Improving predictive models for noble gas transport through natural materials at the field-scale is an essential component of improving US nuclear monitoring capabilities. Several field-scale experiments with a gas transport component have been conducted at the Nevada National Security Site (Non-Proliferation Experiment, Underground Nuclear Explosion Signatures Experiment). However, the models associated with these experiments have not treated zeolite minerals as gas adsorbing phases. This is significant as zeolites are a common alteration mineral with a high abundance at these field sites and are shown here to significantly fractionate noble gases during field-scale transport. This fractionation and associated retardation can complicate gas transport predictions by reducing the signal-to-noise ratio to the detector (e.g. mass spectrometers or radiation detectors) enough to mask the signal or make the data difficult to interpret. Omitting adsorption-related retardation data of noble gases in predictive gas transport models therefore results in systematic errors in model predictions where zeolites are present.Herein is presented noble gas adsorption data collected on zeolitized and non-zeolitized tuff. Experimental results were obtained using a unique piezometric adsorption system designed and built for this study. Data collected were then related to pure-phase mineral analyses conducted on clinoptilolite, mordenite, and quartz. These results quantify the adsorption capacity of materials present in field-scale systems, enabling the modeling of low-permeability rocks as significant sorption reservoirs vital to bulk transport predictions.
Detection of radioxenon and radioargon produced by underground nuclear explosions is one of the primary methods by which the Comprehensive Nuclear-Test–Ban Treaty (CTBT) monitors for nuclear activities. However, transport of these noble gases to the surface via barometric pumping is a complex process relying on advective and diffusive processes in a fractured porous medium to bring detectable levels to the surface. To better understand this process, experimental measurements of noble gas and chemical surrogate diffusivity in relevant lithologies are necessary. However, measurement of noble gas diffusivity in tight or partially saturated porous media is challenging due to the transparent nature of noble gases, the lengthy diffusion times, and difficulty maintaining consistent water saturation. Here, the quasi-steady-state Ney–Armistead method is modified to accommodate continuous gas sampling via effusive flow to a mass spectrometer. An analytical solution accounting for the cumulative sampling losses and induced advective flow is then derived. Experimental results appear in good agreement with the proposed theory, suggesting the presence of retained groundwater reduces the effective diffusivity of the gas tracers by 10–1000 times. Furthermore, by using a mass spectrometer, the method described herein is applicable to a broad range of gas species and porous media.
The success of geological carbon storage (GCS) depends on the sealing properties of caprocks, typically mudrocks, and their laminated variety – shales. In this study, we examined mineralogical changes in carbonate-rich Mancos Shale and corresponding changes in micro-mechanical properties following the reaction with carbon dioxide (CO2). Mineralogical changes of Mancos Shale depended on the pressure of CO2 during its exposure to the CO2-brine mixtures for up to 8 weeks. Dedolomitization was observed in the reactors pressurized with 100 psi of CO2, combined with the precipitation of gypsum. In the reactor pressurized with 2500 psi of CO2, the complete dissolution of calcite, partial dissolution of dolomite, and precipitation of magnesite and anhydrite were observed. Localized mechanical weakening was observed only for dolomite-muscovite-illite-rich laminae following whole shale puck alteration at 2500 psi of CO2, and a decrease of up to 50 ± 20% in scratch toughness was observed. The quartz-calcite-rich laminae did not exhibit a measurable difference in scratch toughness before and after reaction in CO2-rich brine. The predicted changes in mineralogy, porosity, density, and hardness of Mancos Shale are limited, according to the geochemical models describing alteration of shale by CO2-rich brine lasting for 5000 years. This study illustrates a coupled and localized chemical-mechanical response of caprock to the injection of CO2.
Presented herein are laboratory gas migration experiments conducted on samples of tuff with varying lithologies mounted within a triaxial core holder. A pressurized gas mixture standard comprised of known concentrations of argon (Ar), xenon (Xe), nitrogen (N2) and sulfur hexafluoride (SF6used as a tracer) was used based on previous field gas migration studies. The gas mix is applied at known pressure to the upstream side of the samples to induce flow through the pore spaces and/or across fracture surfaces and the gases are detected in real-time on the downstream side using a quadrupole mass spectrometer (QMS). Downstream detection under vacuum is possible by precise metering of the gas mixture through a leak valve with active feedback control. Arrival times and time-variant concentrations of the applied gases downstream are collected for comparison between samples. We intend to determine transport properties of noble gases and SF6, and hypothesize that transport properties vary due to solubility and water content. The parameters derived from this work will provide valuable insight into the three-dimensional structure of damage zones, including fracture networks, the production of temporally variable signatures, and the methods to best detect underground nuclear explosion signatures.