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At least 37 records · Page 2

The Global Methane Budget 2000–2017

Understanding and quantifying the global methane (CH 4 ) budget is important for assessing realistic pathways to mitigate climate change. Atmospheric emissions and concentrations of CH 4 are continuing to increase, making CH 4 the second most important human-influenced greenhouse gas in terms of climate forcing, after carbon dioxide (CO 2 ). Assessing the relative importance of CH 4 in comparison to CO 2 is complicated by its shorter atmospheric lifetime, stronger warming potential, and atmospheric growth rate variations over the past decade, the causes of which are still debated. Two major difficulties in reducing uncertainties arise from the variety of geographically overlapping CH 4 sources and from the destruction of CH 4 by short-lived hydroxyl radicals (OH). To address these difficulties, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate new research aimed at improving and regularly updating the global methane budget. Following Saunois et al. (2016), we present here the second version of the living review paper dedicated to the decadal methane budget, integrating results of top-down studies (atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up estimates (including process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Electrochemical Characterization of Molten Salt Chemistry During Atmospheric Ingressions

This report describes the salt chemistry and sedimentation studies that were completed in FY23 as part of the Pyrochemical Fuel Cycles – ANL project. The primary objective of these activities was to employ electrochemical methods in order to quantify and gain insights into the reaction mechanisms associated with the interaction of O2 and moisture impurities with the molten chloride salts used for the pyrochemical processing of nuclear materials. If not monitored and controlled, the ingression of these atmospheric impurities can lead to changes in the salt redox conditions and initiate the formation of oxide particles, potentially resulting in operational and safeguards challenges. By elucidating the mechanisms underlying the formation of oxide particles, we can effectively monitor the conditions of the salt and design systems to mitigate the influence of atmospheric O2 and H2O. To achieve these goals, we designed a test system that allowed for precisely controlled gas ingressions into the molten salt vessel. This system included on-line monitoring provided by electrochemical probes that enable near real-time measurements of the salt conditions throughout the course of the experiment. Using this system, we systematically varied experimental conditions, including O2/Ar flow rates and O2 concentrations, to comprehensively understand their impact on solid particle formation. We also used a particle size and shape analyzer to characterize the particles that were generated. Tests in FY23 concentrated on the formation of CeO2 particles, but we also prepared a separate apparatus targeting UO2 particles for use in FY24. We additionally conducted extensive modeling activities in support of this work. This included multiphysics simulations of the gas ingressions along with the development of a machine learning workflow to enable accelerated molecular dynamics modeling of the molten salt chemistry of LiCl-KCl-UCl3. The combination of experimental and modeling tools has allowed us to begin to get a more complete understanding of the reactions that occur when atmospheric ingressions occur in pyroprocessing systems.

Guo, Jicheng↗

Probing Interfacial Reaction Pathways in Atomic Layer Deposition on Sulfide Superionic Conductors

Sulfide superionic conductors (e.g., argyrodite Li 6 PS 5 Cl, LPSCl) are extremely promising for all solid-state batteries, but poor atmospheric stability and high interfacial reactivity limit widespread adoption. Coating LPSCl powders with ultrathin coatings using atomic layer deposition (ALD) mitigates these problems, protecting against atmospheric degradation and reducing reactivity with Li metal, yielding more stable cycling. Despite significant promise, the ALD mechanism is unknown, hampering the development of new coating chemistries. In this study, we elucidate the mechanism for Al 2 O 3 ALD on LPSCl using trimethyl aluminum (TMA) and H 2 O by combining in situ Fourier transform infrared spectroscopy, ex situ solid-state magic angle spinning nuclear magnetic resonance, UV Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We determine that ALD Al 2 O 3 nucleates promptly via TMA reaction with native —OH, —SH, and PS 3 -OH groups to form transient C–Al–O(S) species that are rapidly hydrolyzed during the subsequent H 2 O exposure. This reversible transformation maintains surface nucleophilicity and prevents sulfide decomposition. The resulting layer-by-layer growth leads to highly conformal Al 2 O 3 coatings on LPSCl that are readily scalable to ≥ 50 g quantities using a rotating drum fixture. This detailed understanding of ALD surface reactions provides critical insights guiding the selection of future ALD chemistries with improved performance.

atomic layer deposition↗

Characterizing Pore-Scale Geochemical Alterations in Eagle Ford and Barnett Shale from Exposure to Hydraulic Fracturing Fluid and CO 2 /H 2 O

As demand increases for an affordable energy source that is tied to an environmental obligation to reduce greenhouse gas emissions and water usage, there is a growing consideration in shale production utilizing processes such as 1) enhancing hydrocarbon recovery via carbon dioxide (CO 2 ) flooding, 2) using CO 2 as a fracturing agent to minimize water use, and 3) storing CO 2 in depleted shale formations to mitigate emissions to the atmosphere. Understanding the geochemical reactions and alterations that occur as shale is exposed to fluids and CO 2 is necessary to develop and optimize each of these processes for field applications. While the majority of shale formations are stimulated using traditional fracturing fluid, some may be fractured using CO 2 or other non-traditional means. We examine the effect fracturing fluid has on shale and how it behaves with secondary exposure to dry CO 2 or CO 2 -saturated water using in situ Fourier Transform infrared spectroscopy (FTIR), feature relocation scanning electron microscopy (SEM), and surface area and pore size analysis using volumetric gas sorption. These techniques were performed on Eagle Ford and Barnett shale samples that were exposed to fracturing fluid and unexposed (as received). Shales that have been exposed to traditional fracturing fluid experienced two reaction fronts. The first reaction front was formed during exposure to the fracturing fluid (pH of ~1.4). A secondary reaction front was formed as a result of CO 2 -saturated fluid exposure in the form of carbonic acid (pH ~5.6). These two different reaction mechanisms drove multiple dissolution and precipitation cycles which altered petrophysical properties of the shale and could lead to a significant impact on flow pathways. FTIR showed that equilibration of carbonate dissolution and precipitation cycles could take as long as 35 days. Samples exposed to fracturing fluid showed significantly less carbonate reactivity compared to those exposed to water. Pore size analysis results indicate exposure to fracturing fluid blocked small nanopores (10-15 nm) reducing BET surface area and total pore volume. SEM results show barite precipitated heavily during exposure to fracturing fluid. It appeared that carbonic acid was able to extract sulfur from organic matter to form gypsum evaporites. The mineralogical (barite precipitation and calcite dissolution/precipitation) and pore-scale alterations observed in these samples may lead to enhancement of flow pathways for injected CO 2 or produced hydrocarbons.

04 OIL SHALES AND TAR SANDS↗

Persistence of soil organic carbon caused by functional complexity

Soil organic carbon management has the potential to aid climate change mitigation through drawdown of atmospheric carbon dioxide. To be effective, such management must account for processes influencing carbon storage and re-emission at different space and time scales. Achieving this requires a conceptual advance in our understanding to link carbon dynamics from the scales at which processes occur to the scales at which decisions are made. Here, we propose that soil carbon persistence can be understood through the lens of decomposers as a result of functional complexity derived from the interplay between spatial and temporal variation of molecular diversity and composition. For example, co-location alone can determine whether a molecule is decomposed, with rapid changes in moisture leading to transport of organic matter and constraining the fitness of the microbial community, while greater molecular diversity may increase the metabolic demand of, and thus potentially limit, decomposition. This conceptual shift accounts for emergent behaviour of the microbial community and would enable soil carbon changes to be predicted without invoking recalcitrant carbon forms that have not been observed experimentally. Finally, functional complexity as a driver of soil carbon persistence suggests soil management should be based on constant care rather than one-time action to lock away carbon in soils.

54 ENVIRONMENTAL SCIENCES↗

A cryogenic continuously rotating half-wave plate mechanism for the POLARBEAR-2b cosmic microwave background receiver

In this report we present the design and laboratory evaluation of a cryogenic continuously rotating half-wave plate (CHWP) for the POLARBEAR-2b (PB-2b) cosmic microwave background receiver, the second installment of the Simons Array. PB-2b will observe at 5200 m elevation in the Atacama Desert of Chile in two frequency bands centered at 90 GHz and 150 GHz. In order to suppress atmospheric 1/f noise and mitigate systematic effects that arise when differencing orthogonal detectors, PB-2b modulates linear sky polarization using a CHWP rotating at 2 Hz. The CHWP has a 440 mm clear aperture diameter and is cooled to ≈50 K in the PB-2b receiver cryostat. It consists of a low-friction superconducting magnetic bearing and a low-torque synchronous electromagnetic motor, which together dissipate < 2 W. During cooldown, a grip-and-release mechanism centers the rotor to < 0.5 mm, and during continuous rotation, an incremental optical encoder measures the rotor angle with a noise level of 0.1 μrad/Hz. We discuss the experimental requirements for the PB-2b CHWP, the designs of its various subsystems, and the results of its evaluation in the laboratory. The presented CHWP has been deployed to Chile and is expected to see first light on PB-2b in 2020 or 2021.

47 OTHER INSTRUMENTATION↗

The Simons Observatory: Cryogenic half wave plate rotation mechanism for the small aperture telescopes

We present the requirements, design, and evaluation of the cryogenic continuously rotating half-wave plate (CHWP) for the Simons Observatory (SO). SO is a cosmic microwave background polarization experiment at Parque Astronómico de Atacama in northern Chile that covers a wide range of angular scales using both small (Ø0.42 m) and large (Ø6 m) aperture telescopes. In particular, the small aperture telescopes (SATs) focus on large angular scales for primordial B-mode polarization. To this end, the SATs employ a CHWP to modulate the polarization of the incident light at 8 Hz, suppressing atmospheric 1/f noise and mitigating systematic uncertainties that would otherwise arise due to the differential response of detectors sensitive to orthogonal polarizations. The CHWP consists of a 505 mm diameter achromatic sapphire HWP and a cryogenic rotation mechanism, both of which are cooled down to ~50 K to reduce detector thermal loading. Under normal operation, the HWP is suspended by a superconducting magnetic bearing and rotates with a constant 2 Hz frequency, controlled by an electromagnetic synchronous motor. We find that the number of superconductors and the number of magnets that make up the superconducting magnetic bearing are important design parameters, especially for the rotation mechanism’s vibration performance. The rotation angle is detected through an angular encoder with a noise level of 0.07 μrad √ $\overline{s}$. During a cooldown process, the rotor is held in place by a grip-and-release mechanism that serves as both an alignment device and a thermal path. In this paper, we provide an overview of the SO SAT CHWP: its requirements, hardware design, and laboratory performance.

47 OTHER INSTRUMENTATION↗

Solar geoengineering may not prevent strong warming from direct effects of CO2 on stratocumulus cloud cover

Discussions of countering global warming with solar geoengineering assume that warming owing to rising greenhouse gas concentrations can be compensated by artificially reducing the amount of sunlight Earth absorbs. However, here we show that solar geoengineering may not be fail-safe to prevent global warming because CO2 has direct effects on cloud cover: it reduces cloud cover by modulating the longwave radiative cooling within the atmosphere, which is not mitigated by solar geoengineering. We use high-resolution simulations of clouds to show that under a sustained solar geoengineering scenario, the direct CO2 effects may lead to loss of subtropical stratocumulus clouds at concentrations above 1700~ppm. Because stratocumulus clouds cover large swaths of subtropical oceans and cool Earth by reflecting incident sunlight, their loss would trigger strong (about 5 K) global warming. Thus, the results highlight that, at least in an extreme scenario, solar geoengineering may be incapable to counter greenhouse-gas driven global warming.

Schneider, Tapio↗

Decarbonization of Wastewater Treatment with Microalgae Processes.

Microalgae can contribute to the decarbonization of wastewater treatment by municipalities, industries and agriculture, by substituting sunlight for energy intensive conventional treatment processes, while capturing nutrients and carbon in the algal biomass. The carbon fixed into the algal biomass can be converted to renewable natural gas (RNG) using anaerobic digestion or into renewable diesel and sustainable aviation fuel (SAF) using hydrothermal liquefaction (HTL), with greatly reduce the carbon footprints compared to conventional fuels. Bioplastics, biofertilizers and other bioproducts from microalgae biomass also provide potential benefits in greenhouse gas (GHG) reduction and domestic supply chains. Microalgae technologies can counter eutrophication caused by harmful algal blooms by recovering nutrients, N and P, from wastewaters, and even from very low nutrient concentrations found in surface waters. CO2 is required in microalgae cultivation and wastewater treatment to support maximal rates of the photosynthesis, with the CO2 obtained from the wastes themselves, other local sources or even atmospheric CO2. Greenhouse gas mitigation with microalgae processes is based on life cycle assessments, comparing such green processes with current energy intensive wastewater treatment, and nutrient reduction technologies. Microalgae technologies are specifically relevant to smaller, often disadvantaged, communities, where currently about 5,000 algae wastewater treatment ponds are operated by public utilities with many more are operated by industries. However, many, if not most, of these pond facilities require urgent technology upgrades to achieve the potential and goals of low cost GHG mitigation and efficient nutrient recycling. MicroBio Engineering Inc. is developing and has demonstrated several technologies that combine innovative carbon mitigation and decarbonization technologies for a circular economy, with longer-term potential for large-scale biofuels and biofertilizer production.

09 BIOMASS FUELS↗

Decarbonization of Wastewater Treatment with Microalgae Processes.

Microalgae can contribute to the decarbonization of wastewater treatment by municipalities, industries and agriculture, by substituting sunlight for energy intensive conventional treatment processes, while capturing nutrients and carbon in the algal biomass. The carbon fixed into the algal biomass can be converted to renewable natural gas (RNG) using anaerobic digestion or into renewable diesel and sustainable aviation fuel (SAF) using hydrothermal liquefaction (HTL), with greatly reduce the carbon footprints compared to conventional fuels. Bioplastics, biofertilizers and other bioproducts from microalgae biomass also provide potential benefits in greenhouse gas (GHG) reduction and domestic supply chains. Microalgae technologies can counter eutrophication caused by harmful algal blooms by recovering nutrients, N and P, from wastewaters, and even from very low nutrient concentrations found in surface waters. CO2 is required in microalgae cultivation and wastewater treatment to support maximal rates of the photosynthesis, with the CO2 obtained from the wastes themselves, other local sources or even atmospheric CO2. Greenhouse gas mitigation with microalgae processes is based on life cycle assessments, comparing such green processes with current energy intensive wastewater treatment, and nutrient reduction technologies. Microalgae technologies are specifically relevant to smaller, often disadvantaged, communities, where currently about 5,000 algae wastewater treatment ponds are operated by public utilities with many more are operated by industries. However, many, if not most, of these pond facilities require urgent technology upgrades to achieve the potential and goals of low cost GHG mitigation and efficient nutrient recycling. MicroBio Engineering Inc. is developing and has demonstrated several technologies that combine innovative carbon mitigation and decarbonization technologies for a circular economy, with longer-term potential for large-scale biofuels and biofertilizer production.

09 BIOMASS FUELS↗

Decarbonization of Wastewater Treatment with Microalgae Processes.

Microalgae can contribute to the decarbonization of wastewater treatment by municipalities, industries and agriculture, by substituting sunlight for energy intensive conventional treatment processes, while capturing nutrients and carbon in the algal biomass. The carbon fixed into the algal biomass can be converted to renewable natural gas (RNG) using anaerobic digestion or into renewable diesel and sustainable aviation fuel (SAF) using hydrothermal liquefaction (HTL), with greatly reduce the carbon footprints compared to conventional fuels. Bioplastics, biofertilizers and other bioproducts from microalgae biomass also provide potential benefits in greenhouse gas (GHG) reduction and domestic supply chains. Microalgae technologies can counter eutrophication caused by harmful algal blooms by recovering nutrients, N and P, from wastewaters, and even from very low nutrient concentrations found in surface waters. CO2 is required in microalgae cultivation and wastewater treatment to support maximal rates of the photosynthesis, with the CO2 obtained from the wastes themselves, other local sources or even atmospheric CO2. Greenhouse gas mitigation with microalgae processes is based on life cycle assessments, comparing such green processes with current energy intensive wastewater treatment, and nutrient reduction technologies. Microalgae technologies are specifically relevant to smaller, often disadvantaged, communities, where currently about 5,000 algae wastewater treatment ponds are operated by public utilities with many more are operated by industries. However, many, if not most, of these pond facilities require urgent technology upgrades to achieve the potential and goals of low cost GHG mitigation and efficient nutrient recycling. MicroBio Engineering Inc. is developing and has demonstrated several technologies that combine innovative carbon mitigation and decarbonization technologies for a circular economy, with longer-term potential for large-scale biofuels and biofertilizer production.

09 BIOMASS FUELS↗

A Novel Sustainable Process for Multilayer Graphene Synthesis Using CO 2 from Ambient Air

Graphene produced by different methods can present varying physicochemical properties and quality, resulting in a wide range of applications. The implementation of a novel method to synthesize graphene requires characterizations to determine the relevant physicochemical and functional properties for its tailored application. We present a novel method for multilayer graphene synthesis using atmospheric carbon dioxide with characterization. Synthesis begins with carbon dioxide sequestered from air by monoethanolamine dissolution and released into an enclosed vessel. Magnesium is ignited in the presence of the concentrated carbon dioxide, resulting in the formation of graphene flakes. These flakes are separated and enhanced by washing with hydrochloric acid and exfoliation by ammonium sulfate, which is then cycled through a tumble blender and filtrated. Raman spectroscopic characterization, FTIR spectroscopic characterization, XPS spectroscopic characterization, SEM imaging, and TEM imaging indicated that the graphene has fifteen layers with some remnant oxygen-possessing and nitrogen-possessing functional groups. The multilayer graphene flake possessed particle sizes ranging from 2 µm to 80 µm in diameter. BET analysis measured the surface area of the multilayer graphene particles as 330 m 2 /g, and the pore size distribution indicated about 51% of the pores as having diameters from 0.8 nm to 5 nm. This study demonstrates a novel and scalable method to synthesize multilayer graphene using CO 2 from ambient air at 1 g/kWh electricity, potentially allowing for multilayer graphene production by the ton. The approach creates opportunities to synthesize multilayer graphene particles with defined properties through a careful control of the synthesis parameters for tailored applications.

36 MATERIALS SCIENCE↗

Hanford Tank Vapors in Worker Breathing Zones - Source, Dispersion, and Receptor Data - 20373

A wide range of organic and inorganic chemicals from historical Hanford Site processes are now stored in 177 underground storage tanks at the Hanford tank farms. Workers at the Hanford tank farms have expressed concerns about chemical vapor exposures for many years. During the spring of 2014, worker reports of chemical odors and/or symptoms prompted the development of the Savannah River National Laboratory Hanford Tank Vapor Assessment Team (TVAT) and their resulting independent assessment and recommendations concerning tank farm worker reports of vapors. The Tank Vapor Assessment report included a hypothesis that 'vapors coming out of tanks in high concentration (bolus) plumes sporadically intersected with the breathing zones of workers, resulting in brief but intense exposures to some workers.' The focus of this effort is to present current knowledge to describe the mechanisms by which workers may experience short duration vapor concentrations above background in the tank farms environment. The TVAT hypothesis that workers have experienced concentrations approaching 80% of the tank headspace up to 3 meters (10 feet) from tank sources is not supported by sampling data or modeling results. Modeling indicates that concentrations are quickly reduced from the source, and that the upper end of predicted concentrations at worker breathing zones are a factor of 10 or more lower than source concentrations. Area measurements corroborate the fact that worker breathing zone concentrations are 10 to 100 times lower than source concentrations, and events with elevated concentrations are rare. These reduced vapor concentration levels may result in detectable odors or irritation, depending on a worker's specific odor threshold and sensitivity to the chemical species. Short-duration vapor events may be mitigated by evaluating daily atmospheric conditions in conjunction with planned tank farm activities. Monitoring changing conditions related to tank vapors concentrations at the source and within worker breathing zone is also an important step to protect workers from short duration elevated concentration events. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mitigating the allergenicity of peanut allergen Ara h 1 by cold atmospheric pressure argon plasma jet

Abstract BACKGROUND Peanut allergy is recognized as a major food allergy that triggers severe and even fatal symptoms. Avoidance of peanuts in the diet is the main option for current safety management. Processing techniques reducing peanut allergenicity are required to develop other options. Cold plasma is currently considered as a novel non‐thermal approach to alter protein structure and has the potential to alleviate immunoreactivity of protein allergen. RESULTS The application of a cold argon plasma jet to peanut protein extract could reduce the amount of a 64 kDa protein band corresponding to a major peanut allergen Ara h 1 using sodium dodecyl sulfate–polyacrylamide gel electrophoresis, but the overall protein size distribution did not change significantly. A decrease in peanut protein solubility was a possible cause that led to the loss of protein content in the soluble fraction. Immunoblotting and enzyme‐linked immunosorbent assay elucidated that the immunoreactivity of Ara h 1 was significantly decreased with the time treated with plasma. Ara h 1 antigenicity reduced by 38% after five scans (approximately 3 min) of cold argon plasma jet treatment, and the reduction was up to 66% after approximately 15 min of treatment. CONCLUSION The results indicate that cold argon plasma jet treatment could be a suitable platform for alleviating the immunoreactivity of peanut protein. This work demonstrates an efficient, compact, and rapid platform for mitigating the allergenicity of peanuts, and shows great potential for the plasma platform as a non‐thermal technique in the food industry. © 2023 Society of Chemical Industry.

Hsu, Fu‐Chiun↗

Reimagining Earth in the Earth System

Abstract Terrestrial, aquatic, and marine ecosystems regulate climate at local to global scales through exchanges of energy and matter with the atmosphere and assist with climate change mitigation through nature‐based climate solutions. Climate science is no longer a study of the physics of the atmosphere and oceans, but also the ecology of the biosphere. This is the promise of Earth system science: to transcend academic disciplines to enable study of the interacting physics, chemistry, and biology of the planet. However, long‐standing tension in protecting, restoring, and managing forest ecosystems to purposely improve climate evidences the difficulties of interdisciplinary science. For four centuries, forest management for climate betterment was argued, legislated, and ultimately dismissed, when nineteenth century atmospheric scientists narrowly defined climate science to the exclusion of ecology. Today's Earth system science, with its roots in global models of climate, unfolds in similar ways to the past. With Earth system models, geoscientists are again defining the ecology of the Earth system. Here we reframe Earth system science so that the biosphere and its ecology are equally integrated with the fluid Earth to enable Earth system prediction for planetary stewardship. Central to this is the need to overcome an intellectual heritage to the models that elevates geoscience and marginalizes ecology and local land knowledge. The call for kilometer‐scale atmospheric and ocean models, without concomitant scientific and computational investment in the land and biosphere, perpetuates the geophysical view of Earth and will not fully provide the comprehensive actionable information needed for a changing climate.

Meteorology & Atmospheric Sciences↗

Solar Contamination in Extreme-precision Radial-velocity Measurements: Deleterious Effects and Prospects for Mitigation

Solar contamination, due to moonlight and atmospheric scattering of sunlight, can cause systematic errors in stellar radial velocity (RV) measurements that significantly detract from the ∼10 cm s{sup −1} sensitivity required for the detection and characterization of terrestrial exoplanets in or near habitable zones of Sun-like stars. The addition of low-level spectral contamination at variable effective velocity offsets introduces systematic noise when measuring velocities using classical mask-based or template-based cross-correlation techniques. Here we present simulations estimating the range of RV measurement error induced by uncorrected scattered sunlight contamination. We explore potential correction techniques, using both simultaneous spectrometer sky fibers and broadband imaging via coherent fiber imaging bundles, that could reliably reduce this source of error to below the photon-noise limit of typical stellar observations. We discuss the limitations of these simulations, the underlying assumptions, and mitigation mechanisms. We also present and discuss the components designed and built into the NEID (NN-EXPLORE Exoplanet Investigations with Doppler spectroscopy) precision RV instrument for the WIYN 3.5 m telescope, to serve as an ongoing resource for the community to explore and evaluate correction techniques. We emphasize that while “bright time” has been traditionally adequate for RV science, the goal of 10 cm s{sup −1} precision on the most interesting exoplanetary systems may necessitate access to darker skies for these next-generation instruments.

79 ASTRONOMY AND ASTROPHYSICS↗