251 Search Results

Sedimentary geological formations are known to be great candidates for geological carbon sequestration. Published studies suggest the southeast of the United States contains many formations suitable for carbon storage. The Cassville 1 Stratigraphic Borehole well could act as a potential carbon reservoir for nearby energy resource facilities in Georgia, United States. Although studies have shown that porous formations are adequate for geological carbon sequestration, it is important to understand possible geochemical reactions between CO₂ and the targeted geological formation before injecting any fluids. In this study, a sandstone sample from the Cassville 1 well is being considered for geological carbonmore » sequestration in the Conasauga Group in Northwest Georgia. Here, the collected sandstone sample, consisting of quartz, K-feldspar, micas, kaolinite, and carbonate minerals such as calcite and dolomite, has a 6% porosity. Leveraging the formation composition and porosity, a one-dimensional continuum reactive transport model was built using CrunchFlow to assess possible geochemical reactions between injected CO₂ and the geological formation. Simulation results show that the carbonate minerals, calcite and dolomite, dissolve during the injection period of 10,000 days, increasing formation porosity from 6% to as much as 30%. The rate and extent of carbonate mineral dissolution and resulting porosity increase are highly sensitive to mineral reactive surface area values. No evidence of mineral precipitation was observed, suggesting that dissolution reactions will control porosity evolution during the CO₂ injection period.« less

This study details the initial development of a microwave heat-driven reactive CO₂ capture (RCC) process using the SrO/SrCO₃ cycle and graphitic carbon to absorb ppm-levels of CO₂ from humidified room temperature air and selectively convert it into CO. By combining first-principles density functional theory (DFT) simulations with thermogravimetric analysis (TGA) and X-ray diffraction (XRD) verification, it is demonstrated that SrO spontaneously absorbs moisture to generate Sr(OH)₂ followed by Sr(OH)₂*1H₂O, which then can spontaneously react with atmospheric levels of CO₂ to form SrCO₃. The resulting SrCO₃ can then react with solid carbon at elevated temperatures to selectively produce CO and regeneratemore » SrO. Graphitic carbon is an excellent microwave absorber that can quickly generate temperatures approaching 1000 °C and then cool to room temperature within minutes, potentially allowing for integration with intermittent electricity. It is shown that using microwaves to selectively heat a mixture of graphitic carbon and SrCO₃ produced CO with 85 ± 3% selectivity and stable performance over ten cycles. The rapid heating for release and room temperature CO₂ uptake processes appeared to prevent performance loss from particle sintering typically observed with traditional thermal systems. In conclusion, these results demonstrate a new RCC approach that adds to the growing number of potential technologies available for converting CO₂ to useful chemicals.« less

Cupriavidus necator H16 is a facultative chemolithotroph capable of using CO₂ as a carbon source, making it a promising organism for carbon-negative biomanufacturing of petroleum-based product alternatives. In contrast to model microbes, genetic engineering technologies are limited in C. necator, constraining its utility in basic and applied research. Here, we developed a genome engineering technology to efficiently mobilize, integrate, and express synthetic genetic elements (SGEs) in C. necator. We tested the chromosomal expression of four inducible promoters to optimize an engineered genetic landing pad for tunable gene expression. To demonstrate utility, we employed the SGE system to design, mobilize, andmore » express eight heterologous inorganic carbon uptake pathways in C. necator. We demonstrated all inorganic carbon uptake systems’ upregulated intracellular bicarbonate concentrations under heterotrophic conditions. This work establishes the utility of the SGE strategy for expedited integration and tunable expression of heterologous pathways, and enhances intracellular bicarbonate concentrations in C. necator.« less

Electrochemical separation technologies, such as capacitive deionization (CDI), are promising for addressing global energy and water challenges. However, there is a need to improve the performance, better understand property-performance relationships, and evaluate the longevity of CDI electrodes. This study explores the chemical modification of electrodes and the adjustment of CDI operating parameters. Results indicate that nitric acid (HNO3) conditioning of activated carbon cloth (ACC) electrodes removes metal oxides, introduces oxygen and nitrogen functionalities, and increases the specific capacitance (16% at 1 mV/s). Moreover, these changes in electrode properties positively impact device-level CDI performance. Through HNO3-conditioning of the ACC and tuningmore » of the operational parameters, this work demonstrates higher electrosorption capacity (4.0x), greater charge efficiency (90% vs 24%), and lower energy consumption (3.8x). Despite these enhancements, limitations of the HNO₃-conditioned ACC include decreased desorption kinetics and a 32% loss in electrosorption capacity after 200 cycles. Overall, this work provides guidance on using oxidative pretreatment via HNO₃ to modify ACC electrodes for CDI and evaluates the trade-offs associated with varying operational parameters.« less

Loewdin charges from density functional theory calculations were used here to obtain general, univariate linear correlations for the prediction of experimental Hammett parameters and relative reaction rates. While previous studies have established that Hirshfeld and CM5 charges perform strongly as univariate predictors, the near-ubiquitous Loewdin charges have not yet been evaluated. To this end, we assess the predictive capability of Loewdin charges for three chemical systems. First, we show that Loewdin charges outperform Hirshfeld and CM5 charges for Hammett parameter prediction. Second, we see that Loewdin charges generally perform comparably to Hirshfeld charges for predicting the relative rates of olefinmore » cleavage by photoexcited nitroarenes. The single case of poor correlation, between relative rates and the Loewdin charges on nitrogen sites, is ameliorated when considering the net charge on the NO₂ group. Third, we show that Loewdin, Hirshfeld, and CM5 charges all perform very well for generating correlations for relative reaction rates for C–H activation of 9-(4-X-phenyl)-9H-fluorene substrates by a transition metal catalyst. The equations generated throughout the study enable the prediction of Hammett parameters and relative reaction rates. Finally, these tools can accelerate synthetic and experimental studies by enabling the in silico prediction of uncharacterized chemical properties.« less

Modern land management faces unprecedented uncertainty regarding future climates, novel disturbance regimes, and unanticipated ecological feedbacks. Mitigating this uncertainty requires a cohesive landscape management strategy that utilizes multiple methods to optimize benefits while hedging risks amidst uncertain futures. We used a process-based landscape simulation model (LANDIS-II) to forecast forest management, growth, climate effects, and future wildfire dynamics, and we distilled results using a decision support tool allowing us to examine tradeoffs between alternative management strategies. We developed plausible future management scenarios based on factorial combinations of restoration-oriented thinning prescriptions, prescribed fire, and wildland fire use. Results were assessed continuously formore » a 100-year simulation period, which provided a unique assessment of tradeoffs and benefits among seven primary topics representing social, ecological, and economic aspects of resilience. Projected climatic changes had a substantial impact on modeled wildfire activity. In the Wildfire Only scenario (no treatments, but including active wildfire and climate change), we observed an upwards inflection point in area burned around mid-century (2060) that had detrimental impacts on total landscape carbon storage. While simulated mechanical treatments (~ 3% area per year) reduced the incidence of high-severity fire, it did not eliminate this inflection completely. Scenarios involving wildland fire use resulted in greater reductions in high-severity fire and a more linear trend in cumulative area burned. Mechanical treatments were beneficial for subtopics under the economic topic given their positive financial return on investment, while wildland fire use scenarios were better for ecological subtopics, primarily due to a greater reduction in high-severity fire. Benefits among the social subtopics were mixed, reflecting the inevitability of tradeoffs in landscapes that we rely on for diverse and countervailing ecosystem services. This study provides evidence that optimal future scenarios will involve a mix of active and passive management strategies, allowing different management tactics to coexist within and among ownerships classes. Our results also emphasize the importance of wildfire management decisions as central to building more robust and resilient future landscapes.« less

Light element alloying in iron is required to explain density deficit and seismic wave velocities in Earth’s core. However, the light element composition of the Earth’s core seems hard to constrain as nearly all light element alloying would reduce the density and sound velocity (elastic moduli). The alloying light elements include oxidizing elements like oxygen and sulfur and reducing elements like hydrogen and carbon, yet their chemical effects in the alloy system are less discussed. Moreover, Fe-X-ray Absorption Near Edge Structure (Fe-XANES) fingerprints have been studied for silicate materials with ferrous and ferric ions, while not many X-ray absorption spectroscopymore » (XAS) studies have focused on iron alloys, especially at high pressures. To investigate the bonding nature of iron alloys in planetary interiors, we presented X-ray absorption spectroscopy of iron–nitrogen and iron–carbon alloys at high pressures up to 50 GPa. Together with existing literature on iron–carbon, –hydrogen alloys, we analyzed their edge positions and found no significant difference in the degree of oxidation among these alloys. Pressure effects on edge positions were also found negligible. Our theoretical simulation of the valence state of iron, alloyed with S, C, O, N, and P also showed nearly unchanged behavior under pressures up to 300 GPa. This finding indicates that the high pressure bonding of iron alloyed with light elements closely resembles bonding at the ambient conditions. We suggest that the chemical properties of light elements constrain which ones can coexist within iron alloys.« less

Lithium-ion batteries offer the highest energy density of any currently available portable energy storage technology. By using different anode materials, these batteries could have an even greater energy density. One material, tin, has a theoretical lithium capacity (994 mAh/g) over three-times higher than commercial carbon anode materials. Unfortunately, to achieve this high capacity, bulk tin undergoes a large volume expansion, and the material pulverizes during cycling, giving a rapid capacity fade. To mitigate this issue, tin must be scaled down to the nano-level to take advantage of unique micromechanics at the nanoscale. Synthesis techniques for Sn nanoparticle anodes are costlymore » and overly complicated for commercial production. A novel one-step process for producing carbon-coated Sn nanoparticles via spark plasma erosion (SPE) shows great promise as a simple, inexpensive production method. The SPE method, characterization of the resulting particles, and their high-capacity reversible electrochemical performance as anodes are described. With only a 10% addition of these novel SPE carbon-coated Sn particles, one anode composition demonstrated a reversible capacity of ~460 mAh/g, achieving the theoretical capacity of that particular electrode formulation. These SPE carbon-coated Sn nanoparticles are drop-in ready for present commercial lithium-ion anode processing and would provide a ~10% increase in the total capacity of current commercial lithium-ion cells.« less

Fine roots are key to ecosystem-scale nutrient, carbon (C), and water cycling, yet our understanding of fine root trait variation within and among tropical forests, one of Earth’s most C-rich ecosystems, is limited. We characterized root biomass, morphology, nutrient content, and arbuscular mycorrhizal fungal (AMF) colonization to 1.2 m depths across four distinct lowland Panamanian forests, and related root characteristics to soil C stocks. We hypothesized that: (H1) Fine root characteristics vary consistently with depth across seasonal tropical forests, with deeper roots exhibiting more exploratory traits, such as for deep water acquisition; (H2) fine root characteristics vary among tropical forestsmore » mainly in surface soils, where resource availability also varies. Here we found consistent variation with depth across the four forests, including decreased root biomass, root tissue density, and AMF, and increased specific root length. Among the forests, there was variation in some fine root characteristics, including greater surface root biomass and lower SRL in the wettest forest, and smaller fine root diameter in the driest forest. We also found that root characteristics were related to total soil C stocks, which were positively related to root biomass and negatively related to specific root length. These results indicate emergent properties of root variation with depth across tropical forests, and show site-scale variation in surface root characteristics. Future work could explore the flexibility in root characteristics under changing conditions such as drought.« less

Lithium-ion batteries (LIBs) face increasingly stringent demands as their application expands into new areas, including extreme temperatures and fast charging. To meet these demands, the electrolyte should enable fast lithium-ion transport and form stable interphases on electrodes simultaneously. In practice, however, improving one aspect often compromises another. For instance, the trend toward electrolytes forming anion-derived interphases typically reduces transport efficiency due to weak-solvating solvents. Here, we propose that instead of relying on anions to form the interphase, leveraging both solvents and anions to form interphases can potentially lead to a balancing point between robust interphase formation and effective ion transport.more » Guided by this design principle, 2,2-difluoroethyl ethyl carbonate (DFDEC) was identified as the promising solvent. With the new electrolyte using DFDEC as the major solvent and lithium bis(fluorosulfonyl) imide (LiFSI) as the salt, graphite||LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) full cells are capable of fast charging and demonstrate long-term cycling stability with a cutoff voltage of 4.5 V. Notably, the battery shows a capacity retention of 84.3% after 500 cycles with an average Coulombic efficiency (CE) as high as 99.93%. This new electrolyte also enables stable battery cycling across a wide temperature range (-20 to 60 °C), with excellent capacity retention.« less