Patterns of Entrapped Air Dissolution in a Two‐Dimensional Pilot‐Scale Synthetic Aquifer

Past studies of entrapped air dissolution have focused on one‐dimensional laboratory columns. Here the multidimensional nature of entrapped air dissolution was investigated using an indoor tank (180 × 240 × 600 cm³) simulating an unconfined sand aquifer with horizontal flow. Time domain reflectometry (TDR) probes directly measured entrapped air contents, while dissolved gas conditions were monitored with total dissolved gas pressure (P_TDG) probes. Dissolution occurred as a diffuse wedge‐shaped front from the inlet downgradient, with preferential dissolution at depth. This pattern was mainly attributed to increased gas solubility, as shown by P_TDG measurements. However, compression of entrapped air at greater depths, captured by TDR and leading to lower quasi‐saturated hydraulic conductivities and thus greater velocities, also played a small role. Linear propagation of the dissolution front downgradient was observed at each depth, with both TDR and P_TDG, with increasing rates with depth (e.g, 4.1 to 5.7× slower at 15 cm vs. 165 cm depth). P_TDG values revealed equilibrium with the entrapped gas initially, being higher at greater depth and fluctuating with the barometric pressure, before declining concurrently with entrapped air contents to the lower P_TDG of the source water. The observed dissolution pattern has long‐term implications for a wide variety of groundwater management issues, from recharge to contaminant transport and remediation strategies, due to the persistence of entrapped air near the water table (potential timescale of years). This study also demonstrated the utility of P_TDG probes for simple in situ measurements to detect entrapped air and monitor its dissolution.     

In-Well Degassing of Monitoring Wells Completed in Gas-Charged Aquifers

Total dissolved gas pressure (P_TDG) measurements are useful to measure accurate in situ dissolved gas concentrations in groundwater, but challenged by in-well degassing. Although in-well degassing has been widely observed, its cause(s) are not clear. We investigated the mechanism(s) by which gas-charged groundwater in a recently pumped well becomes degassed. Vertical P_TDG and dissolved gas concentration profiles were monitored in the standing water column (SWC) of a groundwater well screened in a gas-charged aquifer for 7 days before and 15 days after pumping. Prior to pumping, P_TDG values remained relatively constant and below calculated bubbling pressure (P_BUB) at all depths. In contrast, significant increases in P_TDG were observed at all depths after pumping was initiated, as fresh groundwater with elevated in situ P_TDG values was pumped through the well screen. After pumping ceased, P_TDG values decreased to below P_BUB at all depths over the 15-day post-pumping period, indicating well degassing was active over this time frame. Vertical profiles of estimated dissolved gas concentrations before and after pumping provided insight into the mechanism(s) by which in-well degassing occurred in the SWC. During both monitoring periods, downward mixing of dominant atmospheric and/or tracer gases, and upwards mixing of dominant groundwater gases were observed in the SWC. The key mechanisms responsible for in-well degassing were (i) bubble exsolution when P_TDG exceeded P_BUB as gas-charged well water moves upwards in the SWC during recovery (i.e., hydraulic gradient driven convection), (ii) microadvection caused by the upward migration of bubbles under buoyancy, and (iii) long-term, thermally driven vertical convection.     

Spatially distributed denitrification in a karst springshed

Karst spring measurements assess biogeochemical processes occurring within groundwater contributing areas to springs (springsheds) but can only provide aggregated information. To better understand spatially distributed processes that comprise these aggregated measures, we investigated aquifer denitrification evidence in groundwater wells (n = 16) distributed throughout a springshed in the Upper Floridan aquifer in northern Florida. Aquifer geochemistry, nitrate isotopes, and dissolved gases were compared against similar measurements at the spring outlet to evaluate spatial heterogeneity of denitrification evidence in relation to land surface–aquifer connectivity. Sample locations spanned spatial variation in recharge processes (i.e., diffuse vs. focused recharge) and proximity to sources of denitrification reactants (e.g., wetlands). Although no distinct spatial pattern in denitrification was uncovered, excess dissolved N₂ gas measurements were only above detection in the unconfined springshed, with some evidence of a wetland proximity effect. Measured oxidation–reduction potential and dissolved oxygen poorly predicted denitrification, indicating that measured denitrification may be occurring upgradient from sampled wells. Despite dramatic spatial chemical heterogeneity across wells, mean values for recharge nitrate concentrations (0.02 to 5.56 mg N L^?1) and excess N₂ from aquifer denitrification (below detection to 1.37 mg N L^?1) corresponded reasonably with mean spring outlet measurements for initial nitrate (0.78 to 1.36 mg N L^?1) and excess N₂ (0.15 to 1.04 mg N L^?1). Congruence between groundwater and spring measurements indicates that combining sampling at the spring outlet and across the springshed is useful for understanding spatial aquifer denitrification. However, this approach would be improved with a high‐density sampling network with transects of wells along distinct groundwater flow paths.     

A Proposed Method to Estimate In Situ Dissolved Gas Concentrations in Gas‐Saturated Groundwater

Gas‐saturated groundwater forms bubbles when brought to atmospheric pressure, preventing precise determination of its in situ dissolved gas concentrations. To overcome this problem, a modeling approach called the atmospheric sampling method is suggested here to recover the in situ dissolved gas concentrations of groundwater collected ex situ under atmospheric conditions at the Horonobe Underground Research Laboratory, Japan. The results from this method were compared with results measured at the same locations using two special techniques, the sealed sampler and pre‐evacuated vial methods, that have been developed to collect groundwater under its in situ conditions. In gas‐saturated groundwater cases, dissolved methane and inorganic carbon concentrations derived using the atmospheric sampling method were mostly within ±4 and ±10%, respectively, of values from the sealed sampler and pre‐evacuated vial methods. In gas‐unsaturated groundwater, however, the atmospheric sampling method overestimated the in situ dissolved methane concentrations, because the groundwater pressure at which bubbles appear (P_critical) was overestimated. The atmospheric sampling method is recommended for use where gas‐saturated groundwater can be collected only ex situ under atmospheric conditions.     

In-Well Degassing Issues for Measurements of Dissolved Gases in Groundwater

Measurement of dissolved gases in groundwater is becoming increasingly common and important. Many of these measurements involve monitoring or sampling within wells or from water pumped from wells. We used total dissolved gas pressure (TDGP) sensors placed in the screened section of various wells (4 to 72 m deep) to assess the dissolved gas conditions for open wells compared to the conditions when sealed (i.e., isolated from the atmosphere) with a hydraulic packer (one well) or when pumped. When the packer was installed (non-pumping conditions), TDGP rose from <1.7 to >3.1 atm (<172 to >314 kPa), with declines noted when the packer was removed or deflated. While pumping, TDGP measured in many of the wells rose to substantially higher levels, up to 4.0 atm (408 kPa) in one case. Thus, when groundwater is gas charged, the background aquifer TDGP, and likewise the dissolved gas concentrations, may be substantially higher than initially measured in open wells, indicating significant in-well degassing. This raises concerns about past and current methods of measuring the dissolved gases in groundwater. Additional procedures that may be required to obtain representative measurements from wells include (1) installing in-well hydraulic packers to seal the well, or (2) pumping to bring in fresh groundwater. However, observed transient decreased TDGPs during pumping, believed to result from gas bubble formation induced by drawdown in the well below a critical pressure (relative to TDGP), may disrupt the measurements made during or after pumping. Thus, monitoring TDGP while pumping gas-charged wells is recommended.     

Numerical Modeling of Methane Leakage from a Faulty Natural Gas Well into Fractured Tight Formations

Horizontal drilling and hydraulic fracturing have enabled hydrocarbon recovery from unconventional reservoirs, but led to natural gas contamination of shallow groundwaters. We describe and apply numerical models of gas‐phase migration associated with leaking natural gas wells. Three leakage scenarios are simulated: (1) high‐pressure natural gas pulse released into a fractured aquifer; (2) continuous slow leakage into a tilted fractured formation; and (3) continuous slow leakage into an unfractured aquifer with fluvial channels, to facilitate a generalized evaluation of natural gas transport from faulty natural gas wells. High‐pressure pulses of gas leakage into sparsely fractured media are needed to produce the extensive and rapid lateral spreading of free gas previously observed in field studies. Transport in fractures explains how methane can travel vastly different distances and directions laterally away from a leaking well, which leads to variable levels of methane contamination in nearby groundwater wells. Lower rates of methane leakage (≤1 Mcf/day) produce shorter length scales of gas transport than determined by the high‐pressure scenario or field studies, unless aquifers have low vertical permeabilities (≤1 millidarcy) and fractures and bedding planes have sufficient tilt (～10°) to allow a lateral buoyancy component. Similarly, in fractured rock aquifers or where permeability is controlled by channelized fluvial deposits, lateral flow is not sufficiently developed to explain fast‐developing gas contamination (0‐3 months) or large length scales (～1 km) documented in field studies. Thus, current efforts to evaluate the frequency, mechanism, and impacts of natural gas leakage from faulty natural gas wells likely underestimate contributions from small‐volume, low‐pressure leakage events.     

Free-Phase Gas Detection in Groundwater Wells via Water Pressure and Continuous Field Parameters

Detection of free-phase gas (FPG) in groundwater wells is critical for accurate assessment of dissolved gas concentrations and the occurrence of FPG in the subsurface, with consequent implications for understanding groundwater contamination and greenhouse gas emissions. However, identifying FPG is challenging during routine groundwater monitoring and there is poor agreement on the best approach to detect the occurrence of FPG in groundwater. In this study, laboratory experiments in a water column were designed to mimic nonflowing and flowing conditions in a groundwater well to evaluate how the presence of FPG affects water pressure and commonly used continuous field parameters. The laboratory results were extrapolated to interpret field data at an abandoned exploration well with episodic release of free-gas CO₂. The FPG effect on water pressure varied between flowing and nonflowing wells, and depending on whether the FPG was above or below the sensor. Electrical conductivity values were decreased and/or behaved erratically when FPG was present in the water column. Findings from this study have shown that the combined measurement of water pressure, electrical conductivity, and total dissolved gas pressure can provide information about the occurrence of FPG in groundwater wells. Measurement of these parameters at different depths can also provide information about relative depths and amounts of FPG within the well water column. This approach can be used for long-term monitoring of groundwater gases, managing gas-locking in production wells with gassy groundwater, and measuring fugitive greenhouse gas emissions from groundwater wells.     

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

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

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

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

Applying the HPT‐GWS for Hydrostratigraphy,Water Quality and Aquifer Recharge Investigations

The primary objective of this study was to evaluate use of the hydraulic profiling tool‐groundwater sampler (HPT‐GWS) log data as an indicator of water quality (level of dissolved ionic species) in an alluvial aquifer. The HPT‐GWS probe is designed for direct push advancement into unconsolidated formations. The system provides both injection pressure logs and electrical conductivity (EC) logs, and groundwater may be sampled at multiple depths as the probe is advanced (profiling). The combination of these three capabilities in one probe has not previously been available. During field work it was observed that when HPT corrected pressure (P_c) indicates a consistent aquifer unit then bulk formation EC can be used as an indicator of water quality. A high correlation coefficient (R ² = 0.93) was observed between groundwater specific conductance and bulk formation EC in the sands and gravels of the alluvial aquifer studied. These results indicate that groundwater specific conductance is exerting a controlling influence on the bulk formation EC of the coarse‐grained unit at this site, and probably many similar sites, consistent with Archie's Law. This simple relationship enables the use of the EC and P_c logs, with targeted water samples and a minimum of core samples, to rapidly assess groundwater quality over extended areas at high vertical resolution. This method was used to identify both a brine impacted zone at the base of the aquifer investigated and a groundwater recharge lens developing below storm water holding ponds in the upper portion of the same aquifer. Sample results for trace level, naturally occurring elements (As, Ba, U) further demonstrate the use of this system to sample for low level groundwater contamination.     

Factors Influencing Variability in Groundwater Monitoring Data Sets

“Random” variability in groundwater monitoring data sets reduces the ability to identify long‐term concentration trends. This, in turn, increases the time and cost required to evaluate the effectiveness of natural attenuation and other groundwater remedies. To better understand the factors influencing variability in groundwater monitoring results, we have analyzed three large groundwater monitoring data sets. For the three data sets, the long‐term trend in contaminant concentration in each well accounted for an average of 30% to 40% of the overall variation in contaminant concentration. Understanding the causes of the remaining variability would support the development of improved groundwater monitoring methods. All three data sets show large differences in the temporal monitoring records between individual wells (e.g., coefficient of variation for monitoring results from individual wells ranges from 0.08 to 4.6) indicating that well and aquifer factors are more important contributors to variability than sample collection and analysis factors. However, the depth to groundwater (R² = 0.020) and distance between water level and screened interval (R² = 0.049) accounted for only a portion of the differences in variability between wells and other aquifer characteristics evaluated and were not correlated with the observed variability in monitoring results. Unidentified factors were apparently much more important contributors to variability than these factors. The monitoring data sets exhibited two distinct timescales for variability: Time‐independent variability that was apparent even when wells were re‐sampled within a few days and a long‐term variability likely associated with the long‐term concentration trend. The observation of time‐independent variability suggests that frequent monitoring of contaminated monitoring wells serves primarily to characterize sources of variability unrelated to the long‐term trend of primary interest.     

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

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

Changes in Entrapped Gas Content and Hydraulic Conductivity with Pressure

Water table fluctuations continuously introduce entrapped air bubbles into the otherwise saturated capillary fringe and groundwater zone, which reduces the effective (quasi‐saturated) hydraulic conductivity, K_quasi, thus impacting groundwater flow, aquifer recharge and solute and contaminant transport. These entrapped gases will be susceptible to compression or expansion with changes in water pressure, as would be expected with water table (and barometric pressure) fluctuations. Here we undertake laboratory experiments using sand‐packed columns to quantify the effect of water table changes of up to 250 cm on the entrapped gas content and the quasi‐saturated hydraulic conductivity, and discuss our ability to account for these mechanisms in ground water models. Initial entrapped air contents ranged between 0.080 and 0.158, with a corresponding K_quasi ranging between 2 and 6 times lower compared to the K_s value. The application of 250 cm of water pressure caused an 18% to 26% reduction in the entrapped air content, resulting in an increase in K_quasi by 1.16 to 1.57 times compared to its initial (0 cm water pressure) value. The change in entrapped air content measured at pressure step intervals of 50 cm, was essentially linear, and could be modeled according to the ideal gas law. Meanwhile, the changes in K_quasi with compression–expansion of the bubbles because of pressure changes could be adequately captured with several current hydraulic conductivity models.     

Structural and Hydrogeological Controls on Hydrocarbon and Brine Migration into Drinking Water Aquifers in Southern New York

Environmental concerns regarding the potential for drinking water contamination in shallow aquifers have accompanied unconventional energy development in the northern Appalachian Basin. These activities have also raised several critical questions about the hydrogeological parameters that control the naturally occurring presence and migration of hydrocarbon gases in shallow aquifers within petroliferous basins. To interrogate these factors, we analyzed the noble gas, dissolved ion, and hydrocarbon gas (molecular and isotopic composition) geochemistry of 98 groundwater samples from south‐central New York. All samples were collected ?1km from unconventional drilling activities and sample locations were intentionally targeted based on their proximity to various types of documented fault systems. In agreement with studies from other petroliferous basins, our results show significant correlations between elevated levels of radiogenic [⁴He], thermogenic [CH₄], and dissolved ions (e.g., Cl, Br, Sr, Ba). In combination, our data suggest that faults have facilitated the transport of exogenous hydrocarbon‐rich brines from Devonian source rocks into overlying Upper Devonian aquifer lithologies over geologic time. These data conflict with previous reports, which conclude that hydrodynamic focusing regulates the occurrence of methane and salt in shallow aquifers and leads to elevated levels of these species in restricted flow zones within valley bottoms. Instead, our data suggest that faults in Paleozoic rocks play a fundamental role in gas and brine transport from depth, regulate the distribution of their occurrence in shallow aquifers, and influence the geochemistry of shallow groundwater in this petroliferous basin.     

Impact of Temperature on Groundwater Source Attenuation Rates at Hydrocarbon Sites

The temperature sensitivity of microbial populations is reflected in measured source attenuation rates at hydrocarbon‐impacted sites. The objective of this study was to evaluate the correlation between temperature and source attenuation rates (concentration vs. time attenuation rate over many years) of benzene and toluene by analyzing groundwater monitoring data from >2000 hydrocarbon sites. Historical monitoring records were obtained from three databases, processed to yield long‐term multiyear source attenuation rates, and then compared with representative temperatures at each site. Statistically significant and positive relationships between temperature and source attenuation rates were established for benzene and toluene, indicating that temperature does impact hydrocarbon degradation, but is one of many factors that contribute to source attenuation. There was an observed 1.1 to 1.6 times increase in attenuation rates per 10 °C increase in temperature, which is less than the rate increases predicted by the Arrhenius equation. The temperature dependence on attenuation rate is consistent with several lines of evidence that methanogenesis plays a key role in the rate of hydrocarbon source zone attenuation rather than being controlled strictly by the availability of electron acceptors. First, methanogenesis is known to be strongly influenced by temperature, with significantly higher rates up to about 35 °C. Second, the temperature‐degradation rate relationship was stronger at sites with deeper water tables (>30 ft) that are less susceptible to oxygen influx than sites with shallow water tables (<15 ft). Third, dissolved methane concentrations were higher at sites with warmer temperatures. Overall, these results provide indirect support for a conceptual model where methanogenesis is a key degradation process at hydrocarbon sites, and that attenuation of these source zones is temperature‐sensitive.     

Dissolved Organic Carbon in Groundwater Overlain by Irrigated Sugarcane

Elevated dissolved organic carbon (DOC) has been detected in groundwater beneath irrigated sugarcane on the Burdekin coastal plain of tropical northeast Australia. The maximum value of 82 mg/L is to our knowledge the highest DOC reported for groundwater beneath irrigated cropping systems. More than half of the groundwater sampled in January 2004 (n = 46) exhibited DOC concentrations greater than 30 mg/L. DOC was progressively lower in October 2004 and January 2005, with a total decrease greater than 90% indicating varying load(s) to the aquifer. It was hypothesized that the elevated DOC found in this groundwater system is sourced at or near the soil surface and supplied to the aquifer via vertical recharge following above average rainfall. Possible sources of DOC include organic‐rich sugar mill by‐products applied as fertilizer and/or sugarcane sap released during harvest. CFC‐12 vertical flow rates supported the hypothesis that elevated DOC (>40 mg/L) in the groundwater results from recharge events in which annual precipitation exceeds 1500 mm/year (average = 960 mm/year). Occurrence of elevated DOC concentrations, absence of electron acceptors (O₂ and NO₃^–) and both Fe²⁺ and Mn²⁺ greater than 1 mg/L in shallow groundwater suggest that the DOC compounds are chemically labile. The consequence of high concentrations of labile DOC may be positive (e.g., denitrification) or negative (e.g., enhanced metal mobility and biofouling), and highlights the need to account for a wider range of water quality parameters when considering the impacts of land use on the ecology of receiving waters and/or suitability of groundwater for irrigated agriculture.     

Numerical modelling of stream–aquifer interaction: Quantifying the impact of transient streambed permeability and aquifer heterogeneity

Stream–aquifer interaction plays a vital role in the water cycle, and a proper study of this interaction is needed for understanding groundwater recharge, contaminants migration, and for managing surface water and groundwater resources. A model‐based investigation of a field experiment in a riparian zone of the Schwarzbach river, a tributary of the Rhine River in Germany, was conducted to understand stream–aquifer interaction under alternative gaining and losing streamflow conditions. An equivalent streambed permeability, estimated by inverting aquifer responses to flood waves, shows that streambed permeability increased during infiltration of stream water to aquifer and decreased during exfiltration. Aquifer permeability realizations generated by multiple‐point geostatistics exhibit a high degree of heterogeneity and anisotropy. A coupled surface water groundwater flow model was developed incorporating the time‐varying streambed permeability and heterogeneous aquifer permeability realizations. The model was able to reproduce varying pressure heads at two observation wells near the stream over a period of 55 days. A Monte Carlo analysis was also carried out to simulate groundwater flow, its age distribution, and the release of a hypothetical wastewater plume into the aquifer from the stream. Results of this uncertainty analysis suggest (a) stream–aquifer exchange flux during the infiltration periods was constrained by aquifer permeability; (b) during exfiltration, this flux was constrained by the reduced streambed permeability; (c) the effect of temporally variable streambed permeability and aquifer heterogeneity were found important to improve the accurate capture of the uncertainty; and (d) probabilistic infiltration paths in the aquifer reveal that such pathways and the associated prediction of the extent of the contaminant plume are highly dependent on aquifer heterogeneity.     

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

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

Biodegradation and transport of benzene,toluene, and xylenes in a simulated aquifer: comparison of modelled and experimental results

Both laboratory experiments and numerical modelling were conducted to study the biodegradation and transport of benzene–toluene–xylenes (BTX) in a simulated semi‐confined aquifer. The factors incorporated into the numerical model include advection, hydrodynamic dispersion, adsorption, and biodegradation. The various physico‐chemical parameters required by the numerical model were measured experimentally. In the experimental portion of the study, BTX compounds were introduced into the aquifer sand. After the contaminants had been transported through the system, BTX concentrations were measured at 12 equally spaced wells. Subsequently, microorganisms obtained from the activated sludge of a sewage treatment plant and cultured in BTX mixtures were introduced into the aquifer through the 12 sampling wells. The distribution data for BTX adsorption by the aquifer sand form a nonlinear isotherm. The degree of adsorption by the sand varies, depending on the composition of the solute. The degradation time, measured from the time since the bacteria were added to the aquifer until a specific contaminant was no longer detectable, was 35–42 h for BTX. The dissolved oxygen, after degradation by BTX compounds and bacteria, was consumed by about 40–60% in the entire simulated aquifer; thus the aerobic conditions were maintained. This study provides insights for the biodegradation and transport of BTX in aquifers by numerical modelling and laboratory experiments. Experimental and numerical comparisons indicate that the results by Monod degradation kinetics are more accurate than those by the first‐order degradation kinetics. Copyright © 2002 John Wiley & Sons, Ltd.