Utilizing Rare Earth Elements as Tracers in High TDS Reservoir Brines in CCS Applications

AbstractIn this paper we report the result of research associated with the testing of a procedures necessary for utilizing natural occurring trace elements, specifically the Rare Earth Elements (REE) as geochemical tracers in Carbon Capture and Storage (CCS) applications. Trace elements, particularly REE may be well suited to serve as in situ tracers for monitoring geochemical conditions and the migration of CO2-charged waters within CCS storage systems. We have been conducting studies to determine the efficacy of using REE as a tracer and characterization tool in the laboratory, at a CCS analogue site in Soda Springs, Idaho, and at a proposed CCS reservoir at the Rock Springs Uplift, Wyoming. Results from field and laboratory studies have been encouraging and show that REE may be an effective tracer in CCS systems and overlying aquifers. In recent years, a series of studies using REE as a natural groundwater tracer have been conducted successfully at various locations around the globe. Additionally, REE and other trace elements have been successfully used as in situ tracers to describe the evolution of deep sedimentary Basins. Our goal has been to establish naturally occurring REE as a useful monitoring measuring and verification (MMV) tool in CCS research because formation brine chemistry will be particularly sensitive to changes in local equilibrium caused by the addition of large volumes of CO2. Because brine within CCS target formations will have been in chemical equilibrium with the host rocks for millions of years, the addition of large volumes of CO2 will cause reactions in the formation that will drive changes to the brine chemistry due to the pH change caused by the formation of carbonic acid. This CO2 driven change in formation fluid chemistry will have a major impact on water rock reaction equilibrium in the formation, which will impart a change in the REE fingerprint of the brine that can measured and be used to monitor in situ reservoir conditions. Our research has shown that the REE signature imparted to the formation fluid by the introduction of CO2 to the formation, can be measured and tracked as part of an MMV program. Additionally, this REE fingerprint may serve as an ideal tracer for fluid migration, both within the CCS target formation, and should formation fluids migrate into overlying aquifers. However application of REE and other trace elements to CCS system is complicated by the high salt content of the brines contained within the target formations. In the United States by regulation, in order for a geologic reservoir to be considered suitable for carbon storage, it must contain formation brine with total dissolved solids (TDS) > 10,000ppm, and in most cases formation brines have TDS well in excess of that threshold. The high salinity of these brines creates analytical problems for elemental analysis, including element interference with trace metals in Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) (i.e. element mass overlap due to oxide or plasma phenomenon). Additionally, instruments like the ICP-MS that are sensitive enough to measure trace elements down to the parts per trillion level are quickly oversaturated when water TDS exceeds much more than 1,000ppm. Normally this problem is dealt with through dilution of the sample, bringing the water chemistry into the instruments working range. However, dilution is not an option when analyzing these formation brines for trace metals, because trace elements, specifically the REE, which occur in aqueous solutions at the parts per trillion levels. Any dilution of the sample would make REE detection impossible. Therefore, the ability to use trace metals as in situ natural tracers in high TDS brines environments requires the development of methods for pre-concentrating trace elements, while reducing the salinity and associated elemental interference such that the brines can be routinely analyzed by standard ICP-MS methods. As part of the Big Sky Carbon Sequestration Project the INL-CAES has developed a rapid, easy to use process that pre-concentrates trace metals, including REE, up to 100x while eliminating interfering ions (e.g. Ba, Cl). The process is straightforward, inexpensive, and requires little infrastructure, using only a single chromatography column with inexpensive, reusable, commercially available resins and wash chemicals. The procedure has been tested with synthetic brines (215,000ppm or less TDS) and field water samples (up to 5,000ppm TDS). Testing has produced data of high quality with REE capture efficiency exceeding 95%, while reducing interfering elements by > 99%

Final Report - Assessment of Testing Options for the NTR at the INL

One of the main technologies that can be developed to dramatically enhance the human exploration of space is the nuclear thermal rocket (NTR). Several studies over the past thirty years have shown that the NTR can reduce the cost of a lunar outpost, reduce the risk of a human mission to Mars, enable fast transits for most missions throughout the solar system, and reduce the cost and time for robotic probes to deep space. Three separate committees of the National Research Council of the National Academy of Sciences have recommended that NASA develop the NTR. One of the primary issues in development of the NTR is the ability to verify a flight ready unit. Three main methods can be used to validate safe operation of a NTR: 1) Full power, full duration test in an above ground facility that scrubs the rocket exhaust clean of any fission products; 2) Full power , full duration test using the Subsurface Active Filtering of Exhaust (SAFE) technique to capture the exhaust in subsurface strata; 3) Test of the reactor fuel at temperature and power density in a driver reactor with subsequent first test of the fully integrated NTR in space. The first method, the above ground facility, has been studied in the past. The second method, SAFE, has been examined for application at the Nevada Test Site. The third method relies on the fact that the Nuclear Furnace series of tests in 1971 showed that the radioactive exhaust coming from graphite based fuel for the NTR could be completely scrubbed of fission products and the clean hydrogen flared into the atmosphere. Under funding from the MSFC, the Center for Space Nuclear Research (CSNR) at the Idaho National laboratory (INL) has completed a reexamination of Methods 2 and 3 for implementation at the INL site. In short, the effort performed the following: 1) Assess the geology of the INL site and determine a location suitable SAFE testing; 2) Perform calculations of gas transport throughout the geology; 3) Produce a cost estimate of a non-nuclear , sub-scale test using gas injection to validate the computational models; 4) Produce a preliminary cost estimate to build a nuclear furnace equivalent facility to test NTR fuel on a green field location on the INL site. The results show that the INL geology is substantially better suited to the SAFE testing method than the NTS site. The existence of impermeable interbeds just above the sub-surface aquifer ensure that no material from the test, radioactive or not, can enter the water table. Similar beds located just below the surface will prevent any gaseous products from reaching the surface for dispersion. The extremely high permeability of the strata between the interbeds allows rapid dispersion of the rocket exhaust. In addition, the high permeability suggests that a lower back-pressure may develop in the hole against the rocket thrust, which increases safety of operations. Finally, the cost of performing a sub-scale, non-nuclear verification experiment was determined to be $3M. The third method was assessed through discussions with INL staff resident at the site. In essence, any new Category I facility on any DOE site will cost in excess of$250M. Based on the results of this study, a cost estimate for testing a nuclear rocket at the INL site appears to be warranted. Given the fact that a new nuclear fuel may be possible that does not release any fission products, the SAFE testing option appears to be the most affordable

Energy in the Mountain West: Colonialism and Independence

In many ways, the mountain west (Alaska, Arizona, Colorado, Idaho, Montana, New Mexico, Nevada, Utah, Wyoming) is an energy colony for the rest of the United States: it is rich in energy resources that are extracted to fuel economic growth in the wealthier and more populous coastal regions. Federal agencies and global corporations often behave as if the mountain west is a place to be exploited or managed for the benefit of customers and consumers elsewhere. Yet, the area. is not vast empty space with a limitless supply of natural resources, but rather a fast-growing region with a diverse economic base dependent on a limited supply of water. New decision processes and collaborations are slowly changing this situation, but in a piecemeal fashion that places local communities at odds with powerful external interests. Proper planning of major development is needed to insure that the west has a strong economic and cultural future after the fossil energy resources decline, even if that might be a century from now. To encourage the necessary public discussions, this paper identifies key differences between the mountain west and the rest of the United States and suggests some holistic approaches that could improve our future. This paper is designed to provoke thought and discussion; it does not report new analyses on energy resources or usage. It is a summary of a large group effort

Groundwater “fast paths” in the Snake River Plain aquifer: Radiogenic isotope ratios as natural groundwater tracers

Preferential flow paths are expected in many groundwater systems and must be located because they can greatly affect contaminant transport. The fundamental characteristics of radiogenic isotope ratios in chemically evolving waters make them highly effective as preferential flow path indicators. These ratios tend to be more easily interpreted than solute-concentration data because their response to water-rock interaction is less complex. We demonstrate this approach with groundwater {sup 87}Sr/{sup 86}Sr ratios in the Snake River Plain aquifer within and near the Idaho National Engineering and Environmental Laboratory. These data reveal slow-flow zones as lower {sup 87}Sr/{sup 86}Sr areas created by prolonged interaction with the host basalts and a relatively fast flowing zone as a high {sup 87}Sr/{sup 86}Sr area

VESTA - Very-High-Temperature Heat Aquifer Storage

Energy storage is one of the key challenges of the energy transition. Eight international partners from Germany, Switzerland and the USA address this challenge in the joint project VESTA. Goal of VESTA is the generic development and demonstration of high-temperature storage in the underground. Four pilot sites in the DACH region in various geologies and project phases allow feedback loops between generic scientific investigations and application of new geothermal technologies. Specifically, pilot sites that shall 1) demonstrate HT-ATES technology, 2) evaluate technical and non-technical barriers, 3) support development and implementation by providing techniques and optimized component design, and 4) support agencies with scientific and technical knowledge as a basis for advancing regulatory provisions. With this scientific program, VESTA shall form a technical-economic bases for future operational concepts

Development Report on the Idaho National Laboratory Sitewide Three-Dimensional Aquifer Model

A sub-regional scale, three-dimensional flow model of the Snake River Plain Aquifer was developed to support remediation decisions for Waste Area Group 10, Operable Unit 10 08 at the Idaho National Laboratory (INL) Site. This model has been calibrated primarily to water levels and secondarily to groundwater velocities interpreted from stable isotope disequilibrium studies and the movement of anthropogenic contaminants in the aquifer from facilities at the INL. The three-dimensional flow model described in this report is one step in the process of constructing a fully three-dimensional groundwater flow and contaminant transport model as prescribed in the Idaho National Engineering and Environmental Laboratory Operable Unit 10-08 Sitewide Groundwater Model Work Plan. An updated three-dimensional hydrogeologic conceptual model is presented along with the geologic basis for the conceptual model. Sediment-dominated three-dimensional volumes were used to represent the geology and constrain groundwater flow as part of the conceptual model. Hydrological, geochemical, and geological data were summarized and evaluated to infer aquifer behavior. A primary observation from development and evaluation of the conceptual model was that relative to flow on a regional scale, the aquifer can be treated with steady-state conditions. Boundary conditions developed for the three-dimensional flow model are presented along with inverse simulations that estimate parameterization of hydraulic conductivity. Inverse simulations were performed using the pilot-point method to estimate permeability distributions. Thermal modeling at the regional aquifer scale and at the sub-regional scale using the inverted permeabilities is presented to corroborate the results of the flow model. The results from the flow model show good agreement with simulated and observed water levels almost always within 1 meter. Simulated velocities show generally good agreement with some discrepancies in an interpreted low-velocity region near the toe of the Arco Hills. This discrepancy persisted in each of the aquifer bottom thickness scenarios that were simulated precluding decisions on which aquifer bottom thickness to use in transport simulations. When joint-calibration was performed using both water levels and velocities assigned as calibration targets, the discrepancy was prevented. This result highlighted the need to consider multiple calibration objectives and not rely solely on calibration to water levels. The next and last step in the process of constructing a fully three-dimensional groundwater flow and contaminant transport model will be calibration directly to transport from facilities. This last step will likely require further modification of the velocity fields resulting from the three-dimensional groundwater flow model presented in this report

Carbon Sequestration in the Kevin Dome, Northern Montana

The Big Sky Carbon Sequestration Partnership examines the ability of geologic systems to safely trap anthropogenic carbon dioxide to mitigate its impact on climate. One such system is the Duperow Formation within Kevin Dome, a large sedimentary trap and cap structure that has a long history of oil and gas production. To test storage potential of the dome, naturally trapped carbon dioxide is extracted, compressed, and reinjected. Geophysical methods and monitoring wells provide evidence of the fate and transport of the re-injected carbon dioxide. This study and others like it demonstrate the efficacy carbon sequestration at an industrial scale

Carbon Issues Task Force Report for the Idaho Strategic Energy Alliance

The Carbon Issues Task Force has the responsibility to evaluate emissions reduction and carbon offset credit options, geologic carbon sequestration and carbon capture, terrestrial carbon sequestration on forest lands, and terrestrial carbon sequestration on agricultural lands. They have worked diligently to identify ways in which Idaho can position itself to benefit from potential carbon-related federal legislation, including identifying opportunities for Idaho to engage in carbon sequestration efforts, barriers to development of these options, and ways in which these barriers can be overcome. These are the experts to which we will turn when faced with federal greenhouse gas-related legislation and how we should best react to protect and provide for Idaho’s interests. Note that the conclusions and recommended options in this report are not intended to be exhaustive, but rather form a starting point for an informed dialogue regarding the way-forward in developing Idaho energy resources

Elucidating Water Sources and Interaction with Hydrogeologic Systems: Enthalpy, Radon, and Rare Earth Elements as Naturally Occurring Tracers

Presented are three studies that utilize three natural tracers (enthalpy, radon gas, and rare earth elements) to characterize hydrologic systems at three different scales. The scale of investigation ranges from 27,900 km2 for the Eastern Snake River Plain (ESRP) regional aquifer to 0.34 km2 for Shepley’s Hill in West Central Massachusetts. In the first study, we use aquifer temperature and wellbore temperature profiles from the ESRP in an integrated effort to trace regional groundwater flow and aquifer thickness and identify zones of elevated geothermal potential under the ESRP. Understanding the hydrologic conditions of the ESRP aquifer is important to the residents of Eastern Idaho, as it is a soul source aquifer for the region. In our second application of natural tracers, we utilize 222Rn to detect fluid-flow pathways in a fractured-rock-hosted vadose zone at Fort Devens, Massachusetts. The vadose zone is believed to be the source of meteoric water infiltrating a contaminated aquifer that underlies a contaminated landfill. Understanding the source of the meteoric water that flows into the contaminated aquifer is an important part of remediation of the contaminated site. Finally, we investigate and test procedures to preconcentrate trace rare earth elements (REEs) to improve detection by ICP-MS and apply these techniques to characterize a leaking CO2 system in Soda Springs, Idaho. Here, we use groundwater REE chemistry as a tracer to track CO2-charged waters at a natural carbon capture and storage (CCS) analogue site. At this site, naturally leaking CO2 and associated brines from depth is migrating into a shallow aquifer. These studies conducted at widely varying scales and using different tracers demonstrate the usefulness of natural tracers to elucidate conditions in the subsurface that cannot be directly measured by anthropogenic tracers.doctoral, Ph.D., Geology -- University of Idaho - College of Graduate Studies, 201