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DOE OSTI2021

DOE Award No.: DE-FE0023919 Phase 4 Scientific/Technical Report

This is the Phase 4 Report for the ‘Deepwater Methane Hydrate Characterization and Scientific Assessment or Genesis of Methane Hydrates in the Gulf of Mexico (GOM2)’ research project (DOE Award No. DE-FE0023919). The report summarizes activities from October 1, 2019 to September 30, 2020. The project is led by the University of Texas at Austin (UT). The project objective is to gain insight into the nature, formation, occurrence and physical properties of methane hydrate-bearing sediments for the purpose of methane hydrate resource appraisal through the planning and execution of drilling, coring, logging, testing and analytical activities that assess the geologic occurrence, regional context, and characteristics of marine methane hydrate deposits in the Gulf of Mexico outer continental shelf (OCS). We published a dedicated American Association of Petroleum Geologists Bulletin volume describing initial results from the UT-GOM2-1 expedition in Sept. 2020. This is part 1 of a multi-volume commitment by AAPG to this project. We further confirmed that the natural gas in hydrate at GC-955 was formed by primary microbial processes (>76.1 %). The in-situ effective permeability hydrate-bearing sandy silts at the GC-955 reservoir ranges from 0.1 md (1.0×10-16 m2) to 2.4 md (2.4×10-15m2) in cores with 83% to 93% hydrate saturation. The intrinsic permeability (the single phase permeability) is estimated from reconstituted samples to be ~12 md (1.2×10-14 m2) to ~41 md (4.1×10-14 m2). We used observation and models to interpret that the core degradation that is found in pressure cores is due to dissociation of the methane hydrate in the outer circumference of the core and dissolution of that methane into the fresh pore water that the core is stored with. We are designing approaches to minimize this core loss in the future. We spent an enormous amount of effort to further improve the ability of the pressure coring tool (the PCTB) to pressure seal correctly. We completed upgrading the upper section of the PCTB to address poor pressure. We successful tested the modifications at Geotek’s test facility in Salt Lake City (Bench Test II). We completed a Land Test of the PCTB at the Schlumberger Cameron Test and Training Facility (CTTF). The tool did not seal in 6 out of 7 tests and we clearly demonstrated that cuttings were wedging in the ball valve assembly, keeping the ball valve from sealing. We reproduced the failure mechanism observed during the land test at Salt Lake City and confirmed the sensitivity of the ball valve assembly to grit. Geotek designed and tested 9 modifications to address this issue and the PCTB is now 100% successfully sealing in the presence of grit. Our science expedition is scheduled for spring 2022 and we are fully focused on preparing for this. UT and Ohio State completed a Shallow Hazard Assessment report for each proposed UT-GOM2-2 drilling location, pursuant to 30 CFR 250.214(f) and 250.244 (f). The Shallow Hazard Reports will accompany the UT-GOM2-2 Exploration Plan that is submitted to BOEM, and completes the geological and geophysical analysis for UT-GOM2-2 permitting efforts. We updated the UT-GOM2-2 Operations Plan (Version 1). We completed the UT-GOM2-2 Science and Sample Distribution Plan (Version 1). We evaluated the scope, budget, and schedule that would result from using a commercial vessel. We developed detailed drilling schedule, mud volume, and resource estimates. We developed a vessel specification document and a well plan, and sent these documents to prospective vessel contractors.

03 NATURAL GAS↗

DOE OSTI2022

Reduced diffusion and enhanced retention of multiple radionuclides from pore structure characterization of barrier materials for enhanced repository performance

Fluid flow and chemical transport in porous media are the macroscopic consequences of pore structure, which integrates geometry (e.g., pore size and surface area, pore-size distribution) and topology (e.g., pore connectivity). Low-permeability geological media whose pores are poorly interconnected will exhibit the characteristics of anomalous diffusion and sample size-dependent effective porosity, which will strongly impact long-term net diffusion and retention of radionuclides in geological repository settings involving different host rocks and barrier materials. A suite of innovative and complementary experimental approaches is utilized to study the microscopic pore structure and macroscopic fluid flow & chemical transport for a range of host rocks and barrier materials, in addition to standard clay minerals and reference rocks. With a particular focus on quantifying the presence and magnitude of “isolated” pores for a reduced effective porosity in low-permeability geomedia, the integrated methodologies for basic properties and pore structure characterization of these geomedia include X-ray diffraction, thin section petrography, grain size distribution, water immersion porosimetry after vacuum-pulling for full saturation, mercury intrusion porosimetry, nitrogen physisorption, scanning electron microscopy, X-ray computed tomography, and (ultra-)small angle neutron (X-ray) scattering. In addition, custom-designed gas diffusion, tracer recipe involving a range of anionic and cationic chemicals with subsequent analyses by laser ablation and inductively coupled plasma-mass spectrometry, along with batch sorption, column transport, and imbibition tests were conducted for coupled effects of pore structure and chemical retention/transport. From the perspectives of pore structure in conjunction with multiple and complementary approaches to examining a range of sample sizes under different observational scales, we find that the poor pore connectivity is prevalent in low-permeability media (mudstone and crystalline rock) that is related to geological processes (e.g., compaction, diagenesis and thermal maturation). For example, the deep and organic matter-rich mudstones have a much smaller effective porosity than the total porosity (as a result of poor pore connectivity) and associated diffusion coefficient, and the effective porosity & diffusion coefficients are also dependent upon the sample sizes used in the measurement. Similarly, most of the pore space in the shallow mudstone is also controlled by pore-throat diameters in the 5-50 nm range of intergranular pore types from its fine-grained nature, but with an overall good pore connectivity. However, the nm-sized pore space (physically pore-network architecture) and strong sorption capacities (chemical retention from clay minerals) of both shallow and deep mudstones lead to the synergistic retention of cationic radionuclides and their utilities as effective host rocks and barrier materials. Our unique approaches of studying how the micro-scale pore structure affect macro-scale fluid flow, diffusion & retention, and chemical transport produce improved mechanistic understanding, and realistic quantification, of diffusion and retention of typical radionuclides in a range of generic host rocks and barrier materials (clay/shale, salt, crystalline rock, and tuff), with the overall results leading to scientifically-based understanding of enhanced isolation (from both diffusion and retention) of radionuclides and improved confidence on the long-term performance of geological repository to store high-level radioactive wastes. In addition to the training of 25 undergraduates, graduates, and postdocs of UTA, the scientists (organizations) involved in performing this work (e.g., discussion, sample sharing, and operation of SANS and SAXS instruments) include Ed Matteo, Yifeng Wang, and Kristopher Kuhlman (Sandia National Laboratories), Jens Birkholzer, Liange Zheng, Tim Kneafsey, and Sharon Borglin (Lawrence Berkeley National Laboratory), Mavrik Zavarin (Lawrence Livermore National Laboratory), Yukio Tachi and Yuta Fukatsu (Japan Atomic Energy Agency), Mieke de Craen (Euridice, Belgium), Markus Bleuel (NIST), Wei-Ren Chen, Gergely Nagy, Changwoo Do, William Heller, Larry Anovitz, and Kenneth Littrell (ORNL), as well as Jan Illvsky, Ivan Kuzmenko, Ju-Sang Park and Jon Almers (ANL). Key deliverables include a total of 13 peer-reviewed journal articles (nine published and three under review), 23 presentations at scientific conferences (AAPG, AAPG Southwest Section, AGU, Asian Clay Conference, GSA, GSA South-Central Section, IHLRWM, InterPore, International Conference on Chemistry and Migration Behavior of Actinides and Fission Products in the Geosphere, International Conference on Coupled Processes in Fractured Geological Media: Observation, Modeling and Application), and academic institutions (UTA, New Mexico State University; University of Poitiers, France; University of Helsinki, Finland; Uppsala University, Sweden; Istanbul Technical University, Turkey) and other organizations (Andra, France; Posiva Oy, Finland).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Mechanical suppression of invasive Northern Pike in Box Canyon Reservoir, Washington

Abstract Objective Northern Pike Esox lucius recently invaded Box Canyon Reservoir, Washington, expanding to over 10,000 individuals by 2011. To limit further impacts, a significant reduction in population abundance was required. Project objectives were to reduce relative abundance (catch per unit effort [CPUE]) to less than 1.7 Northern Pike/net (87% reduction) in the core area and to less than 0.5 Northern Pike/net in the northern reservoir section within 3 years and then maintain those abundance targets thereafter. Methods Using gill nets, we conducted intensive annual (2012–2018) suppression each spring, focusing on spawning aggregations in shallow (<2-m), flooded habitats. To evaluate CPUE, a standardized spring pike index netting (SPIN) survey was conducted annually in May and compared to suppression netting CPUE. Result In total, 17,464 Northern Pike were removed in 4868 net sets, with 92.9% captured in the first 3 years, limiting future recruitment. Mean SPIN CPUE in the core area declined from a presuppression (2011) high of 13.2 Northern Pike/net to less than 1.0 Northern Pike/net by 2014. Effort was reduced by up to 80% as the project transitioned from the initial suppression phase (2012–2014) to a control phase (2015–2018), which explored the minimum effort required to maintain abundance targets. A significant rebound in CPUE occurred from 2017 to 2018, indicating that over 267 net sets annually may be required for long-term control. Although the mean CPUE (±95% confidence interval) increased slightly in 2018 (0.6 ± 0.5 Northern Pike/net), the target abundance in the core area was achieved annually from 2013 to 2018. Changes in suppression CPUE reflected those observed in SPIN surveys, further validating the survey and corroborating abundance trends. Conclusion Results demonstrate that the suppression of Northern Pike in large, complex waters is feasible but requires a substantial long-term commitment. We expect the suppression of this invasive species to become standard practice outside of its native range. The methodology and equipment described here could be applied directly or modified by others to suppress Northern Pike.

Bean, Nicholas J.↗

NASA NTRS2022

An Evaluation of the Liquid Cloud Droplet Effective Radius Derived from MODIS, Airborne Remote Sensing, and in Situ Measurements from CAMP2Ex

The cloud drop effective radius (Re) of the drop size distribution derived from passive satellite sensors is a key variable used in climate research. Validation of these satellite products has often taken place under stratiform cloud conditions that favor the assumption of cloud horizontal homogeneity used by the retrieval techniques. However, many studies have noted concerns with respect to significant biases in retrieved Re arising from cloud heterogeneity, for example, in cumulus cloud fields. Here, we examine data collected during the 2019 “Cloud, Aerosol and Monsoon Processes Philippines Experiment” (CAMP2Ex), which, in part, targeted the objective of providing the first detailed evaluation of Re retrieved across multiple platforms and techniques in a cumulus and congestus cloud region. Our evaluation consists of cross-comparisons of Re between the Moderate Resolution Imaging Spectroradiometer (MODIS) onboard the Terra satellite, the Research Scanning Polarimeter (RSP) onboard the NASA P-3 aircraft, and in situ measurements from both the NASA P-3 and Learjet aircraft that are all taken in close spatiotemporal proximity to the same cloud fields. A particular advantage of our approach lies in the capability of the RSP to retrieve Re using a bi-spectral MODIS approach and a polarimetric approach, which allows for the evaluation of bi-spectral and polarimetric Re retrievals from an airborne perspective using the same samples. Averaged over all P-3 flight segments examined here for warm clouds, the RSP polarimetric method, the in situ method, and the bias-adjusted MODIS method of Fu et al. (2019) show a comparable median (mean ± standard deviation) for the Re samples of 9.6 (10.2 ± 4.0) µm, 11.0 (13.6 ± 11.3) µm, and 10.4 (10.8 ± 3.8) µm, respectively. These values are far lower than the values of 15.1 (16.2 ± 5.5) µm and 17.2 (17.7 ± 5.7) µm from the bi-spectral retrievals of RSP and MODIS, respectively. Similar results are observed when Re is segregated by cloud-top height and in detailed case studies. The clouds sampled during CAMP2Ex consist of mostly small (mean transect length ∼ 1.4 km) and low clouds (mean cloud-top height ∼ 1 km), which had more numerous small clouds than the trade wind cumuli sampled in past field campaigns such as Rain in Shallow Cumulus over the Ocean (RICO) and the Indian Ocean Experiment (INDOEX). The overestimates of Re from the RSP bi-spectral technique compared with the polarimetric technique increased as cloud size and cloud optical depth decreased. Drizzle, cloud-top bumpiness, and solar zenith angle, however, are not closely correlated with the overestimate of bi-spectral Re. For shallow clouds that dominated the liquid cloud cover for the CAMP2Ex region and period, we show that 3-D radiative transfer and cloud heterogeneity, particularly for the optically thin and small clouds, appear to be the leading cause of the large positive biases in bi-spectral retrievals. Because this bias varies with the underlying structure of the cloud field, caution continues to be warranted in studies that use bi-spectral Re retrievals in cumulus cloud fields.

Cloud microphysics↗

DOE OSTI2026

Mesoscale Organization in Cumulus-Coupled Stratocumulus

Marine cloud systems cover a substantial portion of the world’s oceans. Most of these clouds form relatively close to the ocean surface, typically within one to two kilometers, a region referred to by meteorologists as the marine boundary layer. They are composed predominantly of liquid water, although ice particles can occur in mid- and high-latitude marine clouds during winter. In satellite imagery, these clouds appear bright against the darker ocean surface below, reflecting a large fraction of incoming sunlight back into space that would otherwise warm the ocean. Because marine boundary layer clouds cover such an extensive area of the ocean, they exert a significant influence on Earth’s overall transfer of solar energy absorbed by the surface and thermal energy emitted to space, a balance known as the planetary radiation budget. Marine boundary layer clouds are typically thin, and their formation and dissipation depend on a delicate balance between processes acting at the ocean surface below and the warm, dry air above. They are notoriously difficult to simulate accurately in weather forecast models, which often produce too few marine low clouds in midlatitudes and clouds in tropical regions that are excessively bright, meaning they reflect too much solar radiation. The marine boundary layer is frequently characterized by widespread overcast cloud cover that often transitions from a continuous, single-layer deck to more broken cloud fields toward the tropics. These transitions typically proceed through an intermediate stage in which shallow, broken clouds form beneath the overlying stratiform cloud deck. Once broken clouds develop below the overcast, they frequently self-organize into cloud clusters known as marine boundary layer convective complexes (MBLCCs), although the mechanisms governing the formation and organization of MBLCCs remain poorly understood. Accurately representing these transitions in long-range weather forecast models is essential because they influence the properties of air masses advected over the continental United States and Europe, and they become increasingly important for forecasts on seasonal and longer timescales. We employed two complementary approaches to investigate the processes controlling MBLCCs and their impact on marine cloud cover. Long-term observations from the U.S. Department of Energy’s Eastern North Atlantic (ENA) Observatory provided a unique dataset that allowed us to characterize fundamental properties of MBLCCs, including their typical size and frequency of occurrence. These observations were combined with high-resolution numerical simulations performed on supercomputers to examine the evolution of MBLCCs during cold-air outbreaks over the ENA region.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Electronic structure modulation of MoS2 by substitutional Se incorporation and interfacial MoO3 hybridization: Implications of Fermi engineering for electrocatalytic hydrogen evolution and oxygen evolution

The design of earth-abundant electrocatalysts that can facilitate water splitting at low overpotentials, provide high current densities, and enable prolonged operational lifetimes is central to the production of sustainable fuels. The distinctive atomistic and electronic structure characteristics of the edges of MoS2 imbue high reactivity toward the hydrogen evolution reaction. MoS2 is nevertheless characterized by significantly high overpotentials as compared to platinum. Here, we demonstrate that modulation of the electronic structure of MoS2 through interfacial hybridization with MoO3 and alloying of selenium on the anion sublattice allows for systematic lowering of the conduction band edge and raising of the valence band edge, respectively. The former promotes enhanced electrocatalytic activity toward hydrogen evolution, whereas the latter promotes enhanced activity toward the oxygen evolution reaction. Such alloyed heterostructures prepared by sol-gel reactions and hydrothermal selenization expose a high density of edge sites. The alloyed heterostructures exhibit low overpotential, high current density, high turnover frequency, and prolonged operational lifetime. The mechanistic origins of catalytic activity have been established based on electronic structure calculations and x-ray absorption and emission spectroscopy probes of electronic structure, which suggest that interfacial hybridization at the MoO3 interface yields low-lying conduction band states that facilitate hydrogen adsorption. In contrast, shallow Se 4p-derived states give rise to a raised effective valence band maximum, which facilitates adsorption of oxygen intermediates and engenders a low overpotential for the oxygen evolution reaction. The findings illustrate the use of electronic structure modulation through interfacial hybridization and alloying to systematically improve electrocatalytic activity.

Parija, Abhishek↗

NASA NTRS2000

Mineralogical and Geochemical Analyses of Antarctic Lake Sediments: A Reflectance and Moessbauer Spectroscopy Study with Applications for Remote Sensing on Mars

Lakebottom sediments from the Dry Valleys region of Antarctica have been analyzed here in order to study the influence of water chemistry on the mineralogy and geochemistry of these sediments, as well as to evaluate techniques for remote spectral identification of potential biomarker minerals on Mars. Lakes from the Dry Valleys region of Antarctica have been investigated as possible analogs for extinct lake environments on early Mars. Sediment cores were collected in the present study from perennially ice-covered Lake Hoare in the Taylor Valley. These sediments were taken from a core in an oxic region of the lake and another core in an anoxic zone. Differences between the two cores were observed in the sediment color, Fe(II)/Fe(III) ratio, the presence of pyrite, the abundance of Fe, S and some trace elements, and the C, N and S isotope fractionation patterns. The results of visible-infrared reflectance spectroscopy (0.3-25 microns) Mossbauer spectroscopy (77 and 4 K) and X-ray diffraction are combined to determine the mineralogy and composition of these samples. The sediments are dominated by plagioclase, K-feldspar, quartz and pyroxene. Algal mats grow on the bottom of the lake and organic material has been found throughout the cores. Calcite is abundant in some layers of the aerobic core (shallow region) and pyrite is abundant in some layers of the anaerobic core (deep region). Analysis of the spectroscopic features due to organics and carbonates with respect to the abundance of organic C and carbonate contents was performed in order to select optimal spectral bands for remote identification of these components in planetary regoliths. Carbonate bands near 4 and 6.8 microns (approx.2500 and 1500/cm) were detected for carbonate abundances as low as 0.1 wt.% CO2. Organic features at 3.38, 3.42 and 3.51 microns (2960, 2925 and 2850/cm) were detected for organic C abundances as low as 0.06 wt.% C. The d13C trends show a more complex organic history for the anaerobic sediments than for the aerobic sediments. The biogenic pyrite found in the anaerobic core is associated with lighter d34S values and high organic C levels and could be used as a biomarker mineral for paleolakes on Mars.

Froeschl, Heinz↗

DOE OSTI2020

Borehole Disposal of Radioactive Waste in Israel - 20388

Israel is assessing borehole disposal of radioactive waste. With limited geological options for disposal, intermediate-depth borehole disposal is being considered in the arid Yamin Plain region of the northeastern Negev desert at depths of several hundred meters below ground surface in the vadose zone. Unlike deep borehole disposal of several kilometers, which relies on emplacement below the depth of recirculating groundwater, the safety case for intermediate-depth borehole disposal relies more on the aridity of the vadose zone, the robustness of the waste package, and the other engineered barriers (e.g., seals, backfill materials) in the disposal borehole. As a tradeoff, the shallower depth may allow the use of a larger diameter borehole than would be possible for a deeper borehole. To study the suitability of the Yamin Plain region for borehole disposal, a small-diameter characterization borehole is being planned to retrieve core samples and to better understand the vadose zone geomechanical and hydrogeochemical properties and percolation flux. The information from the characterization borehole will inform the safety case, and together with performance assessment analyses will help to identify key areas of uncertainty and guide future research and development activities aimed at demonstrating the feasibility of the intermediate-depth borehole disposal concept in Israel. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1997

Exploring for Martian Life

Terrestrial life appears to have arisen very quickly during late accretion, sometime between approximately 3.5 and 4.2 Ga. During this same time, liquid water appears to have been abundant at the surface of Mars and it is quite plausable that life originated there as well. We now believe that the last common ancestor of terrestrial life was a sulfur-metabolizing microbe that lived at high temperatures. Rooting of the RNA tree in thermophily probably reflects high temperature "bottle-necking" of the biosphere by giant impacts during late accretion, sometime after life had originated. If high temperature bottle-necking is a general property of early biosphere development, Martian life may have also developed in close association with hydrothermal systems. Several independent lines of evidence suggest that hydrothermal processes have played an important role during the geological history of Mars. Because hydrothermal deposits on Earth are known to capture and retain abundant microbial fossil information, they are considered prime targets in the search for an ancient Martian biosphere. An important step in planning for future landed missions to Mars is the selection of priority targets for high resolution orbital mapping. Geotectonic terranes on Mars that provide a present focus for ongoing site selection studies include channels located along the margins of impact crater melt sheets, or on the slopes of ancient Martian volcanoes, chaotic and fretted terranes where shallow subsurface heat sources are thought to have interacted with ground ice, and the floors of calderas and rifted basins. Orbital missions in 1996, 1998 and 2001 will provide opportunities for high resolution geological mapping at key sites in such terranes, as a basis for selecting targets for future landed missions for exopaleontology.

Farmer, Jack D.↗

DOE OSTI2021

The Epoch of Giant Planet Migration Planet Search Program. I. Near-infrared Radial Velocity Jitter of Young Sun-like Stars

We present early results from the Epoch of Giant Planet Migration program, a precise radial velocity (RV) survey of more than 100 intermediate-age (∼20–200 Myr) G and K dwarfs with the Habitable Zone Planet Finder spectrograph (HPF) at McDonald Observatory’s Hobby–Eberly Telescope. The goals of this program are to determine the timescale and dominant physical mechanism of giant planet migration interior to the water ice line of Sun-like stars. Here, we summarize results from the first 14 months of this program, with a focus on our custom RV pipeline for HPF, a measurement of the intrinsic near-infrared RV activity of young Solar analogs, and modeling the underlying population-level distribution of stellar jitter. We demonstrate on-sky stability at the sub-2 m s{sup −1} level for the K2 standard HD 3765 using a least-squares matching method to extract precise RVs. Based on a subsample of 29 stars with at least three RV measurements from our program, we find a median rms level of 34 m s{sup −1}. This is nearly a factor of 2 lower than the median rms level in the optical of 60 m s{sup −1} for a comparison sample with similar ages and spectral types as our targets. The observed near-infrared jitter measurements for this subsample are well reproduced with a log-normal parent distribution with μ = 4.15 and σ = 1.02. Finally, by compiling rms values from previous planet search programs, we show that near-infrared jitter for G and K dwarfs generally decays with age in a similar fashion to optical wavelengths, albeit with a shallower slope and lower overall values for ages ≲1 Gyr.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2025

Flower‐Type Organized Trade‐Wind Cumulus: A Multi‐Day Lagrangian Large Eddy Simulation Intercomparison Study

Shallow cumulus cloud fields in subtropical marine trade wind environments, particularly over the tropical Atlantic Ocean, show distinct organizational patterns. Among these, Flower‐type clouds are characterized by expansive stratiform cloud patches surrounded by regions of scattered convection. The objectives of this study were (a) to construct a case study of a time period during the EUREC 4 A/ATOMIC field campaign when Flower‐type organization was observed, (b) to evaluate the fidelity of a multi‐model ensemble of large eddy simulations of that case, and (c) to analyze the interaction between cloud and precipitation processes and mesoscale organization in the simulations. The simulations follow a quasi‐Lagrangian trajectory, allowing mesoscale features to develop over time in a domain that follows the boundary‐layer airmass. The results show a broad agreement in simulated thermodynamic properties across different LES codes, with Flower‐type cloud patches appearing within hours of each other. The consensus among models is consistent with observations made during the EUREC 4 A/ATOMIC field campaign on the specific day of interest. The cloud structure reveals three distinct peaks in the joint probability densities of cloud base and cloud top height, with the dominant peak at any given time influenced by the stage of cloud organization. The simulated cloud system evolution reveals consistent occurrence of maxima in liquid water path and rain rate before Flower reaches its maximum length scale. Targeted sensitivity tests reveal a weak relationship between Cloud Droplet Number concentration and the extent/degree/type of organization.

EUREC4A↗

DOE OSTI2022

From legacy contamination to watershed systems science: a review of scientific insights and technologies developed through DOE-supported research in water and energy security

Abstract Water resources, including groundwater and prominent rivers worldwide, are under duress because of excessive contaminant and nutrient loads. To help mitigate this problem, the United States Department of Energy (DOE) has supported research since the late 1980s to improve our fundamental knowledge of processes that could be used to help clean up challenging subsurface problems. Problems of interest have included subsurface radioactive waste, heavy metals, and metalloids (e.g. uranium, mercury, arsenic). Research efforts have provided insights into detailed groundwater biogeochemical process coupling and the resulting geochemical exports of metals and nutrients to surrounding environments. Recently, an increased focus has been placed on constraining the exchanges and fates of carbon and nitrogen within and across bedrock to canopy compartments of a watershed and in river–floodplain settings, because of their important role in driving biogeochemical interactions with contaminants and the potential of increased fluxes under changing precipitation regimes, including extreme events. While reviewing the extensive research that has been conducted at DOE’s representative sites and testbeds (such as the Oyster Site in Virginia, Savannah River Site in South Carolina, Oak Ridge Reservation in Tennessee, Hanford in Washington, Nevada National Security Site in Nevada, Riverton in Wyoming, and Rifle and East River in Colorado), this review paper explores the nature and distribution of contaminants in the surface and shallow subsurface (i.e. the critical zone) and their interactions with carbon and nitrogen dynamics. We also describe state-of-the-art, scale-aware characterization approaches and models developed to predict contaminant fate and transport. The models take advantage of DOE leadership-class high-performance computers and are beginning to incorporate artificial intelligence approaches to tackle the extreme diversity of hydro-biogeochemical processes and measurements. Recognizing that the insights and capability developments are potentially transferable to many other sites, we also explore the scientific implications of these advances and recommend future research directions.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2012

High-Speed Transport of Fluid Drops and Solid Particles via Surface Acoustic Waves

A compact sampling tool mechanism that can operate at various temperatures, and transport and sieve particle sizes of powdered cuttings and soil grains with no moving parts, has been created using traveling surface acoustic waves (SAWs) that are emitted by an inter-digital transducer (IDT). The generated waves are driven at about 10 MHz, and it causes powder to move towards the IDT at high speed with different speeds for different sizes of particles, which enables these particles to be sieved. This design is based on the use of SAWs and their propelling effect on powder particles and fluids along the path of the waves. Generally, SAWs are elastic waves propagating in a shallow layer of about one wavelength beneath the surface of a solid substrate. To generate SAWs, a piezoelectric plate is used that is made of LiNbO3 crystal cut along the x-axis with rotation of 127.8 along the y-axis. On this plate are printed pairs of fingerlike electrodes in the form of a grating that are activated by subjecting the gap between the electrodes to electric field. This configuration of a surface wave transmitter is called IDT. The IDT that was used consists of 20 pairs of fingers with 0.4-mm spacing, a total length of 12.5 mm. The surface wave is produced by the nature of piezoelectric material to contract or expand when subjected to an electric field. Driving the IDT to generate wave at high amplitudes provides an actuation mechanism where the surface particles move elliptically, pulling powder particles on the surface toward the wavesource and pushing liquids in the opposite direction. This behavior allows the innovation to separate large particles and fluids that are mixed. Fluids are removed at speed (7.5 to 15 cm/s), enabling this innovation of acting as a bladeless wiper for raindrops. For the windshield design, the electrodes could be made transparent so that they do not disturb the driver or pilot. Multiple IDTs can be synchronized to transport water or powder over larger distances. To demonstrate the transporting action, a video camera was used to record the movement. The speed of particles was measured from the video images.

Bar-Cohen, Yoseph↗

DOE OSTI2023

Subsurface Characterization for Evaluating Geothermal Resource Potential from Existing Oil and Gas Wells in Tuttle, Oklahoma: Preprint

Oil and gas (O&G) wells often encounter co-produced hot water, possibly suitable for geothermal direct-use applications. The City of Tuttle is located on the eastern part of the Anadarko sedimentary basin in Oklahoma with high heat-in-place potential and recovery capability at depth. This study aims at demonstrating the potential of geothermal energy production for direct-use applications in two public schools and 250 nearby houses in Tuttle via repurposing existing O&G wells. In this scope, geochemistry, geology, and borehole log data were collected and incorporated into a 3D conceptual subsurface model. A digital elevation model (DEM) was used to represent the study area topography with four O&G wells. In addition, hydrogeochemical characteristics of the geothermal fluid and scaling potential were analyzed using ternary diagrams and chemical ratios to develop mixing models. The subsurface geology model indicated that the study area primarily consists of Permian to Mississippian Sandstone and Limestone formations, implying a porosity ranging between 12% and 22%, and a permeability up to 3.90E-14 m2 in certain reservoir levels. The reservoir temperature is expected to be ranging between 80 degrees C to 95 degrees C around 3 km depth with an average temperature gradient of 22.8 degrees C/km. Chemical geothermometers also estimated the reservoir temperature as 90 degrees C. Findings of the chemical model demonstrated that the geothermal fluid is Sodium-Potassium-Chloride-Sulfate type and possibly mixed with shallow groundwater resulting in higher Ca and Mg concentrations and lower Na/K ratio implying lower calcite scaling. These results comprehensively characterize the potential of geothermal resources in the study area and imply that geothermal energy production by repurposing existing O&G wells is suitable for low-temperature direct-use applications.

GEOTHERMAL ENERGY↗

DOE OSTI2023

Subsurface Characterization for Evaluating Geothermal Resource Potential from Existing Oil and Gas Wells in Tuttle, Oklahoma

gas wells↗

NASA NTRS2015

Key Recent Scientific Results from the Opportunity Rover's Exploration of Endeavour Crater, Mars

The Opportunity Rover is currently in its 11th year of operations, exploring the rim of the approximately 22 km wide Noachian-age Endeavour Crater. Opportunity spent its 5th winter season in Cook Haven, a gentle swale along Murray Ridge. Two small rocks serendipitously overturned by rover wheel motions show evidence for aqueous precipitation of sulfates, and interaction with a strong oxidant (e.g., O2) to form a thin, high valence state Mn oxide coating. After the winter, Opportunity headed south to Cape Tribulation and explored Shoemaker formation impact breccias, finding numerous Ca-sulfate veins cutting across outcrops. A key target for Opportunity's measurements has been the Spirit of Saint Louis crater (SoSL), which is approximately 25 m wide, oval in plan view, shallow, flat-floored, and has a slightly raised rim. SoSL crater is surrounded by an apron of bright, polygonally-shaped outcrops and is superimposed on a gentle swale in Cape Tribulation. Rocks in a thin reddish zone on the rim are enriched in hematite, Si, and Ge, and depleted in Fe, relative to surrounding rocks. Apron rocks include an outcrop also enriched in Si and Ge, and slightly depleted in Fe. In general rocks in the crater and apron have elevated S relative to Shoemaker formation breccias, tracking values observed in the Cook Haven and the Hueytown (fracture running perpendicular to Cape Tribulation) outcrops. SoSL crater lies just to the west of Marathon Valley, a key target for exploration by Opportunity because five separate CRISM observations indicate the presence of Fe/Mg smectites on the upper valley floor. Opportunity data show that low relief, relatively bright polygonal outcrops dominate the valley floor where not covered by scree and soil shed from surrounding walls. Initial reconnaissance shows that the outcrops are breccias with compositions similar to the typical SoSL crater apron and floor rocks, although only the very upper portion of the valley has been explored as of August 2015. Pervasive but modest aqueous alteration of Endeavour's rim is implied by the combination of CRISM and Opportunity data, providing insight into early aqueous processes dominated in this location by relatively low water to rock ratios, and at least in part associated with enhanced fluid flow along fractures.

Arvidson, R. E.↗

NASA NTRS2013

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope aud Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41º32'N, 120º5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4 2-, respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 oC, and higher than the values measured at orifices (77.3 to 90.0 oC). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The 13C fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 oC) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

NASA NTRS2013

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope and Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41 deg 32'N, 120 deg 5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4(2-), respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 C, and higher than the values measured at orifices (77.3 to 90.0 C). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The C-13 fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 C) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗