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At least 451 records · Page 25

Getting to 100%: Six Strategies for the Challenging Last 10%

This presentation summarizes the challenge of decarbonizing the last 10%" of the power system and discusses six strategies for addressing that challenge. This presentation was given at the IRA, BIL, and the Future of Energy: A Summit to Support State Implementation" workshop in Washington, D.C., in April 2024.

carbon capture↗

lllinois Storage Corridor CarbonSAFE Phase III: Pre-drilling Site Assessment: Prairie State Generating Company

The Illinois Storage Corridor project will drill a stratigraphic test well as part of the Illinois Storage Corridor CarbonSAFE Phase 3 project near the Prairie State Generating Company coal-fired power plant near Marissa, Illinois. The pre-drilling site evaluation has considered the primary target reservoirs, the Potosi Dolomite and St. Peter Sandstone, and primary seal, the Maquoketa Group. Data to be collected from the well include core, fluid samples, in situ well tests, geophysical logs intended to provide information on lithologic, geomechanical, and geophysical characteristics to determine the feasibility for the geologic sequestration of 50 million metric tons or more of injected carbon dioxide. The planned drilling site has been evaluated using available subsurface geologic data and analyses from the Illinois Basin. These data provide lithologic and structural information, shallow groundwater resource distribution, location of known nearby wellbores, and regional drilling characteristics. The data were used to generate geologic structure and isopach maps for the target reservoir and caprock strata and for prognosing the tops of major lithologic units to aid drilling and coring procedures. The regional analyses indicate that no known structural features are expected to negatively impact the target storage reservoir or caprock. No protected and sensitive areas, groundwater resources, or existing resource development are expected to be impacted by the proposed well drilling activities. The well is planned to be drilled to a total depth of approximately 5,600 feet (1,707 m) and terminate in the Precambrian. Cores (up to 5 intervals) will be collected from the Maquoketa Group, confining units above the St. Peter Sandstone, St. Peter Sandstone, confining units of the Potosi Dolomite and the Potosi Dolomite. Water samples will be attempted to be collected from the St. Peter Sandstone and Potosi Dolomite. Potential impact on drilling progress is a lost circulation zone in the Potosi Dolomite, which has been demonstrated to have intermittent cavernous porosity from karstification elsewhere in the Illinois Basin. This document also presents a preliminary coring and sampling program, proposed logging suite, and well testing program, all of which will be reviewed during drilling.

01 COAL, LIGNITE, AND PEAT↗

Numerical Simulations of Geologic Storage Reservoir Management to Support Risk Mitigation Evaluation

This report provides a detailed description of a set of numerical simulations that represent reservoir behavior over time in response to different operational decision scenarios for detection of potential leakage and reduction or avoidance of leakage impact at a hypothetical geological carbon storage (GCS) site. These simulations serve as the basis for a series of GCS leakage risk forecasts that are to be developed using the National Risk Assessment Partnership’s Open-Source Integrated Assessment Model (NRAP-Open-IAM), and a demonstration of a simple decision support workflow for evaluation of mitigation strategies based on results of those system model forecasts. This risk assessment and decision support study is forthcoming. Four injection scenarios were considered: a constant rate carbon dioxide (CO 2 ) injection case (base case), a case with CO 2 injection rate adjustment, a case with early termination of injection operations, and a case with brine extraction. CO 2 injection operations were controlled to ensure that the pressure transient remains below the defined manageable reservoir fracture pressure, with consideration shown to hypothetical locations within the modeled spatial domain where the overburden was weaker and lower transient pressure increases were allowable. Additionally, a brine extraction alternative was considered as a reservoir management and risk mitigation option to reduce reservoir pressure, steer the plume away from any hypothetical geohazard such as fault as needed, and enhance storage capacity. Such operational actions contribute to risk management overtime. This study explores the potential utility of reservoir management for risk reduction at GCS sites. This study shows that the injection design may modify the time to CO 2 breakthrough at a legacy well; in particular, these results show that brine extraction can add value for mitigating risk both by delaying leakage and reducing pressure build-up. For the scenario considered, both pressure plots and pressure distributions demonstrate that pressure build-up was decreased by 3% with brine extraction. Additionally, extraction of brine afforded enhancement of CO 2 storage capacity by 5% compared to the base case. These findings suggest that brine extraction has substantial potential to steer the risk-related reservoir effects away from known geohazards (e.g., faults and legacy wells) by conducting pressure transient effects and CO 2 plume movement toward the production well. Injection rate adjustment scenarios considered in this study show potential value for managing both reservoir pressure transients and CO 2 plume behavior. Operational actions for reducing injection and/or early termination of injection (as compared to the base case), however, require careful design; tailoring both the extent and timing of injection rate adjustment over the injection and post-injection operational period must be thoroughly planned to balance maximizing storage and minimizing subsurface environmental risk. The study also gives preliminary consideration to the effectiveness that monitoring strategy may play in providing useful information to inform reservoir management decisions for risk reduction. Two types of monitoring were considered: 1) pressure build-up or pressure transient; and 2) potential leakage detection from a CO 2 mass or plume. Four hypothetical legacy wells, two plugged and two abandoned, were placed in the model domain. Monitoring along these wells was measured over time in individual stacked reservoir formations and shale formations to support risk mitigation decisions, especially operational decisions that assisted in risk reduction. These simulations will serve as the basis for a series of GCS leakage risk forecasts that are to be developed using NRAP’s Open-IAM, and demonstration of a simple decision support workflow for comparative assessment of mitigation alternatives based on results of those system model forecasts. This risk assessment and decision support study is forthcoming.

54 ENVIRONMENTAL SCIENCES↗

How Today's Hydropower Impacts Tomorrow's Grid: Counterfactual Scenarios Showing Grid Impacts if Hydropower Goes Away

Amidst ongoing discussions about hydropower removals, retirements, and reduced availability due to drought and other environmental considerations, it is important to understand the long-term effects of reduced hydropower resources on the U.S. electric grid. This analysis uses the Regional Energy Deployment System (ReEDS™) grid planning model to compare several representative scenarios of retiring hydropower and pumped storage hydropower (PSH) capacity over time and explore the overall implications on the U.S. grid from present day through 2050. Reduced hydropower capacity and generation is replaced by a mix of both fossil and non-fossil resources, including natural gas, wind, solar, and battery technologies. Additional natural gas usage leads to an increase in cumulative national electric sector carbon dioxide and criteria pollutant operating emissions of less than 1% in many scenarios but up to 4-5.3% in some cases. Total electric sector costs also increase by <1% in many scenarios but up to 3.6% in the most extreme scenarios where nearly all the hydropower and PSH fleet retires, equating to $\$$340 billion in undiscounted costs. National results indicate that absent additional interventions, retiring hydropower and PSH capacity could increase electric sector emissions and direct capital and operating costs. However, more focused analysis is required to evaluate specific asset-level, local, and regional implications, and a broader scope is necessary to weigh these electric sector impacts alongside economic, ecological, water management, and other cross-sectoral effects that could be either negative or positive.

14 SOLAR ENERGY↗

The U.S. Energy System and the Production of Sustainable Aviation Fuel From Clean Electricity

Jet fuel is relatively small in terms of energy consumption and carbon dioxide emissions (10% of U.S. transportation sector in 2021, expected to increase to 14% by 2050). Still airlines have ambitious goals to reduce their greenhouse footprints from carbon-neutral growth beginning this year to reducing greenhouse gas emission for international flights by 50% by 2050 compared to 2005 levels. The challenge is heightened by the longevity of the current fleet (30–50 years) and by the difficulty in electrifying the future fleet because only 5% of the commercial aviation greenhouse gas footprint is from regional flights that might, conceivably be electrified using foreseeable technology. Therefore, large amounts of sustainable aviation fuel will be needed to reach the aggressive targets set by airlines. Only 3 million gallons (11.4 ML) of sustainable aviation fuel (SAF) (with a heat of combustion totaling about 400 TJ = 0.0004 EJ) was produced in the U.S. in 2019 for a 26 billion gallon per year market (3.6 EJ/year). Fischer-Tropsch and ethanol oligomerization (alcohol-to-jet) are considered for producing SAF, including the use of renewable electricity and carbon dioxide. In sequencing the energy transition, cleaning the U.S. grid is an important first step to have the largest greenhouse gas emissions reduction. While carbon dioxide and clean electricity can potentially provide the SAF in the future, an ethanol oligomerization option will require less energy.

25 ENERGY STORAGE↗

Sustainable Valorization of CO2 through Nuclear Power-to-X Pathways

Some of the issues concerning energy security and climate change can be addressed by employing nuclear power (NP) to supply the energy required for the conversion of carbon dioxide (CO2) into chemicals, products, and materials. Nuclear energy represents a neutral carbon source that can be generated sustainably, reliably, and consistently. Nuclear power plants (NPPs) could supply energy in the form of heat, electricity, and ionizing radiation to drive CO2 chemical reactions underpinning NP-to-X type of pathways. CO2 conversion processes are either commercially available or emerging technologies at different developmental maturity stages. This work reviews the published literature (articles and patents) that reports R&D results and the understanding and development of chemical reactions and processes, as well as the efforts in integrating NPPs and chemical processes (CPs). As will be made evident, a new industrial era for the manufacturing of decarbonized chemicals, products, and materials will be possible by developing and implementing new (more energy- and carbon-efficient) processes responding to the NP-to-X pathways. This new decarbonizing platform not only contributes to achieving net zero goals but also broadens the NPP product beyond electricity.

08 HYDROGEN↗

Voucher Opportunity 5-15: Independent Assessment of Monitoring, Reporting, and Verification (MRV) Technologies and Practices for Enhanced Rock Weathering (CRADA 718) Abstract

Development of robust, transparent, and precise monitoring, reporting, and verification (MRV) technologies and practices is critical for carbon dioxide removal (CDR) project developers to comply with regulatory and permitting requirements, voluntary carbon market (VCM) protocols, and to ensure safety while reducing environmental impacts. Enhanced rock weathering (ERW)-based CDR technologies focus on removing atmospheric carbon through conversion into thermodynamically stable solid or aqueous carbonate forms for permanent storage (i.e., mineralization). This highly durable form of CDR enhances naturally occurring silicate rock weathering cycles by optimizing application of finely-ground silicate rock particles (i.e., from basalt) on terrestrial agricultural lands to accelerate natural silicate rock weathering and mineralization. Enhanced rock weathering may also provide improved crop yields and enhance soil health. A critical aspect for commercialization of these technologies is the development of MRV to quantify the net removal and durable storage of atmospheric CO 2 . For ERW systems, it is essential to accurately characterize the mineral feedstock selected for application to establish the baseline geochemical composition, mineral dissolution rates, and carbon removal potential of the feedstocks to estimate overall net removal. Given the difficulty with conducting MRV for ERW in diverse soil/environment types, over large application areas, and due to complex chemical reaction networks, this project will accelerate understanding towards consensus on best practices for MRV. The overall objectives of the proposed voucher project are to: 1) Characterize and analyze feedstock(s) intended for ERW field application by Lithos Carbon (“Voucher Recipient”/ “CRADA Participant”) to determine overall mineralization potential; 2) Facilitate knowledge transfer and documentation of experimental protocols, instrumentation, and other relevant best practices; and 3) Support the Voucher Recipient’s broader technology commercialization and ERW Research Facility development plans. This work will align with the Voucher Recipient’s MRV plans for field sites and build upon complementary efforts conducted by PNNL on mineralization MRV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Depolarized Electro-Membrane System (EDEMS) for Direct Capture of Carbon Dioxide from Ambient Air (Final Report)

The goal of this final project report is to summarize the work conducted on project DE-FE0031962. In accordance with the Statement of Project Objectives (SOPO), the University of Kentucky Center for Applied Energy Research (UK CAER) (Recipient) developed an intensified process to capture CO2 from ambient conditions (400 ppm CO2). The process combines low-temperature solvent-aided membrane capture with electrochemically-mediated solvent regeneration to simultaneously capture ambient CO2 while regenerating the solvent. The technology employs only two primary units (regenerator and absorber/contactor) while generating high purity hydrogen as a co-product that can be sold, used for energy storage, or cost-saving depolarization of the direct air capture (DAC) system during the grid peak demand, allowing for flexible operation. When depolarization is employed, the operating voltage is reduced by more than 1 V. Since the technology is powered directly by DC electricity, it can seamlessly tie in with power sources like solar cells without the need for AC/DC converters, therefore allowing for a remote operation to further mitigate greenhouse gas generation toward deploying a negative carbon emissions technology that is completely decoupled from the carbon emissions from the power source for the DAC unit. The project results verified that UK CAER’s integrated approach addressed the complexities of incumbent DAC systems by demonstrating at ambient conditions, including (1) low gas-side pressure-drop facile CO2 capture via a membrane contactor with in-situ generated hydroxide as capture solvent, (2) multi-functional electrochemical regenerator for hydroxide regeneration, CO2 concentration and hydrogen production, and (3) depolarization using cathode-produced hydrogen to reduce energy requirement. The EH&S Assessment of the process did not identify any obvious concern for the bench-scale operation and no apparent barriers to implementing UK CAER’s carbon capture and solvent regeneration system at a larger scale.

20 FOSSIL-FUELED POWER PLANTS↗

Reaction Pathways over ZnZrO 2 -Based Catalysts and Catalytic Sorbents

Reactive capture and conversion (RCC) is a process intensification approach that integrates CO 2 capture and hydrogenation within a single unit, removing the CO 2 purification and storage steps of traditional process flow schemes. This alters the catalytic step from a traditional steady-state (SS) flow process to a transient capture and conversion cycle, which could lead to product distributions distinct from those observed in conventional SS experiments. Such differences are investigated in the combined capture and hydrogenation of carbon dioxide to methanol over a ZnZrO 2 catalyst and a ZnZrO 2 + NaNO 3 /Mg 3 AlO x catalytic sorbent (CS) using fixed-bed kinetic measurements, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and steady-state isotopic transient kinetic analysis-DRIFTS (SSITKA-DRIFTS). Under SS conditions, ZnZrO 2 produced methanol through sequential hydrogenation of HCOO* and CH 3 O* intermediates. On the contrary, CO was attributed primarily to CO 2 dissociation at oxygen vacancies, as supported by isotopic shifts and measured reaction orders. For the CS, isotopic switching experiments suggested that monodentate carbonate species (CO 3 2− , abbreviated as m-CO 3 2− ) act as active intermediates that can be hydrogenated to HCOO* and subsequently to CH 3 O. Under RCC conditions, in situ DRIFTS and isotopic experiments reveal that m-CO 3 2− species formed during the CO 2 capture step follow two competing routes upon H 2 exposure: (i) direct hydrogenation to methane on the sorbent domain or (ii) migration of m-CO 3 2− to the ZnZrO 2 domain, where they are hydrogenated to methanol through the HCOO pathway. Overall, RCC enables carbonate hydrogenation routes not observed under SS cofeed conditions. Thus, the reaction pathways and rates during RCC can be different from operation under conventional SS conditions, and the product distribution is determined here by competition between carbonate hydrogenation on sorbent sites and migration to ZnZrO 2 for methanol synthesis.

CCUS↗

Reactivity of CO 2 with Utica, Marcellus, Barnett, and Eagle Ford Shales and Impact on Permeability

We report that in order to reduce greenhouse gas emissions while recovering hydrocarbons from unconventional shale formations, processes that make use of carbon dioxide to enhance oil recovery while storing carbon dioxide (CO 2 ) should be considered. Here, we examine samples from three shale basins across the United States (Utica and Marcellus Shales in the Appalachian Basin, Barnett Shale in the Bend Arch-Ft. Worth Basin, and Eagle Ford in the Western Gulf Basin) to address the following questions: (1) do changes from reaction with CO 2 and fluids at the micrometer and nanometer scale alter flow pathways and, in turn, impact hydrocarbon production, CO 2 storage, and seal integrity and (2) can CO 2 or fluid reactivity be predicted based on physical or chemical properties of shale formations? Experiments were conducted at 40 °C and 10.3 MPa to characterize the interaction between CO 2 and shale using X-ray diffraction (XRD), carbon and sulfur analysis, in situ Fourier transform infrared spectroscopy (FT-IR), feature relocation scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), mercury (Hg) intrusion porosimetry, and Brunauer-Emmett-Teller (BET) surface area and pore size analysis coupled with density functional theory (DFT) methods. Changes in mechanical, physical, and flow properties of shale cores due to CO 2 exposure were addressed using a New England Research Autolab 1500 and Xenon X-ray computed tomography (CT) scanning. Results showed that CO 2 did not promote significant reactivity with the shale if water was not present; only shales with swelling clays or residual interstitial pore water reacted with dry CO 2 to promote reactivity in shale. When water was added as a reactant, CO 2 formed carbonic acid and reacted with the shale to dissolve carbonate pockets, etched and pitted the shale matrix surfaces, and increased the microporosity and decreased nanoporosity. Porosity and permeability increased appreciably in core shale samples after exposure to CO 2 saturated fluid due to dissolution of carbonate. Shale mechanical properties were not altered. Trends were not observed that could tie CO 2 or fluid reactivity to physical or chemical properties of the shale formations at the basin scale from the samples we examined. However, if the shale contained significant amounts of carbonate and water was available to react with the CO 2 , pore sizes were altered in the matrix and permeability and porosity increased.

04 OIL SHALES AND TAR SANDS↗

Converting Carbon Dioxide into Carbon Nanotubes by Reacting with Ethane

In this study, the urgency to mitigate environmental impacts from anthropogenic CO 2 emissions has propelled extensive research efforts on CO 2 reduction. The current work reports a novel approach involving transforming CO 2 and ethane into carbon nanotubes (CNTs) using earth-abundant metals (Fe, Co, Ni) at 750 °C. This route facilitates long-term carbon storage via generating high-value CNTs and produces valuable syngas with adjustable H 2 /CO ratios as byproducts. Without CO 2 , direct pyrolysis of ethane undergoes rapid deactivation. The participation of CO 2 not only enhances the durability of the catalyst, but also contributes about 30 % of the CNTs production, presenting a viable solution to CO 2 challenges. The CNT morphology depends on the catalyst used. Co- and Ni-based catalysts produce CNT with a 20 nm diameter and micrometer length, whereas Fe-based catalysts yield bamboo-like structures. This work represents a pioneering effort in utilizing CO 2 and ethane for CNT production with potential environmental and economic benefits.

09 BIOMASS FUELS↗

Computational and Experimental Investigation of Thermal-Mechanical- Chemical Mechanisms of High-burnup Spent Nuclear Fuel (SNF) Processes at Elevated Temperatures and Degradation Behavior in Geologic Repositories

The overarching goal of the combined computational and experimental R&D activities proposed in this project is to enhance understanding of the mechanisms and thermal-mechanical-chemical (TMC) parameters controlling the instant release fraction (IRF) and matrix dissolution of high-burnup (HB; burnup) spent nuclear fuels (SNFs) and the subsequent formation, stability, and phase transformations of SNF alteration products under long-term storage and geological disposal conditions. Uranium dioxide may undergo oxidative corrosion/alteration, and the IRF may be increased for HB SNF, both of which may affect environmental systems associated with SNF long-term storage and disposal. The oxidative matrix dissolution may form various complex uranyl-based phases, including a rich variety of oxides, silicates, carbonates and other secondary minerals in varied geological environments (e.g., studtite, metastudtite, amorphous uranyl peroxide, uranium trioxide, triuranium octoxide, schoepite, dehydrated schoepite, metaschoepite, becquerelite, soddyite, rutherfordine,...). These uranyl phases generally have higher mobility UO 2 +2 species than less soluble U 4+ phases. However, limited information on the thermodynamic properties and formation kinetics of these uranyl-bearing phases is available to predict explicitly paragenesis under the conditions relevant to long-term storage or disposal. The proposed project draws on complementary expertise and research backgrounds from the team members: (i) to apply a combined ab initio modeling (UNLV/UTEP and SNL) and experimental (UNLV) strategy investigating the high-temperature TMC mechanisms of alteration of SNF under α-radiolysis conditions; (ii) to investigate the mechanistic of phase transformations in UNF degradation products under various conditions expected in long-term storage systems (e.g. (UO 2 )O 2 (H 2 O) 4 → (UO 2 )O 2 (H 2 O) 2 → U 2 O 7 → UO 3 → U 3 O 8 ); (iii) to determine high-accuracy TMC parameters for complex uranyl-based phases formed in storage or geological disposal environments (e.g. UO 3 (H 2 O) 2 , Ca[(UO 2 ) 6 O 4 (OH) 8 ] 8 H 2 O, (UO 2 ) 2 (SiO 4 ) 3 2H 2 O,…). The unforeseen COVID-19 pandemic led to the laboratory/campus closure since March 2020, that resulted in a significant delay in reaching milestones in a satisfactory manner, due to (i) the statewide recommendation from stop-working to later limited work in the lab and work-from-home (WFH), (ii) no in-person interactions, and (iii) a hiring freeze at UNLV. Therefore, a no cost extension (10/01/2021- 9/30/2022) was requested to help make up the time we lost during the global pandemic in 2020-2021, leading to paradigm shifts in the focus of the project in the following three main tasks: Task 1 (Computational), Task 2 (Experimental), and Task 3 (Final report, due on 12/29/2022).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Optimization and Techno-Economic Comparison of Regenerators and Recuperators in sCO2 Recompression Brayton Cycles for Concentrating Solar Power Applications

Supercritical CO2 power cycles might be capable of providing the cost reductions and efficiency improvements necessary to reach concentrating solar power (CSP) cost targets, but require large, highly effective recuperators. Fixed-bed regenerators are a periodic heat exchanger that could be an effective yet low-cost alternative to these recuperators. This study presents a techno-economic comparison of regenerators and recuperators for a 100 MWe supercritical CO2 power cycle for CSP applications. We quantify the levelized cost of energy (LCOE) for the power plant with both types of heat exchangers, and explore sensitivity of LCOE to parameters such as CSP-specific capital costs, power cycle component capital costs, and regenerator valve replacements costs. Results indicate that the incumbent printed circuit heat exchangers achieve the lowest LCOE, unless the upper extreme of PCHE capital cost and lower extremes of regenerator and valve capital and O&M costs are realized. Sensitivity analysis also illustrates that the primary heat exchanger cost is the most influential of power cycle components, and that CSP component capital cost is more influential than power cycle capital costs. This illustrates the importance of reducing the cost of heliostats, receivers, and thermal energy storage for achieving CSP LCOE targets.

OTHER INSTRUMENTATION,SOLAR ENERGY↗

Sensitivity of grassland carbon pools to plant diversity, elevated CO 2 , and soil nitrogen addition over 19 years

Significance The long-term effects of rising atmospheric carbon dioxide (CO 2 ), high rates of nitrogen deposition, and declining plant biodiversity on ecosystem carbon pools are uncertain and rarely assessed in concert yet represent key feedbacks to global climate change. In a 19-y study in an open-air grassland experiment, increasing planted species richness substantially enhanced ecosystem carbon storage, while elevated CO 2 and nitrogen addition treatments had only modest effects. Effects of the three global changes were largely additive, and stronger effects of species richness compared with CO 2 or nitrogen resulted from large enhancements in plant productivity relative to ecosystem losses. Our results suggest that biodiversity losses may influence carbon storage as much as or more than rising CO 2 or high nitrogen deposition rates.

54 ENVIRONMENTAL SCIENCES↗

Effects of Carbonic Acid-Rock Interactions on CO2/Brine Multiphase Flow Properties in the Upper Minnelusa Sandstones

Summary Carbon dioxide (CO2) injection into a deep saline aquifer can dissolve into formation brine and generate carbonic acid. The resulting acid can drive fluid-rock geochemical reactions. The impact of these fluid-rock geochemical reactions on porosity, permeability, and multiphase flow responses is relevant to the determination of CO2 storage capacity of deep saline aquifers. In this research, carbonic acid flooding experiments were performed on core samples consisting of poorly sorted, quartz-rich sand with laminated bedding from a possible CO2 storage target in northwest Wyoming. Complementary pre- and post-injection porosity and permeability, thin-section, Brunauer-Emmett-Teller (BET) surface area, mercury intrusion capillary pressure (MICP), and time-domain nuclear magnetic resonance (TD-NMR) measurements were conducted. Overall, both core porosity and permeability increased after a 7-day carbonic acid injection, from 6.2 to 8.4% and 1.6 to 3.7 md, respectively. We attributed these changes to carbonate mineral dissolution, which was evidenced by the effluent brine geochemistry, pore-throat size distribution (PTSD), and BET surface area. To be more specific, within the more-permeable section of core samples containing larger pore size, the permeability increment is apparent due to dolomite mineral grains and cements dissolution. However, for the lower-permeability section corresponding to the smaller pore size, mineral precipitation possibly lessened dissolution effects, leading to insignificant petrophysical properties changes. Consequently, the observed heterogeneous carbonic acid-rock interactions resulted in alterations of CO2/brine relative permeability (i.e., the initial CO2 saturation decreased and the CO2 flow capacity was enhanced). This research provides a fundamental understanding regarding effects of fluid-rock reactions on changes in static and multiphase flow properties of eolian sandstones, which lays the foundation for more accurate prediction/simulation of CO2 injection into deep saline aquifers.

Engineering↗

Reaction Mechanism of Electrodeposited ε-MnO 2 : A Proton-Centered Pathway in Aqueous Zn-Ion Systems

Aqueous Zn/MnO 2 batteries have garnered significant interests owing to their abundance, high theoretical specific capacity, safety, and low cost. However, large-scale application of these systems is limited by the incomplete understanding of the MnO 2 reaction chemistry. The different crystal lattice structures among MnO 2 polymorphs contribute to the variations in reported reaction mechanisms. Among them, ε-MnO 2 polymorph, the dominant phase in electrolytic manganese dioxide (EMD), is notably observed during the charge cycles of aqueous Zn/MnO 2 batteries. Here, in this work, we investigate the electrochemical behavior of an ε-MnO 2 cathode synthesized via electrodeposition from a ZnSO 4 and MnSO 4 electrolyte, onto a 3-dimensional carbon cloth substrate. Proton intercalation emerges as the dominant charge storage mechanism, critically enabling the reversibility of ε-MnO 2 during cycling, as revealed by operando synchrotron X-ray diffraction and X-ray absorption spectroscopy. Additionally, a proton-coupled dissolution/redeposition pathway operates alongside minor Zn 2+ intercalation, as quantified by Rietveld refinement. Morphological and chemical heterogeneities are studied by transmission X-ray microscopy further validates this reaction mechanism. These mechanistic insights provide the foundation for rationally designing Zn/MnO 2 batteries with optimized proton dynamics and charge transfer, advancing these systems as a viable solution for safe, cost-effective grid-scale energy storage.

36 MATERIALS SCIENCE↗

SPRUCE Radiocarbon analyses quantify peat carbon losses with increasing temperature in a whole ecosystem warming experiment, 2014-2020

This data set contains three *.csv data files with measurements of organic and inorganic carbon fractions and radiocarbon fractions in peat porewater profiles. Measurements of carbon fractions from enclosure drainage outflows are also included. Porewater profiles were collected up to four times annually from 2014 to 2020 with a piezometer and outflow samples were collected up to eight times annually in 2016 and 2017. Porewater organic and inorganic fractions were measured using a Finnigan Mat Delta V Isotope Ratio Mass Spectrometer and a Shimadzu Total Organic Carbon. Radiocarbon analyses were conducted at Lawrence Livermore National Laboratory (LLNL). The peat soils were subjected to deep peat heating (DPH) beginning in June of 2014 followed by whole ecosystem warming (WEW) in August of 2015 (Hanson et al. 2017). The experimental work was conducted in a Picea mariana [black spruce] – Sphagnum spp. bog forest in northern Minnesota, 40 km north of Grand Rapids, in the USDA Forest Service Marcell Experimental Forest (MEF).These changes in these inorganic and organic carbon fractions in response to whole ecosystem warming may alter decomposition and microbial communities, as well as overall soil carbon storage.

54 ENVIRONMENTAL SCIENCES↗