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.

Characterizing the Noble Gas Isotopic Composition of the Barnett Shale and Strawn Group and Constraining the Source of Stray Gas in the Trinity Aquifer, North-Central Texas.

This study presents the complete set of stable noble gases for Barnett Shale and Strawn Group production gas together with stray flowing gas in the Trinity Aquifer, Texas. It places new constraints on the source of this stray gas and further shows that Barnett and Strawn gas have distinct crustal and atmospheric noble gas signatures, allowing clear identification of these two sources. Like stray gas, Strawn gas is significantly more enriched in crustal 4He*, 21Ne*, and 40Ar* than Barnett gas. The similarity of Strawn and stray gas crustal noble gas signatures suggests that the Strawn is the source of stray gas in the Trinity Aquifer. Atmospheric 22Ne/36Ar ratios of stray gas mimic also that of Strawn, further reinforcing the notion that the source of stray gas in this aquifer is the Strawn. While noble gas signatures of Strawn and stray gas are consistent with a single-stage water degassing model, a two-stage oil modified groundwater exsolution fractionation model is required to explain the light atmospheric noble gas signature of Barnett Shale production gas. These distinct Strawn and Barnett noble gas signatures are likely the reflection of distinct evolution histories with Strawn gas being possibly older than that of Barnett Shale.

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 (δ13 C 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.

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 δ13 Cmethane (>-55‰) and δDmethane (>-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 δ13 Cmethane and δDmethane 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.

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.

Methane Sources and Migration Mechanisms in Shallow Groundwaters in Parker and Hood Counties, Texas-A Heavy Noble Gas Analysis.

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

Field demonstration of CO2 leakage detection in potable aquifers with a pulselike CO2-release test.

This study presents two field pulselike CO2-release tests to demonstrate CO2 leakage detection in a shallow aquifer by monitoring groundwater pH, alkalinity, and dissolved inorganic carbon (DIC) using the periodic groundwater sampling method and a fiber-optic CO2 sensor for real-time in situ monitoring of dissolved CO2 in groundwater. Measurements of groundwater pH, alkalinity, DIC, and dissolved CO2 clearly deviated from their background values, showing responses to CO2 leakage. Dissolved CO2 observed in the tests was highly sensitive in comparison to groundwater pH, DIC, and alkalinity. Comparison of the pulselike CO2-release tests to other field tests suggests that pulselike CO2-release tests can provide reliable assessment of geochemical parameters indicative of CO2 leakage. Measurements by the fiber-optic CO2 sensor, showing obvious leakage signals, demonstrated the potential of real-time in situ monitoring of dissolved CO2 for leakage detection at a geologic carbon sequestration (GCS) site. Results of a two-dimensional reactive transport model reproduced the geochemical measurements and confirmed that the decrease in groundwater pH and the increases in DIC and dissolved CO2 observed in the pulselike CO2-release tests were caused by dissolution of CO2 whereas alkalinity was likely affected by carbonate dissolution.

Regional assessment of CO2-solubility trapping potential: a case study of the coastal and offshore Texas Miocene interval.

This study presents a regional assessment of CO2-solubility trapping potential (CSTP) in the Texas coastal and offshore Miocene interval, comprising lower, middle, and upper Miocene sandstone. Duan's solubility model [Duan et al. Mar. Chem. 2006, 98, 131-139] was applied to estimate carbon content in brine saturated with CO2 at reservoir conditions. Three approaches (simple, coarse, and fine) were used to calculate the CSTP. The estimate of CSTP in the study area varies from 30 Gt to 167 Gt. Sensitivity analysis indicated that the CSTP in the study area is most sensitive to storage efficiency, porosity, and thickness and is least sensitive to background carbon content in brine. Comparison of CSTP in our study area with CSTP values for seven other saline aquifers reported in the literature showed that the theoretical estimate of CO2-solubility trapping potential (TECSTP) has a linear relationship with brine volume, regardless of brine salinity, temperature, and pressure. Although more validation is needed, this linear relationship may provide a quick estimate of CSTP in a saline aquifer. Results of laboratory experiments of brine-rock-CO2 interactions and the geochemical model suggest that, in the study area, enhancement of CSTP caused by interactions between brine and rocks is minor and the storage capacity of mineral trapping owing to mineral precipitation is relatively trivial.

Potential impacts of CO2 leakage on groundwater chemistry from laboratory batch experiments and field push-pull tests.

Storage of CO2 in deep saline reservoirs has been proposed to mitigate anthropogenically forced climate change. If injected CO2 unexpectedly migrates upward in shallow groundwater resources, potable groundwater may be negatively affected. This study examines the effects of an increase in pCO2 (partial pressure of CO2) on groundwater chemistry in a siliclastic-dominated aquifer by comparing a laboratory batch experiment and a field single-well push-pull test on the same aquifer sediment and groundwater. Although the aquifer mineralogy is predominately siliclastic, carbonate dissolution is the primary geochemical reaction. In the batch experiment, Ca concentrations increase until calcite saturation is reached at ~500 h. The concentrations of the elements Ca, Mg, Sr, Ba, Mn, and U are controlled by carbonate dissolution. Silicate dissolution controls Si and K concentrations and is ~2 orders of magnitude slower than carbonate dissolution. Changing pH conditions through the experiment initially mobilize Mo, V, Zn, Se, and Cd; sorption reactions later remove these elements from solution and concentrations drop to pre-experiment levels. The EPA's primary and secondary MCL's are not exceeded except for Mn, which exceeded the EPA's secondary standard of 0.05 mg/L. Push-pull results also identify carbonate and silicate dissolution reactions ~2 orders of magnitude slower than batch experiments.