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NASA NTRS2015

Enhanced Weathering Strategies for Stabilizing Climate and Averting Ocean Acidification

Chemical breakdown of rocks, weathering, is an important but very slow part of the carbon cycle that ultimately leads to CO2 being locked up in carbonates on the ocean floor. Artificial acceleration of this carbon sink via distribution of pulverized silicate rocks across terrestrial landscapes may help offset anthropogenic CO2 emissions. We show that idealized enhanced weathering scenarios over less than a third of tropical land could cause significant drawdown of atmospheric CO2 and ameliorate ocean acidification by 2100. Global carbon cycle modelling driven by ensemble Representative Concentration Pathway (RCP) projections of twenty-first-century climate change (RCP8.5, business-as-usual; RCP4.5, medium-level mitigation) indicates that enhanced weathering could lower atmospheric CO2 by 30-300 ppm by 2100, depending mainly on silicate rock application rate (1 kg or 5 kg m(exp -2) yr (exp -1)) and composition. At the higher application rate, end-of-century ocean acidification is reversed under RCP4.5 and reduced by about two-thirds under RCP8.5. Additionally, surface ocean aragonite saturation state, a key control on coral calcification rates, is maintained above 3.5 throughout the low latitudes, thereby helping maintain the viability of tropical coral reef ecosystems. However, we highlight major issues of cost, social acceptability, and potential unanticipated consequences that will limit utilization and emphasize the need for urgent efforts to phase down fossil fuel emissions.

Taylor, Lyla L.↗
NASA NTRS2015

Enhanced Weathering Strategies for Stabilizing Climate and Averting Ocean Acidification - Supplementary Information

Chemical breakdown of rocks, weathering, is an important but very slow part of the carbon cycle that ultimately leads to CO2 being locked up in carbonates on the ocean floor. Artificial acceleration of this carbon sink via distribution of pulverized silicate rocks across terrestrial landscapes may help offset anthropogenic CO2 emissions. We show that idealized enhanced weathering scenarios over less than a third of tropical land could cause significant drawdown of atmospheric CO2 and ameliorate ocean acidification by 2100. Global carbon cycle modelling driven by ensemble Representative Concentration Pathway (RCP) projections of twenty-first-century climate change (RCP8.5, business-as-usual; RCP4.5, medium-level mitigation) indicates that enhanced weathering could lower atmospheric CO2 by 30-300 ppm by 2100, depending mainly on silicate rock application rate (1 kg or 5 kg m(exp. -2) yr (exp -1)) and composition. At the higher application rate, end-of-century ocean acidification is reversed under RCP4.5 and reduced by about two-thirds under RCP8.5. Additionally, surface ocean aragonite saturation state, a key control on coral calcification rates, is maintained above 3.5 throughout the low latitudes, thereby helping maintain the viability of tropical coral reef ecosystems. However, we highlight major issues of cost, social acceptability, and potential unanticipated consequences that will limit utilization and emphasize the need for urgent efforts to phase down fossil fuel emissions.

Taylor, Lyla L.↗
NASA NTRS2015

Atmospheric CO2 Variability Observed From ASCENDS Flight Campaigns

Significant atmospheric CO2 variations on various spatiotemporal scales were observed during ASCENDS flight campaigns. For example, around 10-ppm CO2 changes were found within free troposphere in a region of about 200x300 sq km over Iowa during a summer 2014 flight. Even over extended forests, about 2-ppm CO2 column variability was measured within about 500-km distance. For winter times, especially over snow covered ground, relatively less horizontal CO2 variability was observed, likely owing to minimal interactions between the atmosphere and land surface. Inter-annual variations of CO2 drawdown over cornfields in the Mid-West were found to be larger than 5 ppm due to slight differences in the corn growing phase and meteorological conditions even in the same time period of a year. Furthermore, considerable differences in atmospheric CO2 profiles were found during winter and summer campaigns. In the winter CO2 was found to decrease from about 400 ppm in the atmospheric boundary layer (ABL) to about 392 ppm above 10 km, while in the summer CO2 increased from 386 ppm in the ABL to about 396 ppm in free troposphere. These and other CO2 observations are discussed in this presentation.

Lin, Bing↗
NASA NTRS2018

Improved Hydrology over Peatlands in a Global Land Modeling System

Peatlands of the Northern Hemisphere represent an important carbon pool that mainly accumulated since the last ice age under permanently wet conditions in specific geological and climatic settings. The carbon balance of peatlands is closely coupled to water table dynamics. Consequently, the future carbon balance over peatlands is strongly dependent on how hydrology in peatlands will react to changing boundary conditions, e.g. due to climate change or regional water level drawdown of connected aquifers or streams. Global land surface modeling over organic-rich regions can provide valuable global-scale insights on where and how peatlands are in transition due to changing boundary conditions. However, the current global land surface models are not able to reproduce typical hydrological dynamics in peatlands well. We implemented specific structural and parametric changes to account for key hydrological characteristics of peatlands into NASA's GEOS-5 Catchment Land Surface Model (CLSM, Koster et al. 2000). The main modifications pertain to the modeling of partial inundation, and the definition of peatland-specific runoff and evapotranspiration schemes. We ran a set of simulations on a high performance cluster using different CLSM configurations and validated the results with a newly compiled global in-situ dataset of water table depths in peatlands. The results demonstrate that an update of soil hydraulic properties for peat soils alone does not improve the performance of CLSM over peatlands. However, structural model changes for peatlands are able to improve the skill metrics for water table depth. The validation results for the water table depth indicate a reduction of the bias from 2.5 to 0.2 m, and an improvement of the temporal correlation coefficient from 0.5 to 0.65, and from 0.4 to 0.55 for the anomalies. Our validation data set includes both bogs (rain-fed) and fens (ground and/or surface water influence) and reveals that the metrics improved less for fens. In addition, a comparison of evapotranspiration and soil moisture estimates over peatlands will be presented, albeit only with limited ground-based validation data. We will discuss strengths and weaknesses of the new model by focusing on time series of specific validation sites.

Bechtold, M.↗
NASA NTRS2015

Remote Sensing Measurements of the CO2 Mixing Ratio in the Planetary Boundary Layer Using Cloud Slicing with Airborne Lidar

We have measured the CO2 volume mixing ratio (VMR) within the planetary boundary layer (PBL) using cloud slicing with an airborne pulsed integrated path differential absorption (IPDA) lidar from flight altitudes of up to 13 km. During a flight over Iowa in summer 2011, simultaneous measurement of the optical range and CO2 absorption to clouds and the ground were made using time-resolved detection of pulse echoes from each scattering surface.We determined the CO2 absorption in the PBL by differencing the two lidar-measured absorption line shapes, one to a broken shallow cumulus cloud layer located at the top of the PBL and the other to the ground. Solving for the CO2 VMR in the PBL and that of the free troposphere, we measured a ≈15 ppm (4%) drawdown in the PBL. Both CO2 VMRs were within ≈3 ppm of in situ CO2 profile measurements. We have also demonstrated cloud slicing using scatter from thin, diffuse cirrus clouds and cumulus clouds, which allowed solving for the CO2 VMR for three vertical layers. The technique and retrieval algorithm are applicable to a space-based lidar instrument as well as to lidar IPDA measurements of other trace gases. Thus, lidar cloud slicing also offers promise toward space-based remote sensing of vertical trace gas profiles in the atmosphere using a variety of clouds.

VMR↗
NASA NTRS2018

Weathering in the Forelands of Two Rapidly Retreating Alpine Glaciers of Volcanic Bedrock in the Three Sisters, Oregon, USA

The glaciers of the Three Sisters volcanoes in Cascadia have retreated dramatically over the past century. In order to understand ongoing chemical weathering and solute transport in the proglacial valleys, waters were sampled from glacier outwash streams, local snowmelt, and proglacial springs and lakes at Collier and Diller Glaciers. To understand weathering and transport processes in the proglacial plains, infrared orbital remote sensing data was used to map compositional variability and highlight weathering products, which were then ground-truthed with laboratory mineralogical and chemical analyses of sediments. The hydrochemistry is significantly affected by a sub- and proglacial mafic weathering system lacking carbonate minerals. Here we report major ion concentrations in meltwaters for the summer 2016 and 2017 melt seasons. Total cation concentrations range from 3 to 250 μeq/l and dissolved bicarbonate concentrations range from 2 to 200 μeq/l. Other dissolved anions are negligible compared to bicarbonate. Dissolved silica concentrations range from 2 to 260 μmol/l, comparable to total dissolved cation concentrations. The highest cation and silica concentrations were measured in moraine-sourced springs. Compositional remote sensing analysis identified alteration zones in the proglacial plains at both Collier and Diller indicating potential hydrated silica. This analysis is consistent with laboratory analysis of sediment samples, which indicate the presence of poorly crystalline phases weathering products, including hydrated silica. Weathered materials are preferentially deposited on moraines due to aeolian and glacial transport, as well as intra-moraine alteration, and at abandoned stream terraces due to fluvial transport. Geochemical measurements indicate that the predominant form of chemical weathering in these periglacial mafic systems is the carbonation of feldspar as well as reactive volcanic glass. The presence of poorly crystalline silicates, as indicated by remote sensing datasets and laboratory analysis, is consistent with rapid weathering of feldspars and glass and formation of Fe-Al-Si-bearing mineraloids in these proglacial valleys. This weathering regime has wide-ranging implications for atmospheric CO2 drawdown due to cold-climate volcanic rock weathering.

Rutledge, Alicia M.↗
NASA NTRS2020

CMIP6 Historical Simulations (1850‐2014) with GISS‐E2.1

Simulations of the CMIP6 historical period 1850‐‐2014, characterized by the emergence of anthropogenic climate drivers like greenhouse gases, are presented for different configurations of the NASA Goddard Institute for Space Studies (GISS) Earth System ModelE2.1. The GISS‐E2.1 ensembles are more sensitive to forcing than their CMIP5 predecessors (GISS‐E2), but warm less during recent decades due to reduced total forcing. This forcing reduction is attributed to an increase in longwave opacity in pre‐industrial simulations, resulting in an atmosphere less sensitive to further increases in opacity that result from rising greenhouse gas concentrations. This demonstrates the importance of the base climatology to forcing and forced climate trends. Most model versions match observed temperature trends since 1979 from the ocean to the stratosphere. The choice of ocean model is important to the transient climate response, as found in CMIP5 GISS‐E2: the model that more efficiently exports heat to the deep ocean shows a smaller rise in tropospheric temperature. Model sea level rise over the historical period is traced to excessive drawdown of aquifers to meet irrigation demand with a smaller contribution from thermal expansion. This shows how fully coupled models can provide indirect observational constraints upon forcing, in this case, constraining irrigation rates with observed sea level changes. The overall agreement of GISS‐E2.1 with observed trends is familiar from evaluation of its predecessors, as is the conclusion that these trends are almost entirely anthropogenic in origin.

NASA Goddard Institute for Space Studies (GISS) Ea↗
NASA NTRS2019

Industrial-Era Decline in Subarctic Atlantic Productivity

Marine phytoplankton play a critical role in modulating marine-based food webs, fishery yields, and the global drawdown of atmospheric CO2. Due to sparse measurements prior to 21st century satellite monitoring, however, little is known of the long-term response of planktonic stocks to climate forcing. Here we produce the first continuous, multi-century record of subarctic Atlantic marine productivity, showing a marked 10 ± 7% decline has occurred across this highly-productive ocean basin over the last two centuries. We support this conclusion through the application of a novel marine-productivity proxy, established using a unique signal of planktonic-derived aerosol commonly identified across an array of Greenlandic ice cores. Utilizing contemporaneous satellite-era observations, we demonstrate this signal’s use as a robust and high-resolution proxy for spatially-integrated marine productivity variations. We show that the initiation of declining subarctic Atlantic productivity broadly coincides with the onset of Arctic surface warming, and that productivity strongly covaries with regional sea-surface temperatures and basin-wide gyre circulation strength over recent decades. Taken together, our results suggest the industrial era productivity decline may be evidence of the predicted5 collapse of northern Atlantic planktonic stocks in response to a weakened Atlantic Meridional Overturning Circulation (AMOC). Continued AMOC weakening, as projected for the 21st century, may therefore result in further productivity declines across this globally-relevant region.

Climate change↗
NASA NTRS2024

Interim Measures Pilot Study Completion Report, South Repeater Building, Solid Waste Management Unit 121, Hydraulic Containment and Groundwater Treatment System for Per- and Polyfluoroalkyl Substances

This Per- and Polyfluoroalkyl Substances (PFAS) Interim Measures Pilot Study Completion Report was prepared for the National Aeronautics and Space Administration by AECOM Technical Services, Inc. under Contract 80KSC019D0010, Task Order 80KSC021F0096. The purpose of this report is to document the pilot study activities at the South Repeater Building, Solid Waste Management Unit (SWMU) 121. This report details the additional assessment activities completed from June 2023 through November 2023 and the subsequent pilot study completed at the South Repeater Building conducted in December 2023 through February 2024. Initial activities were conducted in accordance with the Pilot Study Work Plan (NASA 2023), submitted to the KSC Remediation Team and accepted by the team on October 26, 2023. The objectives of the pilot study were to: • Provide information on aquifer characteristics and to aid in future modeling and remedial design activities to mitigate off-KSC migration of PFAS compounds. • Develop information on characteristics of the surficial aquifer system, specifically transmissivity, storage coefficient, hydraulic conductivity, and vertical hydraulic conductivity. • Obtain data to support construction and calibration of a groundwater flow model. • Acquire design parameters necessary for future remedial design activities, specifically radius of influence, drawdown, flow rates, and pump settings. The following activities were completed to meet the pilot study objectives: • Groundwater and surface water sampling • Geophysical investigation via Hydraulic Profiling Tool (HPT) and soil sampling • Installation of observation and extraction wells via rotosonic techniques • Slug, step, and pump testing activities • Initial modeling efforts for a groundwater hydraulic containment system. Results of the pilot study and modeling activities are being used in the development of a groundwater containment and treatment system for the site.

PFAS↗
DOE OSTI2018

Potential Experimental Topics for EGS Collab Experiment 3

To facilitate the success of FORGE, the DOE GTO has initiated a new research effort, the EGS Collab project, which will utilize readily accessible underground facilities that can refine our understanding of rock mass response to stimulation and provide a test bed at intermediate (~10 m) scale for the validation of thermal-hydrological-mechanical-chemical modeling approaches as well as novel monitoring tools. The first two EGS Experiments 1 and 2 are planned be performed under different stress/fracture conditions, and will evaluate different stimulation processes: Experiment 1 will focus on hydrofracturing of a competent rock mass, while Experiment 2 will concentrate on hydroshearing of a rock mass that contains natural fractures. Experiment 3 is scheduled to begin in 2019 will build off the lessons learned in Experiments 1 and 2 and will investigate alternate stimulation and operation methods to improve heat extraction in an EGS reservoir. This paper evaluates potential experiments that could potentially be conducted in Experiment 3. The two technical parameters defining energy extracted from EGS reservoirs with the highest economic uncertainty and risk are the production well flow rates and the reservoir thermal drawdown rate. A review of historical and currently on-going EGS studies has identified that over 1/2 of the projects have identified heat extraction challenges during their operation associated with these two parameters as well as some additional secondary issues. At present, no EGS reservoir has continuously produced flow rates on the order of 80 kg/s. Short circuiting (i.e. early thermal breakthrough) has been identified in numerous cases. In addition, working fluid loss (i.e. the difference between the injected fluid mass and the extracted fluid mass as compared to the injected mass) has been as high as 90%. Finally, the engineering aspects of operating a true EGS multi-fracture reservoir such as repairing/modifying fractures and controlling working fluid fluxes within multiple fractures for the effective EGS fracture management has not been sufficiently studied. To examine issues such as these, EGS Collab Experiment 3 may be conducted in the testbeds prepared for Experiments 1 and 2 by improving the previously performed stimulations, or conducted at a new site performing new stimulations with alternate method. Potential experiments may include using different stimulation and working fluids, evaluating different stimulation methods, using proppants to enhance permeability, and other high-risk high-reward methods that can be evaluated at the 10-m scale environment.

15 GEOTHERMAL ENERGY↗
DOE OSTI2018

Potential Experimental Topics for EGS Collab Experiment 3

To facilitate the success of FORGE, the DOE GTO has initiated a new research effort, the EGS Collab project, which will utilize readily accessible underground facilities that can refine our understanding of rock mass response to stimulation and provide a test bed at intermediate (~10 m) scale for the validation of thermal-hydrological-mechanical-chemical modeling approaches as well as novel monitoring tools. The first two EGS Experiments 1 and 2 are planned be performed under different stress/fracture conditions, and will evaluate different stimulation processes: Experiment 1 will focus on hydrofracturing of a competent rock mass, while Experiment 2 will concentrate on hydroshearing of a rock mass that contains natural fractures. Experiment 3 is scheduled to begin in 2019 will build off the lessons learned in Experiments 1 and 2 and will investigate alternate stimulation and operation methods to improve heat extraction in an EGS reservoir. This paper evaluates potential experiments that could potentially be conducted in Experiment 3. The two technical parameters defining energy extracted from EGS reservoirs with the highest economic uncertainty and risk are the production well flow rates and the reservoir thermal drawdown rate. A review of historical and currently on-going EGS studies has identified that over ½ of the projects have identified heat extraction challenges during their operation associated with these two parameters as well as some additional secondary issues. At present, no EGS reservoir has continuously produced flow rates on the order of 80 kg/s. Short circuiting (i.e. early thermal breakthrough) has been identified in numerous cases. In addition, working fluid loss (i.e. the difference between the injected fluid mass and the extracted fluid mass as compared to the injected mass) has been as high as 90%. Finally, the engineering aspects of operating a true EGS multi-fracture reservoir such as repairing/modifying fractures and controlling working fluid fluxes within multiple fractures for the effective EGS fracture management has not been sufficiently studied. To examine issues such as these, EGS Collab Experiment 3 may be conducted in the testbeds prepared for Experiments 1 and 2 by improving the previously performed stimulations, or conducted at a new site performing new stimulations with alternate method. Potential experiments may include using different stimulation and working fluids, evaluating different stimulation methods, using proppants to enhance permeability, and other high-risk high-reward methods that can be evaluated at the 10-m scale environment.

15 GEOTHERMAL ENERGY↗
DOE OSTI2019

Techno-Economic Assessment of Geothermal Power Plants Hybridized with Solar Heat and Thermal Storage

Geothermal power plants may experience a decrease in power output over time due to a reduction in either mass flow rate, temperature or pressure of the resource. A recent study quantified the temperature drawdown of U.S. double-flash geothermal power plants at 0.8% per year. Hybridizing existing geothermal plants with other renewable power sources to exploit the unused capacity of the geothermal power block has become an area of increasing interest. For instance, a geothermal power plant may be retrofitted with heat from a concentrating solar field. In addition, geothermal may be integrated with solar in a new-build site with the aim of combining the benefits of both technologies -- i.e. the baseload generation of geothermal, plus the relatively high efficiency of concentrating solar power. In this article, we give an overview of hybrid geothermal-solar projects undertaken at the National Renewable Energy Laboratory in collaboration with various partners. We investigate the retrofit of double-flash and binary geothermal plants with solar heat. Off-design models are developed and validated with operational data. Annual simulations evaluate the hourly performance, the benefits of thermal storage, and are used to calculate economic metrics. Finally, we discuss the implications of integrating solar and geothermal in a new greenfield site.

15 GEOTHERMAL ENERGY↗
DOE OSTI2018

A Stratigraphic Approach to Characterize the Deposition and Storage of Organic Matter in Reservoir Sediments.

The relationship between carbon burial and sedimentation in reservoirs is unknown, exposing gaps in our fundamental understanding of the transport, processing, and deposition of sediment and organic matter in fluvial and lacustrine systems and contributing to uncertainty in our understanding of the net impact of dams to the global carbon budget. The 2011-2014 removal of two large dams on the Elwha River, Washington State, the largest dam removal yet completed globally, created extensive cutbank exposures of reservoir sediments, allowing the first characterization of the facies architecture of sediments through direct observation in reservoirs worldwide and providing an unparalleled opportunity to 1) assess the relationship between environmental influences, such as and changes in sediment supply, and their expression in the stratigraphic record, 2) assess the relationship between sedimentation processes and detrital organic carbon deposition and storage, and the importance of coarse-grained organic matter and woody debris to the total carbon budget of a reservoir, and 3) apply the insight gained from these reservoirs to evaluate current global estimates of carbon storage in reservoirs and develop a conceptual model of carbon burial in reservoirs to guide further research, as defined by characteristic stratigraphic “types”. Former Lake Mills, the younger, upstream reservoir, was characterized by a tripartite, subaerial Gilbert-style delta which prograded >1 km into the main reservoir from 1927 to 2011. Sediments were composed of coarse-grained topset beds, steeply dipping foreset beds, and a fine-grained, gently dipping prodelta. While individual event horizons were discernible in fine-grained sediments of former Lake Mills, their number and spacing did not correspond to known drawdown or flood events. Former Lake Aldwell, impounded from 1913 to 2011, was initially defined by the rapid progradation of a Gilbert-style, subaerial delta prior to the upstream completion of Glines Canyon Dam. However, the 1927 closure of Glines Canyon Dam upstream caused the delta to evolve to a fine-grained, mouth-bar type delta indicative of low, finer-grained sediment. This evolution, combined with a previously-unrecognized landslide deposit into the upper delta plain, suggests that understanding the exogenic influences on reservoir sedimentation is critical to interpretation and prediction of the sedimentation within individual systems. Former Lake Mills accumulated ~330 Gg of, with depositional-zone average accumulation rates from 229 to 9262 gCm -2 yr -1 , while Former Lake Aldwell accumulated ~ 91 Gg (263 to 2414 gCm -2 yr -1 ). Carbon storage in both reservoirs was dominated by heterogeneous, coarse organic matter and woody debris in the coarse-grained delta slope and relatively coarse-grained prodelta regions of the reservoirs, with little storage in the gravel-dominated, subaerial delta plains. Carbon accumulation in fine-grained lacustrine and prodelta sediments was relatively homogeneous, but turbidity flows from the Gilbert-style delta slope in former Lake Mills delivered significantly more carbon to the prodelta than the mouth-bar style delta of former Lake Aldwell. C:N ratios support interpretation of most organic matter in both reservoirs as allochthonous. Sampling schemes based only on lacustrine and/or prodelta would underestimate of total carbon accumulation by up to 30% in former Lake Aldwell, but the overestimate by up to 47% in former Lake Mills. Global estimates of carbon sequestration rates in reservoir sediments vary by three orders of magnitude, while individual-reservoir estimates vary by four orders of magnitude and over only 37 reservoirs and a literature review of predictive variables suggests weak or contradictory relationships. A conceptual stratigraphic framework of four unique reservoir types suggests that organic matter deposition is intrinsically tied to sedimentation processes and that patterns of carbon storage vary systematically with the stratigraphy of reservoir sediments. Deltaically-dominated reservoirs (whether Gilbert style or shoalwater) appear to store most carbon in their deltaic and prodelta regions, while thalweg-style reservoirs exhibit a bimodal distribution, with allochthonous carbon preferentially routed along the former river thalweg and autochthonous deposited on the former floodplain. Lacustrine-style reservoirs are dominated by suspended sediment deposition and thus relatively homogeneous, but literature suggests these reservoirs are more variable than typically measured. Current methods of reservoir sampling fail to account for this systematic variation and tend to be biased toward fine sediment, suggesting that global reservoir carbon storage is underestimated.

Stratton, Laurel↗
DOE OSTI2013

Used nuclear fuel separations process simulation and testing

Recent efforts in separations process simulation at Argonne have expanded from the traditional focus on solvent extraction flowsheet design in order to capture process dynamics and to simulate other components, processing and systems of a used nuclear fuel reprocessing plant. For example, the Argonne Model for Universal Solvent Extraction (AMUSE) code has been enhanced to make it both more portable and more readily extensible. Moving away from a spreadsheet environment makes the addition of new species and processes simpler for the expert user, which should enable more rapid implementation of chemical models that simulate evolving processes. The dyAMUSE (dynamic AMUSE) version allows the simulation of transient behavior across an extractor. Electrochemical separations have now been modeled using spreadsheet codes that simulate the electrochemical recycle of fast reactor fuel. The user can follow the evolution of the salt, products, and waste compositions in the electro-refiner, cathode processors, and drawdown as a function of fuel batches treated. To further expand capabilities in integrating multiple unit operations, a platform for linking mathematical models representing the different operations that comprise a reprocessing facility was adapted to enable systems-level analysis and optimization of facility functions. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Determination of Activity of Neodymium(III) in Molten Eutectic LiCl-KCl using Electrochemical Methods

The pyrochemical recycling of actinides is a promising option for closing the nuclear fuel cycle. The technology is particularly attractive for recycle of metallic and molten salt fuels. The Republic of Korea is also taking a serious look at the application of pyrochemical treatment of used oxide fuel from Pressurized Water Reactors (PWR). The science behind pyrochemical recycling is being actively studied at the various national labs and universities. The Rare Earth Drawdown process is proposed to be included in a commercial pyrochemical recycling facility in order to minimize the amount of waste generated from the processing that will require permanent disposal in a geological repository. This process involves selective extraction of rare earth elements from electro-refiner salt. The salt can then be further processed to selectively remove Group I-II active metals and eventually be recycled back to the electro-refiner. The preferred method of separation of the rare earths from the salt is using electrolysis due to its inherent selectivity and ease of operation. The purpose of this study is to evaluate the effects of the presence of cesium (Group I) on the electrochemical behavior of neodymium in a molten eutectic LiCl-KCl salt. The activity and by extension the activity coefficient of a species determines many of the key electrochemical properties such as apparent reduction potential. In this study, we have undertaken a series of experiments to experimentally determine the activity coefficient of the dissolved neodymium(III) ions as a function of concentration, both in the presence and absence of cesium. This was done using a first of its kind electrochemical cell. Previously, activity of dissolved species has been determined using electrochemical cells in which equilibrium potentials are measured for the Nd/Nd(III) versus a Ag/AgCl reference electrode. There are several issues associated with such an approach. These electrodes are associated with several sources of errors; indeterminate values of Standard Reduction Potentials of (E{sup θ}) for Ag and Nd in molten salts, unknown liquid junction potentials and potential drifts. These uncertainties contribute errors to the experimental measurements. For this study, we employed a Nd/LiCl-KCl-NdCl{sub 3(Saturatedelectrode)}. There are several advantages with using such an electrode. If the expanded Nernst Equation is written for the aforementioned electrochemical cell, all of the terms cancel out except the activity term. This enables us to directly experimentally measure the activity of the species in solution. When we use a saturated NdCl{sub 3} reference electrode, the activity that is measured is defined as the activity versus a 'Saturated Solid State'. To determine the activity coefficients, we need to determine the activity versus the 'Liquid Standard Sate'. To convert the activity from solid standard state to liquid standard state, we correct for it using the hypothetical Gibbs free energy of fusion for neodymium chloride. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2019

Path Forward for Groundwater Compliance Strategy at the Tuba City, Arizona, Disposal Site - 19581

The Tuba City, Arizona, Disposal Site is located in the Navajo Nation and near the Hopi Reservation. A uranium mill operated at the site from 1956 to 1966. During the operational period, mill tailings were slurried to an unlined impoundment. Excess slurry water was transferred to unlined evaporation ponds. Groundwater contamination resulting from the infiltration of fluids in the mill tailings impoundment and evaporation ponds was characterized in the 1990's. The site's Groundwater Compliance Action Plan was prepared in 1999, and a groundwater extraction and treatment system was constructed in 2002. Issues with aquifer productivity and treatment plant reliability led to the suspension of operations in 2014. The limitations of the remediation system prompted a realization that the site conceptual model should be reevaluated. An integrated study to better understand the geochemical and hydrologic factors affecting contaminant transport, to support the development of a new groundwater compliance strategy, was initiated in 2017 and is ongoing. In addition to the groundwater science components, the study included the evaluation of enhanced evaporation methods. The integrated evaluation will lead to refinement of the site groundwater flow model and development of a contaminant transport model and subsequent development of remedial alternatives. Remedial alternatives will be evaluated to determine a new groundwater compliance strategy. The objectives of geochemical testing were to confirm and quantify geochemical reactions controlling uranium fate and transport. These reactions are important because they control the distribution of uranium on the solid phase; potential for release from the solid phase; mobility of uranium in the water phase; and potential for uranium redistribution onto the currently uncontaminated solid phase. A key outcome is the change in understanding of the mass of uranium in the subsurface that is potentially soluble. These results contradict the previous basis for remediation: that uranium was almost exclusively present in soluble form, within the boundaries of the contaminant plume. Testing showed that uranium sorption downgradient from the plume was measurable but relatively minimal. The movement of other mill-related constituents (nitrate, sulfate, alkalinity) results in the dissolution of naturally occurring uranium and a higher than background concentration of uranium in groundwater. These constituents are not subject to sorption, and their downgradient concentrations are reduced only by diffusion and dispersion. The geochemical testing provides conceptual and quantitative information on potential plume migration. While the testing revealed the potential availability of uranium contaminant sources, the aquifer buffering capacity, pH, and presence of oxygen in groundwater may, individually or in combination, be controlling factors for plume movement. Evaluation of evaporative treatment alternatives was undertaken to determine one or more sustainable and efficient methods capable of treating 151 liters per minute (L/min) (40 gallons per minute), the annual average flow rate. In addition to establishing the baseline capacity for evaporation using the site's existing pond, prospective methods of enhanced evaporation included preheating water before inflow to the evaporation pond, vertical circulation in the pond, dye addition, and Wind-Aided Intensified Evaporation. Consideration of a 151 L/min evaporative treatment arose from previous analysis of extraction well production rates and contaminant mass removal, which indicated that about 80% contaminant removal, relative to full-scale operation of the site's groundwater treatment plant, could be achieved with a smaller capacity system. The lower-flow evaporative option also represented a potentially more sustainable treatment system in comparison to restarting or reconfiguring the groundwater treatment plant. Aquifer pumping tests were designed to develop or improve estimates of hydraulic properties such as transmissivity, horizontal and vertical hydraulic conductivity, storativity, and storage coefficient. Testing involved pumping from one well at a constant flow rate for up to 5 days while monitoring groundwater drawdown in the pumping well and five surrounding wells and then shutting down the pumping well to observe groundwater recovery. The aquifer pumping test results provide insight regarding the hydraulics of the saturated zone. The saturated zone is in a low-conductivity formation with preferential flow in the horizontal direction. The aquifer exhibits low vertical conductance. The use of AQTESOLV software indicates that the saturated zone is a layered system due to the cross-bedded sand-grain orientation within the Navajo Sandstone. These indicators of limited vertical flow provide a potential justification for the observed depth of the contaminant plume of 15-46 meters (50-150 feet) below ground surface). Given the relatively low vertical conductance, groundwater extraction should be focused on the upper portions of the saturated zone. Aquifer response testing provided an improved understanding of aquifer characteristics. However, the primary objective, to identify optimal groundwater extraction strategies, has not been fully addressed. A list of path forward activities for hydrologic analyses was developed, with an overarching objective of providing input parameters for groundwater flow and contaminant transport modeling. Defensible predictions of contaminant transport, through modeling, are critical to the development of a new site groundwater compliance strategy. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Evaluating the Feasibility of Using Strain Measured During Sinusoidal Rate Pumping Tests to Characterize an Aquifer

Pumping tests with sinusoidal variation in pumping rate have been proposed as a method for improving aquifer characterization. These tests can interrogate a larger aquifer volume than slug tests and they can be more sensitive to small variations in drawdown. Current methods of using sinusoidal variations of rate are based on measuring pressure signals from the reservoir or aquifer, which requires access to monitoring wells. An alternative approach has been developed that measures the strain in the vadose zone instead of pressure in the reservoir. An instrument has been developed at Clemson University that can measure small strains using optical fiber sensors, and we propose that it can be used to measure strain during sinusoidal pumping tests. The objective of this project is to evaluate the feasibility of measuring and interpreting the vertical strain in the vadose zone generated during a sinusoidal rate pumping tests to estimate aquifer and/or overburden properties. Pumping tests were performed at a site with a water table at 9 m and saturated saprolite from 9 to 30m depth. Sinusoidal pumping tests in the saprolite used different pumping amplitudes and periods while pressure was measured at three piezometers and vertical strain was measured in the vadose zone from 1 to 7 m depth. The delay time of the pressure increased linearly with distance, and it increased with the square root of the period, while the amplitude of the pressure decreased with distance and increased with amplitude. Vertical strain in the vadose zone varied with the same period as the pumping rate and the delay times were similar to those for pressures measured at similar radial distances. Delay times for the strain increased with an increasing propagation of the strain field. The hydraulic diffusivity was estimated using delay times for pressure and strain, and the results were compared with the values estimated from a constant-rate pumping test. The hydraulic diffusivity from the constant rate test was 0.039 m2/sec, whereas it was 0.053 (±0.05) m2/sec and 0.035 (±0.03) m2/sec from the pressure data and 0.08 (±0.022) m2/sec and 0.035 (±0.001) m2/sec from the strain data from sinusoidal tests of various periods and amplitudes. There is no statistical difference among these values. This study indicates that strain measurements in the vadose zone can be used to estimate aquifer properties during sinusoidal pumping tests.

Blais, Riley↗
DOE OSTI2024

Geothermal Reservoir Simulation Analysis in Support of Electricity Co-Production Feasibility Study at the Blackburn Oil Field, Nevada: Preprint

Geothermal electricity co-production is a viable option for oil reservoirs producing large water cuts with elevated wellhead-observed temperatures. Repurposing existing oil wells significantly reduces initial investment costs historically associated with geothermal resource utilization. The National Renewable Energy Laboratory (NREL), partnering with Gradient Geothermal, Inc. (formerly known as Transitional Energy) and Grant Canyon Oil and Gas, has been tasked to evaluate the feasibility of geothermal electricity co-production at the Blackburn Oil Field with Organic Rankine Cycle (ORC) generators. The Devonian steady-state reservoir has historically been producing high water cuts of 240 degrees F (115.6 degrees C) observed at the wellhead without documented pressure drawdown or thermal breakthrough. An estimated initial reservoir temperature of approx. 260degreesF (126.7 degrees C) has been observed in the field and history-matched in a wellbore production analysis and reservoir simulation. Our objective was to develop a conceptual geological model of the subsurface, simulate a natural-state reservoir, model production scenarios, and complete a technical feasibility analysis to accomplish this task. Through extensive modeling and the use of available proprietary and public data, it was possible simulate three scenarios that indicated minimal thermal decline over the duration of a simulated ten-year production and re-injection scheme.

Blackburn Nevada↗