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At least 937 records · Page 52

The Tropospheric Lifetimes of Halocarbons and Their Reactions with OH Radicals: an Assessment Based on the Concentration of CO-14

Chemical reaction with hydroxyl radicals formed in the troposphere from ozone photolysis in the presence of methane, carbon monoxide and nitrogen oxides provides an important removal mechanism for halocarbons containing C-H and C = C double bonds. The isotropic distribution in atmospheric carbon monoxide was used to quantify the tropospheric hydroxyl radical distribution. Here, this methodology is reevaluated in the light of recent chemical kinetic data evaluations and new understandings gained in the life cycles of methane and carbon monoxide. None of these changes has forced a significant revision in the CO-14 approach. However, it is somewhat more clearly apparent how important basic chemical kinetic data are to the accurate establishment of the tropospheric hydroxyl radical distribution.

Derwent, Richard G.↗

Carbonates, surfates, phosphates, nitrates, and organic materials: Their association in a Martian meteorite

The debate concerning the evolution of CO2 on Mars continues. It would appear that in order to explain the valley networks and other relict fluvial landforms it is necessary to accept that liquid water was once present at the surface of Mars. This in turn requires, at some point in the planet's history, a higher surface temperature than exists today, proposition explained traditionally by an early dense CO2, atmosphere. However, there are a number of problems with this notion: for instance, CO2 alone is not an efficient greenhouse gas because of its tendency to form clouds. Moreover, if there was an early dense CO2 atmosphere, it is necessary to explain where the elemental constituents now reside. There are two possibilities for the latter, namely loss to outer space of atmospheric CO2 or the formation of vast carbonate deposits. While some models of atmospheric loss predict that up to 0.4 bar of CO2 could be removed from the Martian surface, this is still not enough to account for the original atmospheric inventory, usually considered to have been in the range of 1-5 bar. Thus, most models of the evolution of the Martian surface require removal of CO2 from the atmosphere and into carbonate deposits. However, as yet, the evidence for the existence of carbonates on Mars is fairly scant. This is an issue that would have been resolved by results obtained from Mars Observer.

Wright, I. P.↗

Adsorption of Carbon Dioxide, Ammonia, Formaldehyde, and Water Vapor on Regenerable Carbon Sorbents

Results are presented on the development of reversible sorbents for the combined carbon dioxide, moisture, and trace‐contaminant (TC) removal for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). The currently available life support systems use separate units for carbon dioxide, trace contaminants, and moisture control, and the long‐term objective is to replace the above three modules with a single one. Furthermore, the current TC‐control technology involves the use of a packed bed of acid‐impregnated granular charcoal, which is nonregenerable, and the carbon‐based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. In this study, several carbon sorbents were fabricated and tested for simultaneous carbon dioxide, ammonia, formaldehyde, and water sorption. Multiple adsorption/vacuum‐regeneration cycles were demonstrated at room temperature, and also the enhancement of formaldehyde sorption by the presence of ammonia in the gas mixture.

Wojtowicz, Marek A.↗

Stability of IRA-45 solid amine resin as a function of carbon dioxide absorption and steam desorption cycling

The removal of CO2 from the NASA Space Station's cabin atmosphere, which may be undertaken by a solid-amine water (steam)-desorbed system, is presently evaluated with a view to long-term amine resin stability and adsorption/desorption cycling by means of an automated laboratory flow-testing facility. While the CO2-adsorption capacity of the IRA-45 amine resin used gradually decreased over time, the rate of degradation significantly decreased after the first 10 cycles. Attention is given to the presence (and possible need for removal) of trimethylamine in the process air downstream of the resin bed.

Wood, Peter C.↗

Evaluation of Cryofreezer Technology through Simulation and Testing (DRAFT)

A cryofreezer system is being evaluated as a new method of compressing and storing carbon dioxide (CO2) in an Advanced Life Support (ALS) Environmental Control and Life Support System (ECLSS). A cryocooler is used to provide cold temperatures and heat removal while CO2 freezes and accumulates around a coldtip. The CO2 can then be stored as a liquid or high-pressure gas after it has been accumulated. This system was originally conceived as an In-Situ Resource Utilization (ISRU) application for collecting CO2 from the Mars atmosphere to be converted to methane fuel with a Sabatier reaction. In the ALS application, this system could collect CO2 from the International Space Station (ISS) Carbon Dioxide Removal Assembly (CDRA) for delivery to the Sabatier reactor. The Sabatier reaction is an important part of proposed Air Revitalization System (ARS) for ALS, and technology sharing is often possible between ISRU and ARS applications in CO2 processing systems. A prototype system developed and initially tested by Lockheed Martin Astronautics is now being evaluated in the Air Revitalization Technology Evaluation Facility (ARTEF) at NASA Johnson Space Center (JSC). This paper will discuss testing conducted through December 2004 to examine the performance and capacity of the system under a variety of input conditions. A simulation of the system was developed simultaneously using the Aspen Custom Modeler (ACM) software package. Several approaches using varying levels of detail could be used when modeling the system, and this paper will discuss the assumptions and choices made in this simulation, as well as the validity of the simulation for predicting performance of the prototype unit.

Anderson, Molly↗

The Effect of a Carbon Fiber Layer Between the Cathode and the Current Collector on Battery Cell Performance

Contact resistance between the cathode active material (CAM) and the Al current collector can be reduced by applying carbon coatings to the Al current collector surface. However, this process requires an additional step of carbon layer coating on the current collector, which increases both manufacturing costs and processing time. In the present work, an interlayer of continuous unsized carbon fibers aligned in one direction (CF interlayer), is introduced between the Al current collector and the NMC811 cathode during cathode deposition on the Al current collector. This single-step approach eliminates the need for the additional carbon layer coating on the current collector. Additionally, this approach removes the use of toxic solvents and insulative polymers used for making the carbon coating. The CF interlayer improves the rate capability at higher C-rates. The CF interlayer lowers the contact resistance between the cathode particles and the current collector while improving the activation energy of charge transfer. The peel test showed that the CF interlayer does not affect the adhesion strength of the cathode layer with the current collector.

25 ENERGY STORAGE↗

Co-Adsorption of Ammonia and Formaldehyde on Regenerable Carbon Sorbents for the Primary Life Support System (PLSS)

Results are presented on the development of a reversible carbon sorbent for trace-contaminant (TC) removal for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). The current TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal, which is deemed non-regenerable, while the carbon-based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. Data on concurrent sorption and desorption of ammonia and formaldehyde, which are major TCs of concern, are presented in this paper. A carbon sorbent was fabricated by dry impregnation of a reticulated carbon-foam support with polyvinylidene chloride, followed by carbonization and thermal oxidation in air. Sorbent performance was tested for ammonia and formaldehyde sorption and vacuum regeneration, with and without water present in the gas stream. It was found that humidity in the gas phase enhanced ammonia-sorption capacity by a factor larger than two. Co-adsorption of ammonia and formaldehyde in the presence of water resulted in strong formaldehyde sorption (to the point that it was difficult to saturate the sorbent on the time scales used in this study). In the absence of humidity, adsorption of formaldehyde on the carbon surface was found to impair ammonia sorption in subsequent runs; in the presence of water, however, both ammonia and formaldehyde could be efficiently removed from the gas phase by the sorbent. The efficiency of vacuum regeneration could be enhanced by gentle heating to temperatures below 60 deg.

Wojtowicz, Marek A.↗

A bioenergy-focused versus a reforestation-focused mitigation pathway yields disparate carbon storage and climate responses

Limiting global warming to 2 °C requires urgent action on land-based mitigation. This study evaluates the biogeochemical and biogeophysical implications of two alternative land-based mitigation scenarios that aim to achieve the same radiative forcing. One scenario is primarily driven by bioenergy expansion (SSP226Lu-BIOCROP), while the other involves re/afforestation (SSP126Lu-REFOREST). We find that overall, SSP126Lu-REFOREST is a more efficient strategy for removing CO2 from the atmosphere by 2100, resulting in a net carbon sink of 242 ~ 483 PgC with smaller uncertainties compared to SSP226Lu-BIOCROP, which exhibits a wider range of -78 ~ 621 PgC. However, SSP126Lu-REFOREST leads to a relatively warmer planetary climate than SSP226Lu-BIOCROP, and this relative warming can be intensified in certain re/afforested regions where local climates are not favorable for tree growth. Despite the cooling effect on a global scale, SSP226Lu-BIOCROP reshuffles regional warming hotspots, amplifying summer temperatures in vulnerable tropical regions such as Central Africa and Southeast Asia. Our findings highlight the need for strategic land use planning to identify suitable regions for re/afforestation and bioenergy expansion, thereby improving the likelihood of achieving the intended climate mitigation outcomes.

54 ENVIRONMENTAL SCIENCES↗

Development of an In-Situ Leaching Technology for Extracting Residual Uranium from Remediated Soil - 20099

Site-specific chemical solutions for extracting uranium were developed and evaluated for treating previously remediated soil at a former thorium mill tailings site, known as the Former Rare Earths Facility (REF), in West Chicago, Illinois. Prior remediation efforts had resulted in residual sand and gravel aggregate that met the soil cleanup standards. The target soil contains residual levels of uranium, which continues to leach into the site groundwater at levels exceeding groundwater protection standards (GWPS). A series of bench-scale tests were conducted to evaluate the efficacy and viability of in-situ leaching (ISL) technology to treat the target soil for the purposes of attaining uranium GWPS at the REF. Specific objectives of the bench-scale tests entailed identification and selection of optimal leaching, quantification of the extent and rate of uranium released as a function of chemical composition, chemical concentrations, chemical residence times, and obtaining critical data to estimate treatment costs. A combination of sodium bicarbonate and sodium carbonate reagent was the most effective leaching solution. In general, leaching solutions containing a higher concentration of sodium carbonate demonstrated superior uranium leaching capabilities. Removal of 50% of the uranium mass from the soil matrix was adequate for achieving compliance with the site-specific GWPS. After six to seven pore volume flushes (PVFs), the uranium leaching effectiveness of all leaching solutions was similar. The amount of initial uranium removed with each subsequent PVF was minimal, suggesting limited solubility of the remaining mass of uranium. The effects of leaching duration were significant and persisted through at least the first five consecutive PVFs. Leaching of uranium also resulted in leaching of several non-uranium constituents, many of which exceeded applicable National Pollutant Discharge Elimination System (NPDES) standards. Given historical operations and waste disposal practices at the site, leaching of non-uranium constituents was expected. Hydrochloric acid was used to stabilize treated soil. Savings of approximately $148 million in direct and indirect remediation costs are expected with an ISL alternative compared to the excavation and landfill disposal remediation option. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Trends and limits of CO 2 capture in solid and liquid sorbents at standard conditions

Carbon capture and storage (CCS) plays a critical role in achieving climate change mitigation targets, offering a pathway to decarbonize power generation, industrial processes, and heat production while addressing atmospheric CO 2 removal. While CCS technologies are technically advanced, the widespread adoption of 100 % CO 2 capture capacities such as 1 mol of CO 2 /mol of material and 1 g CO 2 /g storage (targeted by the DARPA, Defense Sciences Office, USA Govt.) has raised questions about the feasibility of achieving higher capture capacities. In the context of limiting global warming to 1.5°C, reaching 100 % CO 2 capture capacity is increasingly necessary, with residual emissions requiring complementary carbon dioxide removal (CDR) technologies. This review exclusively focuses on the CO 2 capture capacities of various sorbents under standard conditions, using different evaluation metrics. This study explores the performance of solid and liquid sorbents under standard conditions, analyzing factors including surface area, pore structure, solvent type, and functionalization to identify materials optimized for industrial-scale CCS applications. Emerging sorbents, including ILs, MOFs, COFs, POPs, DES, RCC, hybrid materials, and reactive sorbents, offer significant potential for enhanced selectivity and energy-efficient regeneration. Through a systematic assessment of gravimetric, volumetric, and molar capacities, the study provides insights into material efficiencies and trade-offs, offering guidance on optimizing sorbent selection for specific applications. The research advances understanding of scalable CCS technologies, contributing to global efforts to achieve net-zero emissions and address the pressing challenge of climate change.

Absorption↗

Reviving the carbon sink: The influence of moderate wind disturbance in a secondary temperate mixed forest

Global forests are increasingly exposed to climate-driven perturbations, which may in turn alter their climate mitigation potential. As tropical cyclones expand poleward due to climate warming, wind disturbances in temperate forests have become increasingly frequent. The consequences of moderate wind disturbances remain poorly understood, hindering efforts to quantify their role in the global carbon cycle. Here, we used 16 years of continuous eddy covariance and biometric measurements to investigate the impacts of moderate wind disturbances on the structure and carbon sink dynamics of a temperate forest in Northeast China. Following Typhoon Maysak in 2020, the mortality of large trees (particularly the aging pioneer species) increased ninefold, whereas that of small trees decreased by nearly half. Both stand basal area and leaf area index were reduced between 2019 and 2023, with aging pioneer tree species being more vulnerable than mid-to-late species to wind disturbances. Shifts in species composition altered the environmental sensitivity of forest carbon sink function. Unexpectedly, wind disturbances reversed the declining trends in net ecosystem production and ecosystem carbon use efficiency of this secondary forest. A novel composite structural indicator—the standardized leaf area index (the maximum leaf area supported by per basal area of the stand)—provided robust predictions (R 2 > 0.4) of carbon sink dynamics throughout the study period. The selective removal of less efficient pioneer trees accelerated succession and reversed the aging-related decline in forest carbon sink strength and carbon use efficiency. In conclusion, these findings highlight the potential role of moderate wind disturbances in enhancing forest carbon sink function and offer a framework for understanding, assessing, and predicting forest carbon dynamics under increasing disturbance frequencies driven by climate change.

Carbon sink↗

Generating Aromatics From CO2 on Mars or Natural Gas on Earth

Methane to aromatics on Mars ( METAMARS ) is the name of a process originally intended as a means of converting Martian atmospheric carbon dioxide to aromatic hydrocarbons and oxygen, which would be used as propellants for spacecraft to return to Earth. The process has been demonstrated on Earth on a laboratory scale. A truncated version of the process could be used on Earth to convert natural gas to aromatic hydrocarbon liquids. The greater (relative to natural gas) density of aromatic hydrocarbon liquids makes it more economically feasible to ship them to distant markets. Hence, this process makes it feasible to exploit some reserves of natural gas that, heretofore, have been considered as being "stranded" too far from markets to be of economic value. In the full version of METAMARS, carbon dioxide is frozen out of the atmosphere and fed to a Sabatier reactor along with hydrogen (which, on Mars, would have been brought from Earth). In the Sabatier reactor, these feedstocks are converted to methane and water. The water is condensed and electrolyzed to oxygen (which is liquefied) and hydrogen (which is recycled to the Sabatier reactor). The methane is sent to an aromatization reactor, wherein, over a molybdenum-on-zeolite catalyst at a temperature 700 C, it is partially converted into aromatic hydrocarbons (specifically, benzene, toluene, and naphthalene) along with hydrogen. The aromatics are collected by freezing, while unreacted methane and hydrogen are separated by a membrane. Most of the hydrogen is recycled to the Sabatier reactor, while the methane and a small portion of the hydrogen are recycled to the aromatization reactor. The partial recycle of hydrogen to the aromatization reactor greatly increases the catalyst lifetime and eases its regeneration by preventing the formation of graphitic carbon, which could damage the catalyst. (Moreover, if graphitic carbon were allowed to form, it would be necessary to use oxygen to remove it.) Because the aromatics contain only one hydrogen atom per carbon atom, METAMARS produces four times as much propellant from a given amount of hydrogen as does a related process that includes the Sabatier reaction and electrolysis but not aromatization. In the terrestrial version of METAMARS, the Sabatier reactor and electrolyzer would be omitted, while the hydrogen/ methane membrane-separating membrane, the aromatization reactor, and the unreacted-gas-recycling subsystem would be retained. Natural gas would be fed directly to the aromatization reactor. Because natural gas consists of higher hydrocarbons in addition to methane, the aromatization subprocess should be more efficient than it is for methane alone.

Muscatello, Anthony C.↗

The Staged, Pressurized Oxy-Combustion Technology: Status and Application to Boiler Retrofits to Yield Carbon-Negative Power via Biomass

Recognizing the benefits of pressurization and fuel staging on the efficiency of oxy-combustion, the staged, pressurized oxy-combustion (SPOC) process was introduced in 2012. The combination of fuel staging and pressurized oxy-combustion results in a more compact plant, a higher plant efficiency and reduced costs for pollutant and greenhouse gas removal compared with plants equipped with conventional carbon capture. This approach to power generation enables a modular boiler design and optimizes the plant for flexible operation, which is essential to meet the demands of the modern grid when it contains intermittent power sources. Originally designed to burn coal, the SPOC process is well-suited for biomass because the combustion of biomass leads to a high moisture content in the flue gas and the SPOC process is able to recover the latent heat of this moisture, enhancing system performance over that of traditional biomass combustion at atmospheric pressure. The present work is focused on evaluating the potential for utilizing the SPOC process in retrofit applications wherein the boilers of an existing plant are replaced with the SPOC process, and woody biomass is used as the fuel to yield carbon-negative power. Two applications are considered: power generation and cogeneration (heat and power). Modeling these systems in Aspen Plus demonstrates that the SPOC process surpasses the performance of baseline plants with post-combustion capture (PCC) for both power generation and cogeneration. Specifically, compared to a PCC equipped plant, the SPOC power plant has 33% higher efficiency, and the SPOC cogeneration plant reaches 42% higher net energy. Experimentally, the existing SPOC facility was fired for the first time with 100% biomass and after minor improvements were made to the feeding system, the facility demonstrated excellent performance during startup, steady-state operation and turndown.

Carbon capture and storage↗

Thermal Processing Conditions for the Synthesis of Near Theoretical Density Li 5 La 3 Ta 2 O 12 Ceramics for Ceramic Dual-Mode Detectors

A family of Li-containing garnet compounds, extensively investigated for Li-ion solid electrolyte applications, show great potential to be developed into transparent ceramic dual-mode scintillators. In particular, Li 5 La 3 Ta 2 O 12 (LLTaO) shows promise as an efficient dual-mode scintillator due to its high Li content, high density, non-hygroscopicity, and high effective-Z. Often the synthesis of LLTaO ceramics involves solid state processing techniques starting with oxide and carbonate powders, calcining, sintering for the removal of residual porosity, and post-processing. This study focuses on two objectives: (1) establishing thermal processing boundary conditions for a flexible alkoxide-based sol-gel method for synthesizing fine-grained powders; and (2), consolidating powders via hot-pressing to form high-density ceramics. In this study, near single-phase ceramics were achieved by hot-pressing sol-gel powders with varying amounts of excess Li. Rietveld refinements were used to analyze X-ray diffraction data and provide a quantitative evaluation of the phases present in the hot pressed ceramics. Some of the diffraction data showed large low angle peak asymmetry, suggesting the presence of two cubic Li 5 La 3 Ta 2 O 12 garnet phases with different lattice parameters. Depending on the synthesis and processing conditions, the refinement revealed ~ 90 wt% concentration of a phase with a ≈ 12.8 Å and ~ 10 wt% concentration of a phase with a ≈ 12.9 Å, indicating a remaining excess of Li in the hot pressed ceramics in the large lattice parameter phase. These synthesis experiments allowed for the determination of a baseline for Li loss during hot-pressing. X-ray excited radioluminescence and photoluminescence excitation and emission spectra were obtained from the hot pressed ceramics. In conclusion, the measured emission spectra featured broad tantalate emission and line emissions likely from a rare-earth impurity.

36 MATERIALS SCIENCE↗

Closed-loop recycling of mixed polyesters via catalytic methanolysis and monomer separations

A sustainable plastics future will require high recycling rates and the use of biogenic feedstocks, which together are catalyzing interest in replacing fossil fuel-derived, noncircular polyolefin packaging materials with bio-based, chemically recyclable polyesters. Here, in this study, we present a catalytic methanolysis process capable of depolymerizing both fossil fuel- and bio-based polyesters, including polyethylene terephthalate (PET), polylactic acid, polybutylene adipate terephthalate and polybutylene succinate in one reactor under mild conditions with high monomer yields. We scaled this process to 1 kg and integrated separations engineering using activated carbon, crystallization, extraction and distillation to remove contaminants and recover individual monomers from depolymerized mixed polyesters with high yield and purity. PET synthesized from monomers isolated from postconsumer materials showed comparable mechanical and thermal properties to PET from commercial monomers. Techno-economic analysis and life cycle assessment show that this process is economically viable and exhibits lower environmental impacts than primary production of respective polymers.

09 BIOMASS FUELS↗

Production of C-14 and Stable Ion Beams at the Argonne Tandem Linac Accelerator System with the ECR3 Ion Source

The Argonne Tandem Linac Accelerator System (ATLAS) at Argonne National Laboratory (ANL) paused production of carbon-14 ion beams with the removal of the Tandem Van de Graaff in 2013. Installation of ECR3, an Electron Cyclotron Resonance Ion Source, returned that production capability to ATLAS, with the first C-14 beam delivered in December 2020. Information is presented on C-14 beam current, gas consumption and N-14 filtering techniques using stripping foils at different sections of ATLAS. ECR3 also fulfilled the operational goal of adding flexibility to ATLAS stable beam production capabilities. Beneficial impacts to ATLAS operation, beam development and experimental programs are discussed.

Scott, R. H.↗

Atmosphere control

Atmospheric control studies emphasized the carbon dioxide problem. Trace contaminants are removed by solid adsorbents and by catalytic oxidation. Humidity control and storage systems for atmospheric constituents are briefly summarized.

Jones, W. L.↗

Removal of ammonia from urine vapor by a dual-catalyst system

The feasibility of removing ammonia from urine vapor by a low-temperature dual-catalyst system has been demonstrated. The process is based on the catalytic oxidation of ammonia to a mixture of nitrogen, nitrous oxide, and water, followed by a catalytic decomposition of the nitrous oxide into its elements. Potential ammonia oxidation and nitrous oxide decomposition catalysts were first screened with artificial gas mixtures, then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual-catalyst bed arrangement was found that achieved the removal of ammonia and also organic carbon, and recovered water of good quality from urine vapor.

Budininkas, P.↗