersected by a fully penetrating borehole. This succession of geological units is representative of the region targeted for shale gas exploration in the St. Lawrence Lowlands (Québec, Canada). The simulations aimed at assessing the impact of well casing cementation quality on methane and brine leakage at the base of a surficial aquifer. The leakage of fluids can subsequently lead to the contamination of groundwater resources and/or, in the case of methane migration to ground surface, to an increase in greenhouse gas emissions. The minimum reported surface casing vent flow (measured at ground level) for shale gas wells in Quebec (0.01 m3/d) is used as a reference to evaluate the impact of well casing cementation quality on methane and brine migration. The simulations suggest that an adequately cemented borehole (with a casing annulus permeability kc ≤ 1 mD) can prevent methane and brine leakage over a time scale of up to 100 years. However, a poorly cemented borehole (kc ≥ 10 mD) could yield methane leakage rates at the base of an aquifer ranging from 0.04 m3/d to more than 100 m3/d, depending on the permeability of the target shale gas formation after abandonment and on the quantity of mobile gas in the formation. These values are compatible with surface casing vent flows reported for shale gas wells in the St. Lawrence Lowlands (Quebec, Canada). The simulated travel time of methane from the target shale formation to the surficial aquifer is between a few months and 30 years, depending on cementation quality and hydrodynamic properties of the casing annulus. Simulated long-term brine leakage rates after 100 years for poorly cemented boreholes are on the order of 10−5 m3/d (10 mL/d) to 10−3 m3/d (1 L/d). Based on scoping calculations with a well-mixed aquifer model, these rates are unlikely to have a major impact on groundwater quality in a confined aquifer since they would only increase the chloride concentration in a pristine aquifer to 1 mg/L, which is significantly below the commonly recommended aesthetic objective of 250 mg/L for chloride.

Abstract:
Northeastern Pennsylvania has rapidly changed over the past 5 years from an area with no unconventional natural gas drilling, to the most productive shale gas region within the Marcellus shale play, causing concerns about environmental safety. One issue that has caught the attention of homeowners and media is the possibility that flow-back fluids from drilling and fracturing processes have contaminated private water wells. Major and trace ion water chemistry was analyzed from 21 groundwater wells suspected by homeowners to be contaminated by flow-back fluids. These data, collected in 2012-2013, were compared to historical groundwater data, Marcellus flow-back fluid, and other sources of common groundwater contamination in rural areas (agricultural waste, septic waste, and road salt). Results from graphical and statistical tests indicate that flow-back fluids have not impacted these wells. However, some of the 2012-2013 wells do plot graphically within zones identified as waters that have been influenced by animal waste, septic, or road salt. The remaining 2012-2013 wells are geochemically similar to historical groundwater wells. These findings suggest that the major and trace element geochemistry of local groundwater in the northeastern Pennsylvania study area has not been detectably influenced by flow-back fluid spills.

Abstract:
High-volume hydraulic fracturing (HVHF) has revolutionized the oil and gas industry worldwide but has been accompanied by highly controversial incidents of reported water contamination. For example, groundwater contamination by stray natural gas and spillage of brine and other gas drilling-related fluids is known to occur. However, contamination of shallow potable aquifers by HVHF at depth has never been fully documented. We investigated a case where Marcellus Shale gas wells in Pennsylvania caused inundation of natural gas and foam in initially potable groundwater used by several households. With comprehensive 2D gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS), an unresolved complex mixture of organic compounds was identified in the aquifer. Similar signatures were also observed in flowback from Marcellus Shale gas wells. A compound identified in flowback, 2-n-Butoxyethanol, was also positively identified in one of the foaming drinking water wells at nanogram-per-liter concentrations. The most likely explanation of the incident is that stray natural gas and drilling or HF compounds were driven ∼1–3 km along shallow to intermediate depth fractures to the aquifer used as a potable water source. Part of the problem may have been wastewaters from a pit leak reported at the nearest gas well pad—the only nearby pad where wells were hydraulically fractured before the contamination incident. If samples of drilling, pit, and HVHF fluids had been available, GCxGC-TOFMS might have fingerprinted the contamination source. Such evaluations would contribute significantly to better management practices as the shale gas industry expands worldwide.

Abstract:
Salinization is a global threat to the quality of streams and rivers, but it can have many causes. Oil and gas development were investigated as one of several potential causes of changes in the salinity of Muddy Creek, which drains 2470 km(2) of mostly public land in Wyoming, U.S.A. Stream discharge and salinity vary with seasonal snowmelt and define a primary salinity-discharge relationship. Salinity, measured by specific conductance, increased substantially in 2009 and was 53-71% higher at low discharge and 33-34% higher at high discharge for the-years 2009-2012 compared to 2005-2008. Short-term processes (e.g., flushing of efflorescent salts) cause within-year deviations from the primary relation but do not obscure the overall increase in salinity. Dissolved elements associated with increased salinity include calcium, magnesium, and sulfate, a composition that points to native soil salts derived from marine shales as a likely source. Potential causes of the salinity increase were evaluated for consistency by using measured patterns in stream chemistry, slope of the salinity-discharge relationship, and inter-annual timing of the salinity increase. Potential causes that were inconsistent with one or more of those criteria included effects from precipitation, evapotranspiration, reservoirs, grazing, irrigation return flow, groundwater discharge, discharge of energy co-produced waters, and stream habitat restoration. In contrast, surface disturbance of naturally salt-rich soil by oil and gas development activities, such as pipeline, road, and well pad construction, is a reasonable candidate for explaining the salinity increase. As development continues to expand in semiarid lands worldwide, the potential for soil disturbance to increase stream salinity should be considered, particularly where soils host substantial quantities of native salts.

Abstract:
Abandoned oil and gas (AOG) wells can provide pathways for subsurface fluid migration, which can lead to groundwater contamination and gas emissions to the atmosphere. Little is known about the millions of AOG wells in the U.S. and abroad. Recently, we acquired data on methane emissions from 42 plugged and unplugged AOG wells in five different counties across western Pennsylvania. We used historical documents to estimate well depths and used these depths with the emissions data to estimate the wells effective permeabilities, which capture the combined effects of all leakage pathways within and around the wellbores. We find effective permeabilities to range from 10(-6) to 10(2) millidarcies, which are within the range of previous estimates. The effective permeability data presented here provide perspective on older AOG wells and are valuable when considering the leakage potential of AOG wells in a wide range of applications, including geologic storage of carbon dioxide, natural gas storage, and oil and gas development.

Abstract:
The environmental impacts of shale,gas development on water resources, including methane migration to shallow groundwater, have been difficult to assess. Monitoring around gas wells is generally limited to domestic water-supply well's, which often are not situated along predominant groundwater flow paths. A new concept is tested here: combining stream hydrocarbon and noble-gas measurements with reach mass-balance modeling to estimate thermogenic methane concentrations and fluxes in groundwater discharging to streams and to constrain methane sources. In the Marcellus Formation shalegas play of northern Pennsylvania (U.S.A.), we sampled methane in 15 streams as a reconnaissance tool to locate methane-laden groundwater discharge: concentrations up to 69 mu gL(-1) were observed, with four streams >= 5 mu g L-1. Geochemical analyses of water from one stream with high methane (Sugar Run, Lycoming County) were consistent with Middle Devonian gases. After sampling was completed, we learned of a state regulator investigation of stray-gas migration from a nearby Marcellus Formation gas well. Modeling indicates a groundwater thermogenic methane flux of about 0.5 kg d(-1) discharging into Sugar Run, possibly from this fugitive gas source. Since flow paths often coalesce into gaining streams, stream methane monitoring provides the first watershed-scale method to assess grOundwatet contamination from shale-gas development.

Abstract:
Hydrocarbon production from unconventional resources and the use of reservoir stimulation techniques, such as hydraulic fracturing, has grown explosively over the last decade. However, concerns have arisen that reservoir stimulation creates significant environmental threats through the creation of permeable pathways connecting the stimulated reservoir with shallower freshwater aquifers, thus resulting in the contamination of potable groundwater by escaping hydrocarbons or other reservoir fluids. This study investigates, by numerical simulation, gas and water transport between a shallow tight-gas reservoir and a shallower overlying freshwater aquifer following hydraulic fracturing operations, if such a connecting pathway has been created. We focus on two general failure scenarios: (1) communication between the reservoir and aquifer via a connecting fracture or fault and (2) communication via a deteriorated, preexisting nearby well. We conclude that the key factors driving short-term transport of gas include high permeability for the connecting pathway and the overall volume of the connecting feature. Production from the reservoir is likely to mitigate release through reduction of available free gas and lowering of reservoir pressure, and not producing may increase the potential for release. We also find that hydrostatic tight-gas reservoirs are unlikely to act as a continuing source of migrating gas, as gas contained within the newly formed hydraulic fracture is the primary source for potential contamination. Such incidents of gas escape are likely to be limited in duration and scope for hydrostatic reservoirs. Reliable field and laboratory data must be acquired to constrain the factors and determine the likelihood of these outcomes.

Abstract:
Unconventional drilling (the combination of hydraulic fracturing and horizontal drilling) to extract oil and natural gas is expanding rapidly around the world. The rate of expansion challenges scientists and regulators to assess the risks of the new technologies on drinking water resources. One concern is the potential for subsurface drinking water resource contamination by naturally occurring radioactive materials co-extracted during unconventional drilling activities. Given the rate of expansion, opportunities to test drinking water resources in the pre- and post-fracturing setting are rare. This pilot study investigated the levels of natural uranium, lead-210, and polonium-210 in private drinking wells within 2000 m of a large-volume hydraulic fracturing operation – before and approximately one-year following the fracturing activities. Observed radionuclide concentrations in well waters tested did not exceed maximum contaminant levels recommended by state and federal agencies. No statistically-significant differences in radionuclide concentrations were observed in well-water samples collected before and after the hydraulic fracturing activities. Expanded monitoring of private drinking wells before and after hydraulic fracturing activities is needed to develop understanding of the potential for drinking water resource contamination from unconventional drilling and gas extraction activities.

Abstract:
Recent studies in northeastern Pennsylvania report higher concentrations of dissolved methane in domestic water wells associated with proximity to nearby gas-producing wells [Osborn et al. Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 8172] and [Jackson et al. Proc. Natl. Acad. Sci. U. S. A., 2013, 110, 11250]. We test this possible association by using Chesapeake Energy?s baseline data set of over 11,300 dissolved methane analyses from domestic water wells, densely arrayed in Bradford and nearby counties (Pennsylvania), and near 661 pre-existing oil and gas wells. The majority of these, 92%, were unconventional wells, drilled with horizontal legs and hydraulically fractured. Our data set is hundreds of times larger than data sets used in prior studies. In contrast to prior findings, we found no statistically significant relationship between dissolved methane concentrations in groundwater from domestic water wells and proximity to pre-existing oil or gas wells. Previous analyses used small sample sets compared to the population of domestic wells available, which may explain the difference in prior findings compared to ours.

Abstract:
Hydraulic fracturing is becoming an important technique worldwide to recover hydrocarbons from unconventional sources such as shale gas. In Quebec (Canada), the Utica Shale has been identified as having unconventional gas production potential. However, there has been a moratorium on shale gas exploration since 2010. The work reported here was aimed at defining baseline concentrations of methane in shallow aquifers of the St. Lawrence Lowlands and its sources using δ13C methane signatures. Since this study was performed prior to large-scale fracturing activities, it provides background data prior to the eventual exploitation of shale gas through hydraulic fracturing. Groundwater was sampled from private (n=81), municipal (n=34) and observation (n=15) wells between August 2012 and May 2013. Methane was detected in 80% of the wells with an average concentration of 3.8 ± 8.8 mg/L, and a range of < 0.0006 to 45.9 mg/L. Methane concentrations were linked to groundwater chemistry and distance to the major faults in the studied area. The methane δ13C signature of 19 samples was > -50‰, indicating a potential thermogenic source. Localized areas of high methane concentrations from predominantly biogenic sources were found throughout the study area. In several samples, mixing, migration and oxidation processes likely affected the chemical and isotopic composition of the gases, making it difficult to pinpoint their origin. Energy companies should respect a safe distance from major natural faults in the bedrock when planning the localization of hydraulic fracturation activities to minimize the risk of contaminating the surrounding groundwater since natural faults are likely to be a preferential migration pathway for methane.

Abstract:
Reports of ground water contamination in a southwestern Pennsylvania community coincided with unconventional shale gas extraction activities that started late 2009. Residents participated in a survey and well water samples were collected and analyzed. Available pre-drill and post-drill water test results and legacy operations (e.g., gas and oil wells, coal mining) were reviewed. Fifty-six of the 143 respondents indicated changes in water quality or quantity while 63 respondents reported no issues. Color change (brown, black, or orange) was the most common (27 households). Well type, when known, was rotary or cable tool, and depths ranged from 19 to 274 m. Chloride, sulfate, nitrate, sodium, calcium, magnesium, iron, manganese and strontium were commonly found, with 25 households exceeding the secondary maximum contaminate level (SMCL) for manganese. Methane was detected in 14 of the 18 houses tested. The 26 wells tested for total coliforms (2 positives) and E. coli (1 positive) indicated that septic contamination was not a factor. Repeated sampling of two wells in close proximity (204 m) but drawing from different depths (32 m and 54 m), revealed temporal variability. Since 2009, 65 horizontal wells were drilled within a 4 km (2.5 mile) radius of the community, each well was stimulated on average with 3.5 million gal of fluids and 3.2 million lbs of proppant. PA DEP cited violations included an improperly plugged well and at least one failed well casing. This study underscores the need for thorough analyses of data, documentation of legacy activity, pre-drill testing, and long term monitoring.

Abstract:
Mercury (Hg) is a persistent element in the environment that has the ability to bioaccumulate and biomagnify up the food chain with potentially harmful effects on ecosystems and human health. Twenty-four streams remotely located in forested watersheds in northwestern PA containing naturally reproducing Salvelinus fontinalis (brook trout), were targeted to gain a better understanding of how Marcellus shale natural gas exploration may be impacting water quality, aquatic biodiversity, and Hg bioaccumulation in aquatic ecosystems. During the summer of 2012, stream water, stream bed sediments, aquatic mosses, macroinvertebrates, crayfish, brook trout, and microbial samples were collected. All streams either had experienced hydraulic fracturing (fracked, n = 14) or not yet experienced hydraulic fracturing (non-fracked, n = 10) within their watersheds at the time of sampling. Analysis of watershed characteristics (GIS) for fracked vs non-fracked sites showed no significant differences (P > 0.05), justifying comparisons between groups. Results showed significantly higher dissolved total mercury (FTHg) in stream water (P = 0.007), lower pH (P = 0.033), and higher dissolved organic matter (P = 0.001) at fracked sites. Total mercury (THg) concentrations in crayfish (P = 0.01), macroinvertebrates (P = 0.089), and predatory macroinvertebrates (P = 0.039) were observed to be higher for fracked sites. A number of positive correlations between amount of well pads within a watershed and THg in crayfish (r = 0.76, P < 0.001), THg in predatory macroinvertebrates (r = 0.71, P < 0.001), and THg in brook trout (r = 0.52, P < 0.01) were observed. Stream-water microbial communities within the Deltaproteobacteria also shared a positive correlation with FTHg and to the number of well pads, while stream pH (r = −0.71, P < 0.001), fish biodiversity (r = −0.60, P = 0.02), and macroinvertebrate taxa richness (r = −0.60, P = 0.01) were negatively correlated with the number of well pads within a watershed. Further investigation is needed to better elucidate relationships and pathways of observed differences in stream water chemistry, biodiversity, and Hg bioaccumulation, however, initial findings suggest Marcellus shale natural gas exploration is having an effect on aquatic ecosystems.

Abstract:
A necessary element during unconventional gas exploration is the identification of possible environmental hazards. These hazards require quantitative and qualitative assessment to ensure groundwater protection. This is realized using legal-administrative and technical tools. In shale gas exploration areas, the most important method of groundwater protection is groundwater monitoring. Correct design of a monitoring system is based on studies allowing for early recognition of the real impact on groundwater. An optimally operating monitoring network should allow explicit determination of the direction, range and area of water pollution during shale gas exploration. In Poland and other countries, the existing solutions and legal regulations related to water monitoring are generalized and usually not specifically dedicated to assessment of hazard caused by shale gas exploration. There is a need for an individual approach to the concept and design of the monitoring network for each specific investment.

Abstract:
Baseline groundwater geochemical mapping of inorganic and isotopic parameters across 44,000 km2 of southwestern Ontario (Canada) has delineated a discreet zone of natural gas in the bedrock aquifer coincident with an 8,000-km2 exposure of Middle Devonian shale. This study describes the ambient geochemical conditions in these shales in the context of other strata, including Ordovician shales, and discusses shale-related natural and anthropogenic processes contributing to hydrogeochemical conditions in the aquifer. The three Devonian shales—the Kettle Point Formation (Antrim equivalent), Hamilton Group and Marcellus Formation—have higher DOC, DIC, HCO3, CO2(aq), pH and iodide, and much higher CH4(aq). The two Ordovician shales—the Queenston and Georgian-Bay/Blue Mountain Formations—are higher in Ca, Mg, SO4 and H2S. In the Devonian shale region, isotopic zones of Pleistocene-aged groundwater have halved in size since first identified in the 1980s; potentiometric data implicate regional groundwater extraction in the shrinkage. Isotopically younger waters invading the aquifer show rapid increases in CH4(aq), pH and iodide with depth and rapid decrease in oxidized carbon species including CO2, HCO3 and DIC, suggesting contemporary methanogenesis. Pumping in the Devonian shale contact aquifer may stimulate methanogenesis by lowering TDS, removing products and replacing reactants, including bicarbonate, derived from overlying glacial sedimentary aquifers.

Abstract:
The data provided by the PA DEP are incomplete because confidential data are not released. It is impossible to make firm conclusions about water quality impacts when data availability is limited. Nonetheless, the PA experience appears to be characterized by a low rate of problems per gas well or unit of gas produced. Only about 160 of the complaints from homeowners about groundwater to the PA DEP between 2008 and 2012 were problems attributed to oil and gas activity—and only half of these were caused by companies known to drill unconventional shale wells. These problematic wells in turn represent only 0.1 to 1% of the unconventional shale gas wells drilled in that time period (Brantley et al. 2014). Management practices appear to be improving as well; the rate of problems has decreased since 2010 (Figure 1). Apparently, however, the public responds not only to the number of problems per gas well or per unit of gas produced but rather to the number of problems per unit time and per unit area. Thus, even though the r ate of problems with shale gas wells has remained small on a per well basis, pushback has grown in areas of increasing density of drilling and fracking. This may be especially true when consequences are fearsome such as flaming tapwater, toxic contamination, or earthquakes. It is natural that the social license for shale gas development is influenced by short-term, local thinking. But, such thinking may not be helpful given that Marcellus Shale gas wells generate one third the waste per unit volume of gas as compared to conventional shallow gas wells (Vidic et al. 2013). In addition, the release of pollutants such as carbon dioxide, particulates, mercury, nitrogen, and sulfur generated per unit of heat energy is lower f or unconventional shale gas than for fuels such as coal (Heath et al. 2014). Public pushback could nonetheless be a blessing. After all, pushback represents intensified interest in environmental issues. This interest may be seen in the PA DEP data for the rate of well integrity issues in conventional oil and gas wells—the increase in problem rate from 2008 to 2012 (Figure 1) is more likely due to heightened public attention and inspector scrutiny rather than a sudden deterioration in the management practices of the drilling companies (Brantley et al. 2014) During the next decades, the rate of hydraulic fracturing in PA will eventually slow. At some point, the use of produced brines to hydrofracture new wells will cease. Once recycling of brine to frack new wells stops, hundreds of gallons of brine will accumulate as waste at each well per day (Rahm et al. 2013). Disposal of this slightly radioactive brine will then become increasingly problematic. Interest on the part of the public for such issues is warranted. Public engagement today is needed to develop sustainable waste management and sustainable energy practices for the future.

Abstract:
Heightened concern regarding the potential effects of unconventional oil and gas development on regional water quality has emerged, but the few studies on this topic are limited in geographic scope. Here we evaluate the potential utility of national and publicly available water-quality data sets for addressing questions regarding unconventional oil and gas development. We used existing U.S. Geological Survey and U.S. Environmental Protection Agency data sets to increase understanding of the spatial distribution of unconventional oil and gas development in the U.S. and broadly assess surface water quality trends in these areas. Based on sample size limitations, we were able to estimate trends in specific conductance (SC) and chloride (Cl−) from 1970 to 2010 in 16% (n = 155) of the watersheds with unconventional oil and gas resources. We assessed these trends relative to spatiotemporal distributions of hydraulically fractured wells. Results from this limited analysis suggest no consistent and widespread trends in surface water quality for SC and Cl− in areas with increasing unconventional oil and gas development and highlight limitations of existing national databases for addressing questions regarding unconventional oil and gas development and water quality.

Abstract: