Uncertainty in 1D Heat‐Flow Analysis to Estimate Groundwater Discharge to a Stream

Temperature measurements have been used by a variety of researchers to gain insight into groundwater discharge patterns. However, much of this research has reduced the problem to heat and fluid flow in one dimension for ease of analysis. This approach is seemingly at odds with the goal of determining spatial variability in specific discharge, which implies that the temperature field will vary in more than one dimension. However, it is unclear how important the resulting discrepancies are in the context of determining groundwater discharge to surface water bodies. In this study, the importance of these variations is examined by testing two popular one‐dimensional analytical solutions with stochastic models of heat and fluid flow in a two‐dimensional porous medium. For cases with low degrees of heterogeneity in hydraulic conductivity, acceptable results are possible for specific discharges between 10^?7 and 10^?5 m/s. However, conduction into areas with specific discharges less than 10^?7 m/s from adjacent areas can lead to significant errors. In some of these cases, the one‐dimensional solutions produced estimates of specific discharge of nearly 10^?6 m/s. This phenomenon is more likely in situations with greater degrees of heterogeneity.     

Electrical Resistivity Imaging of a Permanganate Injection During In Situ Treatment of RDX‐Contaminated Groundwater

Groundwater beneath the former Nebraska Ordnance Plant (NOP) is contaminated with the explosive hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and trichloroethene (TCE). Previous treatability experiments confirmed that permanganate could mineralize RDX in NOP aquifer material. The objective of this study was to determine the efficacy of permanganate to transform RDX in the field by monitoring a pilot‐scale in situ chemical oxidation (ISCO) demonstration. In this demonstration, electrical resistivity imaging (ERI) was used to create two‐dimensional (2‐D) images of the test site prior to, during, and after injecting sodium permanganate. The ISCO was performed by using an extraction‐injection well configuration to create a curtain of permanganate. Monitoring wells were positioned downgradient of the injection zone with the intent of capturing the permanganate‐RDX plume. Differencing between ERI taken preinjection and postinjection determined the initial distribution of the injected permanganate. ERI also quantitatively corroborated the hydraulic conductivity distribution across the site. Groundwater samples from 12 downgradient wells and 8 direct‐push profiles did not provide enough data to quantify the distribution and flow of the injected permanganate. ERI, however, showed that the permanganate injection flowed against the regional groundwater gradient and migrated below monitoring well screens. ERI combined with monitoring well samples helped explain the permanganate dynamics in downgradient wells and support the use of ERI as a means of monitoring ISCO injections.     

Discrete‐Storm Water‐Table Fluctuation Method to Estimate Episodic Recharge

We have developed a method to identify and quantify recharge episodes, along with their associated infiltration‐related inputs, by a consistent, systematic procedure. Our algorithm partitions a time series of water levels into discrete recharge episodes and intervals of no episodic recharge. It correlates each recharge episode with a specific interval of rainfall, so storm characteristics such as intensity and duration can be associated with the amount of recharge that results. To be useful in humid climates, the algorithm evaluates the separability of events, so that those whose recharge cannot be associated with a single storm can be appropriately lumped together. Elements of this method that are subject to subjectivity in the application of hydrologic judgment are values of lag time, fluctuation tolerance, and master recession parameters. Because these are determined once for a given site, they do not contribute subjective influences affecting episode‐to‐episode comparisons. By centralizing the elements requiring scientific judgment, our method facilitates such comparisons by keeping the most subjective elements openly apparent, making it easy to maintain consistency. If applied to a period of data long enough to include recharge episodes with broadly diverse characteristics, the method has value for predicting how climatic alterations in the distribution of storm intensities and seasonal duration may affect recharge.     

Total Dissolved Gas Pressure Measurements for Assessing Contaminant Degradation Processes in Groundwater

The total dissolved gas pressure (P_TDG ) probe has been used in groundwater studies for over a decade, but rarely in assessing contaminant degradation, despite the many degradation reactions that produce or consume dissolved gases. Here we present three studies to demonstrate the application of P_TDG measurements to groundwater experiencing contaminant degradation, with discussion of its benefits and limitations. The first study is a pilot‐scale laboratory experiment simulating dissolved ethanol contamination of an anaerobic sand aquifer. Continuous monitoring of P_TDG showed the rapid onset of microbial hydrocarbon degradation via denitrification and fermentation. The subsequent formation of a gas phase was revealed when P_TDG began mimicking the bubbling pressure (P_G *; sum of hydrostatic and atmospheric pressure), fluctuating with atmospheric pressure. Some deviations of P_TDG above P_G * occurred also, which may hold promise for signalling substantial changes in the rate or type of degradation process (here, the onset of methanogenesis). In the second study, synoptic field measurements at a petroleum plume site demonstrated how elevated P_TDG could identify wells with evidence of hydrocarbon degradation (denitrification and/or methanogenesis). And finally, combined field measurements of dissolved oxygen (DO) and P_TDG in monitoring wells of a nitrate‐contaminated aquifer (Abbottsford‐Sumas) revealed areas where denitrification was likely occurring. Limitations to P_TDG use identified in these studies included the masking of degradation processes by the presence of a gas phase, as when trapped following water table fluctuations or formed from rigorous degradation reactions, and confounded assessment of P_TDG patterns from other natural or anthropogenic processes that can also influence groundwater P_TDG .     

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).     

A Low‐Cost,In Situ Resistivity and Temperature Monitoring System

We present a low‐cost, reliable method for long‐term in situ autonomous monitoring of subsurface resistivity and temperature in a shallow, moderately heterogeneous subsurface. Probes, to be left in situ, were constructed at relatively low cost with an electrode spacing of 5 cm. Once installed, these were wired to the CR‐1000 Campbell Scientific Inc. datalogger at the surface to electrically image infiltration fronts in the shallow subsurface. This system was constructed and installed in June 2005 to collect apparent resistivity and temperature data from 96 subsurface electrodes set to a pole‐pole resistivity array pattern and 14 thermistors at regular intervals of 30 cm through May of 2008. From these data, a temperature and resistivity relationship was determined within the vadose zone (to a depth of ~1 m) and within the saturated zone (at depths between 1 and 2 m). The high vertical resolution of the data with resistivity measurements on a scale of 5‐cm spacing coupled with surface precipitation measurements taken at 3‐min intervals for a period of roughly 3 years allowed unique observations of infiltration related to seasonal changes. Both the vertical resistivity instrument probes and the data logger system functioned well for the duration of the test period and demonstrated the capability of this low‐cost monitoring system.     

A Simple Field Method for Assessing Near‐Surface Saturated Hydraulic Conductivity

This technical note describes an effective and inexpensive field technique for measuring the saturated hydraulic conductivity of both undisturbed cores and repacked soil samples. The method requires no specialized equipment; everything that is required can be obtained in a hardware store. The method is a straightforward field implementation of the widely used falling‐head laboratory analysis directly derived from Darcy's law. As such, it sidesteps the need for empirical assumptions about soil texture and the relationship between saturated and unsaturated flow components which many permeameter‐based methods rely upon. The method is shown to produce results that are consistent with K values obtained elsewhere in the same homogeneous sand formation. Furthermore, the proposed method is useful for measuring hydraulic conductivity in drill cuttings obtained from direct push or auguring drill techniques, which cannot be done with any other field method. The range of hydraulic conductivity values that this test is appropriate for is on the order of 1E ? 7 m/s to 1E ? 3 m/s.     

A Tube Seepage Meter for In Situ Measurement of Seepage Rate and Groundwater Sampling

We designed and evaluated a “tube seepage meter” for point measurements of vertical seepage rates (q), collecting groundwater samples, and estimating vertical hydraulic conductivity (K) in streambeds. Laboratory testing in artificial streambeds show that seepage rates from the tube seepage meter agreed well with expected values. Results of field testing of the tube seepage meter in a sandy‐bottom stream with a mean seepage rate of about 0.5 m/day agreed well with Darcian estimates (vertical hydraulic conductivity times head gradient) when averaged over multiple measurements. The uncertainties in q and K were evaluated with a Monte Carlo method and are typically 20% and 60%, respectively, for field data, and depend on the magnitude of the hydraulic gradient and the uncertainty in head measurements. The primary advantages of the tube seepage meter are its small footprint, concurrent and colocated assessments of q and K, and that it can also be configured as a self‐purging groundwater‐sampling device.     

Temperature‐Activated Auto‐Decomposition Reactions: An Under‐Utilized In Situ Remediation Solution

The remediation industry has witnessed multiple innovations arising from a greater understanding of the physical, chemical, and biological processes that control the fate and transport of chemicals in the subsurface environment. In addition, increasing emphasis is being placed on remediation solutions that are greener, simpler, and more resource efficient. The positive impacts that can be derived from this emphasis include reduced energy consumption, reduced waste emissions, and lower costs. Temperature‐activated auto‐decomposition reactions represent a potentially underutilized option for the in situ remediation of certain organic contaminants, and an option that can be both highly effective and greener than other available technologies.     

Modeling Variably Saturated Multispecies Reactive Groundwater Solute Transport with MODFLOW‐UZF and RT3D

A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated‐Zone Flow (UZF1) package and MODFLOW. Referred to as UZF‐RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS‐1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one‐dimensional, two‐dimensional, and three‐dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF‐RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run‐time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic‐wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF‐RT3D can be used for large‐scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary‐pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run‐time and the ability to include site‐specific chemical species and chemical reactions make UZF‐RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large‐scale subsurface systems.     

A Stream‐Based Methane Monitoring Approach for Evaluating Groundwater Impacts Associated with Unconventional Gas Development

Gaining streams can provide an integrated signal of relatively large groundwater capture areas. In contrast to the point‐specific nature of monitoring wells, gaining streams coalesce multiple flow paths. Impacts on groundwater quality from unconventional gas development may be evaluated at the watershed scale by the sampling of dissolved methane (CH₄) along such streams. This paper describes a method for using stream CH₄ concentrations, along with measurements of groundwater inflow and gas transfer velocity interpreted by 1‐D stream transport modeling, to determine groundwater methane fluxes. While dissolved ionic tracers remain in the stream for long distances, the persistence of methane is not well documented. To test this method and evaluate CH₄ persistence in a stream, a combined bromide (Br) and CH₄ tracer injection was conducted on Nine‐Mile Creek, a gaining stream in a gas development area in central Utah. A 35% gain in streamflow was determined from dilution of the Br tracer. The injected CH₄ resulted in a fivefold increase in stream CH₄ immediately below the injection site. CH₄ and δ¹³C_CH4 sampling showed it was not immediately lost to the atmosphere, but remained in the stream for more than 2000 m. A 1‐D stream transport model simulating the decline in CH₄ yielded an apparent gas transfer velocity of 4.5 m/d, describing the rate of loss to the atmosphere (possibly including some microbial consumption). The transport model was then calibrated to background stream CH₄ in Nine‐Mile Creek (prior to CH₄ injection) in order to evaluate groundwater CH₄ contributions. The total estimated CH₄ load discharging to the stream along the study reach was 190 g/d, although using geochemical fingerprinting to determine its source was beyond the scope of the current study. This demonstrates the utility of stream‐gas sampling as a reconnaissance tool for evaluating both natural and anthropogenic CH₄ leakage from gas reservoirs into groundwater and surface water.     

Bioaugmentation and Propane Biosparging for In Situ Biodegradation of 1,4‐Dioxane

Propane biosparging and bioaugmentation were applied to promote in situ biodegradation of 1,4‐dioxane at Site 24, Vandenberg Air Force Base (VAFB), CA. Laboratory microcosm and enrichment culture testing demonstrated that although native propanotrophs appeared abundant in the shallow water‐bearing unit of the aquifer (8 to 23 ft below ground surface [bgs]), they were difficult to be enriched from a deeper water‐bearing unit (82 to 90 feet bgs). Bioaugmentation with the propanotroph Rhodococcus ruber ENV425, however, supported 1,4‐dioxane biodegradation in microcosms constructed with samples from the deep aquifer. For field testing, a propane‐biosparging system consisting of a single sparging well and four performance monitoring wells was constructed in the deep aquifer. 1,4‐dioxane biodegradation began immediately after bioaugmentation with R. ruber ENV425 (36 L; 4 × 10⁹ cells/mL), and apparent first‐order decay rates for 1,4‐dioxane ranged from 0.021 day^?1 to 0.036 day^?1. First‐order propane consumption rates increased from 0.01 to 0.05 min^?1 during treatment. 1,4‐dioxane concentrations in the sparging well and two of the performance monitoring wells were reduced from as high as 1090 µg/L to <2 µg/L, while 1,4‐dioxane concentration was reduced from 135 µg/L to 7.3 µg/L in a more distal third monitoring well. No 1,4‐dioxane degradation was observed in the intermediate aquifer control well even though propane and oxygen were present. The demonstration showed that propane biosparging and bioaugmentation can be used for in situ treatment of 1,4‐dioxane to regulatory levels.