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DOE OSTI2020

Efficient 3-D velocity model building using joint inline and crossline plane-wave wave-equation migration velocity analyses

SUMMARY Wave-equation migration velocity analysis (WEMVA) is an image-domain inversion method for velocity model building. Automatic plane-wave WEMVA (PWEMVA) calculates the moveouts of plane-wave common-image gathers (CIGs) by searching a best-fitting parabola with semblance analysis and backprojects residual CIG moveouts into wavefield wave paths with a reflection tomographic kernel. However, 3-D PWEMVA is very computationally expensive because 3-D reflection tomographic inversion requires at least five 3-D reverse-time migrations per iteration and stores two types of source wavefields at model boundaries. We develop a joint inline and crossline PWEMVA method for efficient 3-D velocity model building. We alternatively implement the inline and crossline PWEMVAs with a constraint for each other, in which we iteratively construct the 3-D velocity model update through 1-D spline interpolation of 2-D gradients. The inline and crossline joint inversion is practical since PWEMVA only inverts for low-wavenumber velocity perturbations along wave paths, and the method can take less than 1 per cent of the computational cost of full 3-D PWEMVA. To construct unaliased plane waves for our joint inline and crossline PWEMVA, we develop a 3-D data interpolation method in the frequency–wavenumber (FK) domain to recover regularly and randomly missing traces. The method minimizes the misfit on sufficiently localized data subsets with iterative optimal step lengths and a gradient preconditioner that iteratively selects dominant dips along different azimuths. In numerical experiments, we use a 3-D synthetic seismic data set and a land 3-D field seismic data set acquired at the Farnsworth CO2-EOR (enhanced oil recovery) field to demonstrate the efficacy of our velocity model building and data interpolation methods.

Liu, Xuejian↗

DOE OSTI2022

Single-column cryogenic air separation: enabling efficient oxygen production with rapid startup and low capital costs—application to low-carbon fossil-fuel plants

The rapid integration of intermittent renewable sources into the electricity grid is driving the need for more flexible, low-carbon fossil-fuel plants with lower capital costs. This then drives the need to improve the cryogenic air separation unit (ASU). To address this changing landscape, we explore a Praxair single-column ASU (PSC-ASU) design with the goal of reducing costs and improving flexibility, compared to a conventional double-column ASU. The PSC-ASU incorporates partial air condensation and air pre-separation in the bottom reboiler with a phase separator as well as N2-enriched vapor condensation in the upper reboiler to decrease energy consumption, as compared to Linde's single-column ASU. All three of the above-mentioned ASU designs are simulated in Aspen Plus and analyzed. An economic analysis is applied to evaluate the relative cost savings of the PSC-ASU compared to the double-column ASU. Results suggest that the specific energy consumption of the PSC-ASU is significantly lower than that of Linde's single-column ASU due to a drastically improved oxygen recovery rate. Although this improved oxygen recovery rate is still lower than that of the double-column ASU, the required pressure ratio of the main air compressor is 21% lower than that of the double-column ASU. As a result, the specific energy consumption of the PSC-ASU is only 1.9% greater than that of the double-column ASU for producing 95.1 mol% O2. However, the PSC-ASU reduces the hourly capital cost by 19% due to the elimination of a high-pressure column. This would effectively decrease the total hourly cost of the ASU, and thus the total hourly cost of low-carbon, fossil-fuel power plants that require oxygen.

Cheng, Mao↗

NASA NTRS2006

Thermal Band Atmospheric Correction Using Atmospheric Profiles Derived from Global Positioning System Radio Occultation and the Atmospheric Infrared Sounder

This Rapid Prototyping Capability study explores the potential to use atmospheric profiles derived from GPS (Global Positioning System) radio occultation measurements and by AIRS (Atmospheric Infrared Sounder) onboard the Aqua satellite to improve surface temperature retrieval from remotely sensed thermal imagery. This study demonstrates an example of a cross-cutting decision support technology whereby NASA data or models are shown to improve a wide number of observation systems or models. The ability to use one data source to improve others will be critical to the GEOSS (Global Earth Observation System of Systems) where a large number of potentially useful systems will require auxiliary datasets as input for decision support. Atmospheric correction of thermal imagery decouples TOA radiance and separates surface emission from atmospheric emission and absorption. Surface temperature can then be estimated from the surface emission with knowledge of its emissivity. Traditionally, radiosonde sounders or atmospheric models based on radiosonde sounders, such as the NOAA (National Oceanic & Atmospheric Administration) ARL (Air Resources Laboratory) READY (Real-time Environmental Application and Display sYstem), provide the atmospheric profiles required to perform atmospheric correction. Unfortunately, these types of data are too spatially sparse and too infrequently taken. The advent of high accuracy, global coverage, atmospheric data using GPS radio occultation and AIRS may provide a new avenue for filling data input gaps. In this study, AIRS and GPS radio occultation derived atmospheric profiles from the German Aerospace Center CHAMP (CHAllenging Minisatellite Payload), the Argentinean Commission on Space Activities SAC-C (Satellite de Aplicaciones Cientificas-C), and the pair of NASA GRACE (Gravity Recovery and Climate Experiment) satellites are used as input data in atmospheric radiative transport modeling based on the MODTRAN (MODerate resolution atmospheric TRANsmittance) radiative transport software to separate out the atmospheric component of measured top of atmosphere radiance. Simulated water bodies across a variety of MODTRAN model atmospheres including desert, mid-latitude, tropical and sub-artic conditions provide test bed conditions. Atmospherically corrected radiance and surface temperature results were compared to those obtained using traditional radiosonde balloon data and models. In general, differences between the different techniques were less than 2 percent indicating the potential value satellite derived atmospheric profiles have to atmospherically correct thermal imagery.

Pagnutti, Mary↗

DOE OSTI2012

Thermal Removal Of Tritium From Concrete And Soil To Reduce Groundwater Impacts

Legacy heavy-water moderator operations at the Savannah River Site (SRS) have resulted in the contamination of equipment pads, building slabs, and surrounding soil with tritium. At the time of discovery the tritium had impacted the shallow (< 3-m) groundwater at the facility. While tritium was present in the groundwater, characterization efforts determined that a significant source remained in a concrete slab at the surface and within the associated vadose zone soils. To prevent continued long-term impacts to the shallow groundwater a CERCLA non-time critical removal action for these source materials was conducted to reduce the leaching of tritium from the vadose zone soils and concrete slabs. In order to minimize transportation and disposal costs, an on-site thermal treatment process was designed, tested, and implemented. The on-site treatment consisted of thermal detritiation of the concrete rubble and soil. During this process concrete rubble was heated to a temperature of 815 deg C (1,500 deg F) resulting in the dehydration and removal of water bound tritium. During heating, tritium contaminated soil was used to provide thermal insulation during which it's temperature exceeded 100 deg C (212 deg F), causing drying and removal of tritium. The thermal treatment process volatiles the water bound tritium and releases it to the atmosphere. The released tritium was considered insignificant based upon Clean Air Act Compliance Package (CAP88) analysis and did not exceed exposure thresholds. A treatability study evaluated the effectiveness of this thermal configuration and viability as a decontamination method for tritium in concrete and soil materials. Post treatment sampling confirmed the effectiveness at reducing tritium to acceptable waste site specific levels. With American Recovery and Reinvestment Act (ARRA) funding three additional treatment cells were assembled utilizing commercial heating equipment and common construction materials. This provided a total of four units to batch treat concrete rubble and soil. Post treatment sampling verified that the activity in the treated soil and concrete met the treatment standards for each medium which allowed the treated concrete rubble and soil to be disposed of on site as backfill. During testing and operations a total of 1,261-m{sup 3} (1,650-yd{sup 3}) of contaminated concrete and soils were treated with an actual incurred cost of $3,980,000. This represents a unit treatment cost of $3,156/m{sup 3} ($2,412/yd{sup 3}). In 2011 the project was recognized with an e-Star Sustainability Award by DOE's Office of Environmental Management.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2013

Thermal Removal of Tritium from Concrete and Soil to Reduce Groundwater Impacts - 13197

Legacy heavy-water moderator operations at the Savannah River Site (SRS) have resulted in the contamination of equipment pads, building slabs, and surrounding soil with tritium. At the time of discovery the tritium had impacted the shallow (< 3-m) groundwater at the facility. While tritium was present in the groundwater, characterization efforts determined that a significant source remained in a concrete slab at the surface and within the associated vadose zone soils. To prevent continued long-term impacts to the shallow groundwater a CERCLA non-time critical removal action for these source materials was conducted to reduce the leaching of tritium from the vadose zone soils and concrete slabs. In order to minimize transportation and disposal costs, an on-site thermal treatment process was designed, tested, and implemented. The on-site treatment consisted of thermal detritiation of the concrete rubble and soil. During this process concrete rubble was heated to a temperature of 815 deg. C (1,500 deg. F) resulting in the dehydration and removal of water bound tritium. During heating, tritium contaminated soil was used to provide thermal insulation during which it's temperature exceeded 100 deg. C (212 deg. F), causing drying and removal of tritium. The thermal treatment process volatiles the water bound tritium and releases it to the atmosphere. The released tritium was considered insignificant based upon Clean Air Act Compliance Package (CAP88) analysis and did not exceed exposure thresholds. A treatability study evaluated the effectiveness of this thermal configuration and viability as a decontamination method for tritium in concrete and soil materials. Post treatment sampling confirmed the effectiveness at reducing tritium to acceptable waste site specific levels. With American Recovery and Reinvestment Act (ARRA) funding three additional treatment cells were assembled utilizing commercial heating equipment and common construction materials. This provided a total of four units to batch treat concrete rubble and soil. Post treatment sampling verified that the activity in the treated soil and concrete met the treatment standards for each medium which allowed the treated concrete rubble and soil to be disposed of on-site as backfill. During testing and operations a total of 1,261-m{sup 3} (1,650-yd{sup 3}) of contaminated concrete and soils were treated with an actual incurred cost of $3,980,000. This represents a unit treatment cost of $3,156/m{sup 3} ($2,412/yd{sup 3}). In 2011 the project was recognized with an e-Star Sustainability Award by DOE's Office of Environmental Management. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Precursor Analysis Report: Ryuk Ransomware Attack on Universal Health Services 2020

The Ryuk Ransomware Attack on Universal Health Services (UHS) 2020 Precursor Analysis Report leverages publicly available information about the 2020 UHS cyber attack and catalogs anomalous observables for each technique employed in the attack. This analysis is based upon the methodology of the Cybersecurity for the Operational Technology Environment (CyOTE) program. UHS manages over 400 hospitals and is one of the largest healthcare providers in the United States with 3.5 million patients each year. On 27 September 2020, UHS suffered a widespread ransomware attack that resulted in a denial of service to critical internet-dependent healthcare systems including workstations, phones, and data centers. Employees resorted to filing patient details with pen and paper, while other facilities had to redirect ambulances and urgent patients to other facilities for adequate care. Adversaries carried out the attack with Ryuk, a ransomware that encrypts data and generates a RyukReadMe.txt ransom note with the ransom fee to decrypt the data, varying from 15 Bitcoin (BTC) to 50 BTC, equivalent to roughly $\$$353,892 to $\$$964,617. UHS did not pay the ransom and was able to recover data through backups, but still reported an impact of $\$$67 million dollars in recovery costs. On 29 October, one month after the attack, UHS made an official statement that their systems had been restored and they were resuming normal operations. Researchers and analysts identified 18 unique techniques (used in a sequence of 19 steps) utilized during the attack with a total of 185 observables using MITRE ATT&CK® for Industrial Control Systems. The CyOTE program assesses observables accompanying techniques used prior to the triggering event to identify opportunities to detect malicious activity. If observables accompanying the attack techniques are perceived and investigated prior to the triggering event, earlier comprehension of malicious activity can take place. Fourteen of the identified techniques used during the UHS cyber attack were precursors to the triggering event. Analysis identified 106 observables associated with these precursor techniques, 82 of which were assessed to have an increased likelihood of being perceived in the 30 days to two hours preceding the triggering event. The response and comprehension time could have been reduced if the observables had been identified earlier. The information gathered in this report contributes to a library of observables tied to a repository of artifacts, data sources, and technique detection references for practitioners and developers to support the comprehension of indicators of attack. Asset owners and operators can use these products if they experience similar observables or to prepare for comparable scenarios.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

DOE OSTI2010

CO2 interaction with geomaterials.

This work compares the sorption and swelling processes associated with CO2-coal and CO2-clay interactions. We investigated the mechanisms of interaction related to CO2 adsortion in micropores, intercalation into sub-micropores, dissolution in solid matrix, the role of water, and the associated changes in reservoir permeability, for applications in CO2 sequestration and enhanced coal bed methane recovery. The structural changes caused by CO2 have been investigated. A high-pressure micro-dilatometer was equipped to investigate the effect of CO2 pressure on the thermoplastic properties of coal. Using an identical dilatometer, Rashid Khan (1985) performed experiments with CO2 that revealed a dramatic reduction in the softening temperature of coal when exposed to high-pressure CO2. A set of experiments was designed for -20+45-mesh samples of Argonne Premium Pocahontas No.3 coal, which is similar in proximate and ultimate analysis to the Lower Kittanning seam coal that Khan used in his experiments. No dramatic decrease in coal softening temperature has been observed in high-pressure CO2 that would corroborate the prior work of Khan. Thus, conventional polymer (or 'geopolymer') theories may not be directly applicable to CO2 interaction with coals. Clays are similar to coals in that they represent abundant geomaterials with well-developed microporous structure. We evaluated the CO2 sequestration potential of clays relative to coals and investigated the factors that affect the sorption capacity, rates, and permanence of CO2 trapping. For the geomaterials comparison studies, we used source clay samples from The Clay Minerals Society. Preliminary results showed that expandable clays have CO2 sorption capacities comparable to those of coal. We analyzed sorption isotherms, XRD, DRIFTS (infrared reflectance spectra at non-ambient conditions), and TGA-MS (thermal gravimetric analysis) data to compare the effects of various factors on CO2 trapping. In montmorillonite, CO2 molecules may remain trapped for several months following several hours of exposure to high pressure (supercritical conditions), high temperature (above boiling point of water) or both. Such trapping is well preserved in either inert gas or the ambient environment and appears to eventually result in carbonate formation. We performed computer simulations of CO2 interaction with free cations (normal modes of CO2 and Na+CO2 were calculated using B3LYP / aug-cc-pVDZ and MP2 / aug-cc-pVDZ methods) and with clay structures containing interlayer cations (MD simulations with Clayff potentials for clay and a modified CO2 potential). Additionally, interaction of CO2 with hydrated Na-montmorillonite was studied using density functional theory with dispersion corrections. The sorption energies and the swelling behavior were investigated. Preliminary modeling results and experimental observations indicate that the presence of water molecules in the interlayer region is necessary for intercalation of CO2. Our preliminary conclusion is that CO2 molecules may intercalate into interlayer region of swelling clay and stay there via coordination to the interlayer cations.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2018

Boil-off losses along LH2 pathway

Losses along the LH 2 pathway are intrinsic to the utilization of a cryogenic fluid. They occur when the molecule is transferred between 2 vessels (liquefaction plant to trailer, trailer to station storage, station storage to pump or compressor, then fuel cell electric vehicles …) and when the fluid is warmed up due to heat transfer with the environment. Those losses can be estimated with good accuracy using thermodynamic models based on conservation of mass and energy, providing the thermodynamic states are correctly described. Indeed, the fluid undergoes various changes as it moves along the entire pathway (2 phase transition, super-heated warming, non-uniform temperature distributions across the saturation film) and accurate equations of state and 2 phase behavior implementations are essential. The balances of mass and energy during the various dynamics processes then enable to quantify the boil-off losses. In this work, a MATLAB code previously developed by NASA to simulate rocket loading is used as the basis for the LH 2 transfer model. This code implements complex physical phenomena such as the competition between condensation and evaporation and the convection vs. conduction heat transfer as a function of the relative temperatures on both sides of the saturated film. The original code was modified to consider real gas equations of state, and some semi-empirical relationships, such as between the heat of vaporization and the critical temperature, were also replaced by a REFPROP equivalent expression, assumed to be more accurate. Non-constant liquid temperature equations were added to simulate sub-cooled conditions. It is shown that although trailer depressurization and transfer losses from the receiving vessel during a LH 2 delivery may constitute the largest sources of losses, those can be greatly reduced and even eliminated if CFR/DOT regulations are properly applied and if no-vent fill methods are implemented, particularly for a stationary LH2 storage operating at reasonably low pressure (45 psia or so). As such, it is expected that the only remaining boil-off losses for a refueling station would come from the LH 2 pump (utilization and idling), pump vessel cool down/warm up, and environment heat transfer. Based on experimental data measured at LLNL on the Linde 875 bar LH 2 cryo-pump and results from the model, and extrapolating for refueling stations of various sizes, it can be shown that boil-off losses can vary from 15% of delivered LH 2 for a 100 kg/day, 5% at 400 kg/day, and down to less than 2% for stations above 1,800 kg/day (for a system similar to the one at LLNL). Less boil-off is to be expected for LH 2 pumps dispensing at 350 bar, so that less than 0.7% can be expected above 1,800 kg/day station capacities. At last, boil-off recovery solutions are briefly analyzed, including compressors, cryo-coolers and stationary fuel cell. Their economic value is strongly related to the costs of H2 and of the electricity needed to perform the recovery, on top of the initial capital expenditures. Effective boil-off could be reduced to 0.6-1% for a 2,000 kg/day station if adequate recovery solutions are used.

08 HYDROGEN↗

DOE OSTI2025

Findings on subtask 3.3 – applicability of automated brine chemistry determinations for treatment and recovery processes through facility automation/modularization: engineering design study

Under the Energy & Environmental Research Center’s (EERC’s) ~$\$$22 million Phase II Brine Extraction and Storage Test (BEST) Program, a multimillion-dollar brine treatment technology test bed facility was established in western North Dakota to provide a platform for evaluating developing technologies and approaches for brine treatment and volume reduction. The initial facility, and associated research effort, was funded by the U.S. Department of Energy (DOE), with in-kind contributions provided by several industry participants and the state of North Dakota. Since its opening, the Brine Technology Test Facility (BTTF) has supported performance evaluations of desalination technologies capable of treating high-salinity produced water (PW) and enabled data collection for multiple approaches of PW management and critical material recovery. As part of the decommissioning process for the original project, facility ownership and liability were transferred to Select Water, which is providing the EERC with a continuing site access option for state or federal research and/or commercial technology development. This report documents the findings from a design study conducted by the EERC and the engineering firm that was originally contracted to design and construct the facility (Advanced Engineering and Environmental Services, LLC [AE2S]) that evaluated the current status of BTTF and its systems and developed a retrofit design to increase the facility’s capabilities through automation and modularization of its PW treatment infrastructure. The proposed retrofit will provide DOE and industry with an expanded range of conditioned PW that can be produced at the facility for evaluating fit-for-purpose water treatment technologies, online instrumentation for brine chemistry determination, and systems that recover critical materials like lithium and magnesium. The current facility consists of an 9600-square-foot facility that includes a 40-foot by 65-foot Class 1, Division 2-rated demonstration area and associated control rooms and lab-ready space capable of sourcing oil and gas PW and wastewater from industrial sources or tailoring brine compositions up to 300,000 mg/L total dissolved solids (TDS) and supplying them at rates up to 25 gpm for extended-duration technology demonstrations. The colocation of the facility with Select Water’s water management facilities allows for access and unloading of more than 10,000 bbl/day of trucked water delivered to site and associated access to on-site Class I and Class II brine disposal wells and nearby hazardous waste landfills operated and/or contracted by Select Water to dispose of concentrate and/or effluents associated with the testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Utilizing geothermal heat for hydrothermal liquefaction of algae

The distribution of utilizable geothermal reservoirs in the US is concentrated in areas of low population density. In order to increase the scale of geothermal operations, we proposed to develop a modular biofuel production facility that directly uses geothermal heat. By transforming geothermal heat to chemical potential energy (rather than electricity), the scale of existing or new geothermal operations can be increased and distributed to areas of higher population density. Simultaneously, the economics of producing biocrude oil is improved significantly where geothermal heat is used, instead of natural gas-fired systems for providing heat and power. In the Phase I project, we demonstrated that it was economically feasible to sustainably produce a biofuel by integrating geothermal heat. It was found that, for the best case scenario at a scale of 10T(biomass)/hr, it was possible to produce a biofuel for $0.26/L, as compared to crude oil at $0.3/L (current selling price). Ultimately this demonstrates that this technology can be economically sustainable when integrated with geothermal heat. We also demonstrated that the addition of modular biofuel-production technologies can be more profitable for a geothermal plant operator. For 1000kg/day scale, it was found that it could be 2.5 times more profitable for a geothermal plant operator to sell bio-oil rather than electricity (with a waste source within 20 miles of the processing facility). Furthermore, as the design of the proposed technology recycles significant heat, requiring between 5% and 20% of the total heat load of the biofuel process to be supplied by the geothermal plant, it is feasible for an operator to initially implement the technology at small scale (i.e. less than 100gal/day) with the plans of scaling up operations in the future. Implementing the technology incrementally may minimize initial the investment and financial risk for the operator. Finally, in the Phase I project, we built and tested a hydrothermal system developed at ARI. We tested three different feedstock types, pure algae feed, algae mixed with manure, and algae with in-situ catalysts (molybdenum trioxide), over a range of temperatures and residence times. In terms of oil products, our results (yield, process times and elemental balance) were similar to what was obtained at PNNL. As such our experiments matched well with the techno-economic design (mass throughput specifications), and will thus well inform the Phase II process design. The experimental data obtained on the hydrothermal treatment of algae indicated that the highest recovery of oil occurred at 250°C. This shows that HTL can be carried out 100°C lower than what is currently considered ‘state of the art’, and thus save significant energy savings. Further, it was found that oil-recovered fractions had lower amounts of nitrogen at lower temperatures, indicating that oil produced at 250°C is of higher quality than if we were to produce fuel at 350°C.

09 BIOMASS FUELS↗

DOE OSTI2012

Seismic Monitoring at the Underground Nuclear Research Laboratory in Mol, Belgium - 12461

Micro-seismic piezoelectric transmitters installed in the Boom Clay at HADES produce predominantly high frequency signals, above 5 kHz, which favour the generation of P waves. However, above 5 kHz shear (S) waves are not detected by the installation. Recent studies at HADES indicate that it is possible to detect S waves with the current setup when applying a low (5 kHz) cut-off filter. The results also show that S waves have frequencies mainly below 1 kHz, while P waves are detectable at all of the eight transmitted frequencies but show optimum resolution in the range of 7 to 23 kHz. Although the system offers great potential for monitoring the evolution of a geological disposal site, further improvements in signal generation and treatment are necessary. One of these includes the design and testing of a new S-wave source at HADES planned in the framework of the EC MoDeRn project (http://www.modern-fp7.eu/). The seismic installation at HADES continues to provide useful information on the changing properties of the Boom Clay in the near and far field around the PRACLAY gallery since its start of operation in 2006. In the future, the system will also monitor the PRACLAY heater experiment that will start in 2012 and go on for 10 years. So far, the results of long term seismic monitoring show that S waves contain frequencies mainly below 1 kHz. The P waves are detectable at all of the eight transmitted frequencies but show optimum resolution in the range of 7 to 23 kHz. To improve the signal-to-noise ratio and detection of S waves at HADES it is, therefore, necessary to apply a strong low-pass filter that matches the S-wave frequency content. Due to the different frequency ranges observed for the P and S waves, it is recommended to treat them separately. The evolution of both P and S wave velocities in the EDZ around the PRACLAY gallery show continued recovery since its construction in 2007. Modelling results of the variation in crack density obtained from the inversion of the modelled P-wave transmission velocities further confirm the recovery of the EDZ and the self-healing properties of the Boom Clay. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2014

Subsurface Sources of CO 2 in the Contiguous United States. Volume 1: Discovered Reservoirs

Twenty-one CO 2 fields in the contiguous states contain an estimated 311 Tcf of CO 2 gas-initially-in-place (GIIP). Of that, 168 Tcf (54 percent) is estimated to be accessible and technically recoverable. The estimated economically recoverable resource (ERR) is 96.4 Tcf, based on a CO 2 price of 1.06 $/mcf ($20/tonne) at the field gate. Cumulative production to date is 18.9 Tcf, leaving 77.5 Tcf remaining or net ERR. The Big Piney-LaBarge field in Wyoming contains an estimated net ERR of 52 Tcf, 67 percent of the total for the United States. The remaining ERR in reservoirs that feed into the Permian Basin and Gulf Coast is on the order of 10-20 years of supply.

03 NATURAL GAS↗

DOE OSTI2020

Pore size effect on selective gas transport in shale nanopores

In shale gas production, gas composition may vary over time. To understand this phenomenon, we use molecular dynamics simulations to study the permeation of CH 4 , C 2 H 6 and their mixture from a source container through a pyrophyllite nanopore driven by a pressure gradient. For a pure gas, the flow rate of CH 4 is always higher than that of C 2 H 6 , regardless of pore size. For a 1:1 C 2 H 6 : CH 4 mixture, however, C 2 H 6 :CH 4 flow rate ratio is higher than the compositional ratio in the container (i.e., 1:1) when the pore size is smaller than ~1.8 nm. The selective transport is caused by the competitive adsorption of C 2 H 6 over CH 4 in the nanopore. The selectivity is also determined by the interplay between the surface diffusion of the adsorbed molecules and the viscous flow in the center of the pore, and it diminishes as the viscous flow becomes to dominate the surface diffusion when the pore size becomes larger than 1.8 nm. Our work shows that compositional differentiation of shale gas in production is a consequence of nanopore confinement and therefore a key characteristic of an unconventional reservoir. Finally, the related compositional information can potentially be used for monitoring the status of a production well such as its recovery rate.

03 NATURAL GAS↗

DOE OSTI2023

Insights into Waterflooding in Hydrocarbon-Bearing Nanochannels of Varying Cross Sections from Mesoscopic Multiphase Flow Simulations

Waterflooding is one of the geotechnique used to recover fuel sources from nanoporous geological formations. The scientific understanding of the process that involves the multiphase flow of nanoconfined fluids, however, has lagged, mainly due to the complex nanopore geometries and chemical compositions. To enable benchmarked flow of nanoconfined fluids, the architected geomaterials, such as synthesized mesoporous silica with tunable pore shapes and surface chemical properties, are used for designing and conducting experiments and simulations. This work uses a modified many-body dissipative particle dynamics (mDPD) model with accurately calibrated parameters to perform parametric flow simulations for studying the influences of waterflooding driven power, pore shape, surface roughness, and surface wettability on the multiphase flow in heptane-saturated silica nanochannels. Remarkably, up to 80\% reduction in the effective permeability is found for water-driven heptane flow in a baseline 4.5 nm-wide slit channel, when compared with the Hagen–Poiseuille equation. In the 4.5 nm-wide channels with architected surface roughness, the flow rate is found either higher or lower than the baseline case, depending on the shape and size of cross-sections. High wettability of the solid surface to water is essential for achieving high recovery of heptane, regardless of surface roughness. When the solid surface is less wetting or non-wetting to water, the existence of an optimal waterflooding driven power is found to allow for the highest possible recovery. A detailed analysis on the evolution of the transient water-heptane interface in those nanochannels is presented to elucidate the underlying mechanisms that impact or dictate the multiphase flow behaviors.

58 GEOSCIENCES↗

DOE OSTI2018

Effects of roasting additives and leaching parameters on the extraction of rare earth elements from coal fly ash

Coal fly ash is a promising alternative source for rare earth elements (REE), which are critical materials in many technologies. REEs are entrained in the aluminosilicate glass of the fly ash particles, hindering their ability to solubilize during acid leaching. The purpose of this research was to test the effectiveness of roasting techniques to improve extraction of REEs from fly ash, determine key parameters controlling REE extraction, and understand trade-offs in reagent use. Representative coal ash samples from major U.S. coal basins (Appalachian, Illinois, and Powder River basins) were roasted using a variety of chemical additives (Na 2 O 2 , NaOH, CaO, Na 2 CO 3 , CaSO 4 , (NH 4 ) 2 SO 4 ). Further experiments investigated the effects of additive:ash ratio, roasting temperature, and leachate pH on REE extraction. We found here that NaOH roasting often recovered >90% of total REE content, equivalent to the USGS-recommended method (Na 2 O 2 sintering). Other additives tested recovered <50% of total REE content; the 450 °C sinter temperature, which was well below the melting points of these agents, may have been a contributing factor. Decreasing the NaOH-ash ratio did not significantly inhibit in REE recoveries, while increasing the leachate pH led to a sharp decline. There was a strong positive correlation between REE extraction and leachate H + molarity. Recoveries of ~100% were observed for the Powder River Basin ash sample regardless of the roasting agent and additive:ash ratio used. This suggests that acid leaching alone is sufficient for recovering REEs from more soluble Powder River Basin ashes. For Appalachian and Illinois Basin ashes, the recommended roasting conditions for >70% REE extraction are a 1:1 NaOH-ash ratio and leaching with 1–2 mol/L HNO 3 .

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2026

Chemical beneficiation of cobaltiferous pyrite: a thermodynamic and parametric study

Despite ongoing efforts to identify substitute materials, cobalt remains indispensable for the production of rechargeable batteries essential to the global energy transition. Currently, most cobalt is sourced as a by-product of nickel and copper extraction from politically and ethically unstable regions. To address this vulnerability, certain primary cobalt deposits—where cobalt occurs within the crystal lattice of pyrite (FeS 2 )—have been identified as potential alternatives. Nonetheless, conventional beneficiation methods have proven largely ineffective for the potential processing of these minerals. This study investigated the thermal decomposition of cobaltiferous pyrite contained in flotation concentrates as a subsequent chemical beneficiation stage aimed at (i) selectively removing sulfur to further increase cobalt grades and (ii) producing a ferromagnetic product suitable for downstream magnetic separation. A thermodynamic analysis was first conducted to evaluate the feasibility of the decomposition reactions and the temperature-dependent evolution of sulfur species. A parametric experimental study then assessed the influence of temperature, residence time, and gas flow rate under N 2 and CO 2 atmospheres. Under the most favorable experimental conditions tested (650 °C, 15 min), cobalt grades increased by up to 15% with negligible cobalt losses and the co-production of high-purity sulfur (>95%). Magnetic separation of the resulting calcine yielded a final concentrate containing 2.09% cobalt at 82.5% recovery, representing a 16–74% improvement over previous baseline studies on similar feedstocks.

Beneficiation↗

DOE OSTI2024

Enrichable consortia of microbial symbionts degrade macroalgal polysaccharides in Kyphosus fish

ABSTRACT Coastal herbivorous fishes consume macroalgae, which is then degraded by microbes along their digestive tract. However, there is scarce genomic information about the microbiota that perform this degradation. This study explores the potential of Kyphosus gastrointestinal microbial symbionts to collaboratively degrade and ferment polysaccharides from red, green, and brown macroalgae through in silico study of carbohydrate-active enzyme and sulfatase sequences. Recovery of metagenome-assembled genomes (MAGs) from previously described Kyphosus gut metagenomes and newly sequenced bioreactor enrichments reveals differences in enzymatic capabilities between the major microbial taxa in Kyphosus guts. The most versatile of the recovered MAGs were from the Bacteroidota phylum, whose MAGs house enzyme collections able to decompose a variety of algal polysaccharides. Unique enzymes and predicted degradative capacities of genomes from the Bacillota (genus Vallitalea ) and Verrucomicrobiota (order Kiritimatiellales ) highlight the importance of metabolic contributions from multiple phyla to broaden polysaccharide degradation capabilities. Few genomes contain the required enzymes to fully degrade any complex sulfated algal polysaccharide alone. The distribution of suitable enzymes between MAGs originating from different taxa, along with the widespread detection of signal peptides in candidate enzymes, is consistent with cooperative extracellular degradation of these carbohydrates. This study leverages genomic evidence to reveal an untapped diversity at the enzyme and strain level among Kyphosus symbionts and their contributions to macroalgae decomposition. Bioreactor enrichments provide a genomic foundation for degradative and fermentative processes central to translating the knowledge gained from this system to the aquaculture and bioenergy sectors. IMPORTANCE Seaweed has long been considered a promising source of sustainable biomass for bioenergy and aquaculture feed, but scalable industrial methods for decomposing terrestrial compounds can struggle to break down seaweed polysaccharides efficiently due to their unique sulfated structures. Fish of the genus Kyphosus feed on seaweed by leveraging gastrointestinal bacteria to degrade algal polysaccharides into simple sugars. This study reconstructs metagenome-assembled genomes for these gastrointestinal bacteria to enhance our understanding of herbivorous fish digestion and fermentation of algal sugars. Investigations at the gene level identify Kyphosus guts as an untapped source of seaweed-degrading enzymes ripe for further characterization. These discoveries set the stage for future work incorporating marine enzymes and microbial communities in the industrial degradation of algal polysaccharides.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

SECARB Regional Project Assessment

The SECARB Cranfield Early Test Project was designed to safely demonstrate large-scale, long-term CO 2 injection and storage in a CO 2 -enhanced oil recovery (EOR) operation and associated saline reservoir. Storage during EOR operations has the potential to offset commercial costs, holding a significant promise for future large-scale deployment in the southeastern United States. Denbury Onshore LLC began CO 2 -EOR operations in July 2008 at the Cranfield oilfield located east of Natchez, Mississippi (Figure 1). The location offered an ideal setting to investigate storage monitoring at a commercial CO 2 -EOR operation. The field team, led by the Gulf Coast Carbon Center of the Bureau of Economic Geology at the University of Texas at Austin, deployed the largest suite of monitoring, verification, accounting (MVA) technologies to collect data to assess long-term CO 2 utilization and storage. The CO 2 injection interval is within the 3,000-meter-deep fluvial lower Tuscaloosa Formation, a large and regionally extensive saline reservoir, at a broad four-way structural closure that defines the Cranfield oilfield. Tests were conducted in the oil-producing area as well as in the non-oil-producing brine aquifer. The CO 2 used during EOR operation was transported via pipeline from the Jackson Dome, a natural source of CO 2 . The study focused on four integrated research areas: (1) the High-Volume Injection Test area (HiVIT); (2) the Detailed Area of Study (DAS); (3) the Geomechanical area; and (4) the near-surface observatory, also called the “P-site.” CO 2 injection occurred at the HiVIT and the DAS (Figure 2 and Figure 3). The DAS was located down-dip of the oil-water interface of the Cranfield oilfield. The well layout included one injection well and two down-dip observation wells. The team was the first of the regional partnerships to monitor more than 1 million metric tons of CO 2 . At the end of the project, the team monitored more than 11 million metric tons of CO 2 injected and 5 million metric tons of CO 2 stored. The Cranfield Project was the fifth project worldwide, and the first such project in the United States, to reach this CO 2 injection volume while being monitored to demonstrate storage effectiveness.

01 COAL, LIGNITE, AND PEAT↗