Prof. James (Jerry) Spivey: a tribute to an extraordinary researcher and mentor
The manuscript describes Prof. Sovey's contribution to Catalysis.
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The manuscript describes Prof. Sovey's contribution to Catalysis.
Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.
Decarbonizing the industrial sector is critical to achieve carbon dioxide (CO2) emissions reductions goals of the Biden Administration. Currently available decarbonization options include electrification, fuel switching to zero carbon fuels like green hydrogen (H2) and carbon capture and storage (CCS). Application of post-combustion carbon capture (PCCC) technology in the power sector, as well as research at the U.S. Department of Energy's Fossil Energy and Carbon Management (FECM) Office has shown that its application in the industrial sector could have co-benefits in the form of emissions reductions of non-CO2 regulated pollutants. For example, solvent based PCCC systems require pre-conditioning of flue gas to remove sulfur and particulate matter (PM) upstream of the CO2 absorber. However, there is a lack of understanding about the type of non-CO2 pollutants which can be captured and the amount of reduction possible. PCCC application differs across industrial sectors as it depends on the availability of decarbonization options, characteristics of industrial processes and the amount and composition of pollutant flows. Certain facilities can also have multiple effluent flows with or without a CO2 stream. As such, understanding industrial processes and their effluent flows in detail is required to quantify the co-benefits opportunities presented by PCCC. Considering this requirement, the goal of this analysis is to develop a high-resolution inventory of effluent flows from facilities of 8 industrial sectors in the U.S. These industrial sectors - ethanol, ammonia, cement, steel, natural gas processing, hydrogen, petroleum refining and wood and pulp products - have carbon-intensive effluent flows, and thus are prime candidates for PCCC applications. In this study, we map the composition of pollutant flow from flue stacks across the identified facilities. Using data available in three Environmental Protection Agency (EPA) databases - the Green House Gas Reporting Program (GHGRP), the National Emissions Inventory (NEI) and the Toxic Release Inventory (TRI), we create a combined inventory which lists the type, amount, and concentration of pollutant flows. Using total weight of the pollutant flow back calculated from observed data for CO2 concentrations in flue gas for individual sectors, we calculate the concentration of each pollutant in the flue gas stream. Thus, the resultant emissions inventory includes the following details for each facility in the sector: facility-level and if possible, process-level pollutant flows, concentrations of pollutants in the flue gas, and geographical coordinates of the facilities. A detailed statistical analysis and summary allows us to search for erroneous data and remove them from the final inventory. The generation of the inventory is achieved using a python-based framework which can recreate this inventory for other industrial sectors as well as using newer releases of emission inventories from EPA. The statistical analysis performed on the inventory is also calibrated and automated to identify outliers efficiently.
There are increasing concerns that anthropogenic inputs of carbon dioxide into the Earth system have the potential for climate change. In response to these concerns, the GSFC Laboratory for Hydrospheric Processes has formed the Ocean Carbon Science Team (OCST) to contribute to greater understanding of the global ocean carbon cycle. The overall goals of the OCST are to: 1) detect changes in biological components of the ocean carbon cycle through remote sensing of biooptical properties, 2) refine understanding of ocean carbon uptake and sequestration through application of basic research results, new satellite algorithms, and improved model parameterizations, 3) develop and implement new sensors providing critical missing environmental information related to the oceanic carbon cycle and the flux of CO2 across the air-sea interface. The specific objectives of the OCST are to: 1) establish a 20-year time series of ocean color, 2) develop new remote sensing technologies, 3) validate ocean remote sensing observations, 4) conduct ocean carbon cycle scientific investigations directly related to remote sensing data, emphasizing physiological, empirical and coupled physical/biological models, satellite algorithm development and improvement, and analysis of satellite data sets. These research and mission objectives are intended to improve our understanding of global ocean carbon cycling and contribute to national goals by maximizing the use of remote sensing data.
In this paper, we review relevant technologies—primarily thermochemical and plasma conversion processes—that use natural gas to produce solid carbon and hydrogen, and recent research progress and commercial activities. Technical challenges include the high energetic requirements necessary for methane activation and, for some catalytic processes, the separation of solid carbon product from the spent catalyst. We assess current and new carbon product markets that could be served given technological advances, and we discuss technical barriers and potential areas of research to address these needs. We provide preliminary economic analysis where it was concluded that the cost of pyrolytically produced CO2-free hydrogen can be potentially reduced to <$4/kg target levels with the co-production and sale of sufficiently high-value carbon products.
Recent advances in remote sensing technology and its use for global studies of the biospheric processes are described. Special consideration is given to research related to two issues: (1) quantifying the impacts of natural vegetation and its changing patterns of occurrence on the atmospheric CO2 budget and (2) assessing wetlands (such as the swamps and marshes of Florida's Everglades) as sources of atmospheric CH4. The results include the data from NOAA-AVHRR sensors and from experiments in remote detection of plant growth rate.
Total column measurements of CO2 (XCO2) have been proposed as a possible way to estimate emissions from large urban regions. Using calculations from the Weather Research and Forecasting (WRF) model with a 1km emissions field, we investigate the viability of both real and proposed observing systems consisting of surface and/or column measurements for constraining emission sources of various types and sizes in the San Francisco Bay Area. We find that column observations are best suited for assessing enhancements downwind of very large emissions sources. For smaller sources (such as highways), in situ surface monitors are required to provide sufficient sensitivity. We explore methods for estimating emissions from the real and simulated observations.
A high-performance spontaneous Raman scattering (SRS) system for measuring quantitative species concentration and temperature in high-pressure flames is now operational. The system is located in Glenn s Engine Research Building. Raman scattering is perhaps the only optical diagnostic technique that permits the simultaneous (single-shot) measurement of all major species (N2, O2, CO2, H2O, CO, H2, and CH4) as well as temperature in combustion systems. The preliminary data acquired with this new system in a 20-atm hydrogen-air (H2-air) flame show excellent spectral coverage, good resolution, and a signal-to-noise ratio high enough for the data to serve as a calibration standard. This new SRS diagnostic system is used in conjunction with the newly developed High- Pressure Gaseous Burner facility (ref. 1). The main purpose of this diagnostic system and the High-Pressure Gaseous Burner facility is to acquire and establish a comprehensive Raman-scattering spectral database calibration standard for the combustion diagnostic community. A secondary purpose of the system is to provide actual measurements in standardized flames to validate computational combustion models. The High-Pressure Gaseous Burner facility and its associated SRS system will provide researchers throughout the world with new insights into flame conditions that simulate the environment inside the ultra-high-pressure-ratio combustion chambers of tomorrow s advanced aircraft engines.
Longer duration missions to the moon, to Mars, and on the International Space Station (ISS) increase the likelihood of accidental fires. NASA's fire safety program for human-crewed space flight is based largely on removing ignition sources and controlling the flammability of the material on-board. There is ongoing research to improve the flammability characterization of materials in low gravity; however, very little research has been conducted on fire suppression in the low-gravity environment. Although the existing suppression systems aboard the Space Shuttle (halon 1301, CF3Br) and the ISS (CO2 or water-based form) may continue to be used, alternative effective agents or techniques are desirable for long-duration missions. The goal of the present investigation is to: (1) understand the physical and chemical processes of fire suppression in various gravity and O2 levels simulating spacecraft, Mars, and moon missions; (2) provide rigorous testing of analytical models, which include detailed combustion-suppression chemistry and radiation sub-models, so that the model can be used to interpret (and predict) the suppression behavior in low gravity; and (3) provide basic research results useful for advances in space fire safety technology, including new fire-extinguishing agents and approaches.
Biomass burning is an important source of trace gases and particles which can influence air quality on local, regional, and global scales. With wildfire events increasing due to changes in land use, increasing population, and climate change, characterizing wildfire emissions and their evolution is vital. In this work we report in situ airborne measurements of carbon dioxide (CO2), methane (CH4), water vapor (H2O), ozone (O3), and formaldehyde (HCHO) from nine wildfire events in California between 2013 and 2016, which were sampled as part of the Alpha Jet Atmospheric eXperiment (AJAX) based at NASA Ames Research Center. One of those fires, the Soberanes Megafire, began on 22 July 2016 and burned for three months. During that time, five flights were executed to sample emissions near and downwind of the Soberanes wildfire. In situ data are used to determine enhancement ratios (ERs), or excess mixing ratio relative to CO2, as well as assess O3 production from the fire. Changes in the emissions as a function of fire evolution are explored. Air quality impacts downwind of the fire are addressed using ground-based monitoring site data, satellite smoke products, and the Community Multiscale Air Quality (CMAQ) photochemical grid model.
Listed are various graphs and tables for illustrations related to Point IX of a list of works conducted by the USSR in accordance with the Joint Soviet-American Research Program on improving methods of thermal sounding from satellites.
The development of high power nuclear pumped lasers is discussed. The excitation mechanism of continuous wave (CW) HeNe nuclear pumped lasers is studied and a CO2 nuclear pumped laser is used to demonstrate the CW output in the order of watts. The assumption that high power densities are only achievable by volume fission fragment sources is used to identify laser gases which are compatible with UF6 by excited states lifetime measurements. The examination of Xe2, XeF, and KrF under nuclear irradiation to determine if they are good candidates for nuclear-pumped lasers is described.
NREL is developing robust microbial strains and scalable fermentation technologies for converting biomass sugars to fuels and biochemicals, and one-carbon (C1) gaseous substrates (e.g., CO2, CO, CH4) to high-value products. Core capabilities include: (1) Fermentation optimization of aerobic, microaerophilic, and anaerobic cultivation processes of gas and traditional liquid fermentation R&D; (2) Gas mass transfer R&D and CFD modeling for improved reactor design and gas mixing (3) Metabolic engineering in CRISPR editing tools to improve titer, rates, and yields; (4) Probing and optimizing carbon, redox, and energy flux using transcriptomics and fluxomic techniques; and (5) Consolidated bioprocessing (CBP) using cellulose and hemicellulose directly to minimize pretreatment.
Recent interest in monitoring atmospheric CO2 focuses attention on infrared remote sensing using the 2-micron lidar/differential absorption lidar (DIAL) technique. Quantum detectors are critical components in this technique, and many research efforts concentrate on developing such devices for the 2-micron wavelength. Characterization results of InGaAsSb quantum detectors for the 2-micron wavelength range are presented, including experimental setup and procedure. Detectors are prototype devices manufactured by using separate absorption and multiplication (SAM) structures. Characterization experiments include V-I measurements, spectral response and its variation with bias voltage and temperature, noise measurements, noise-equivalent-power (NEP) and detectivity calculations, and signal-to-noise ratio (SNR) estimation. A slight increase in the output signal occurred with increased bias voltage and was associated with a noise level increase. Cooling down the detectors reduces noise and shifts the cutoff wavelength to shorter values. Further improvement in the design and manufacturing process, by increasing the device gain and lowering its noise level, is necessary to meet the required CO2 lidar/DIAL specifications.
Recent interest in monitoring atmospheric CO2 focuses attention on infrared remote sensing using the 2-micron lidar/differential absorption lidar (DIAL) technique. Quantum detectors are critical components in this technique, and many research efforts concentrate on developing such devices for the 2-micron wavelength. Characterization results of InGaAsSb quantum detectors for the 2-micron wavelength range are presented, including experimental setup and procedure. Detectors are prototype devices manufactured by using separate absorption and multiplication (SAM) structures. Characterization experiments include V-I measurements, spectral response and its variation with bias voltage and temperature, noise measurements, noise-equivalent-power (NEP) and detectivity calculations, and signal-to-noise ratio (SNR) estimation. A slight increase in the output signal occurred with increased bias voltage and was associated with a noise level increase. Cooling down the detectors reduces noise and shifts the cutoff wavelength to shorter values. Further improvement in the design and manufacturing process, by increasing the device gain and lowering its noise level, is necessary to meet the required CO2 lidar/DIAL specifications.
During the Atmospheric Carbon and Transport–America (ACT–America) suborbital mission (ACT-America) Mission Spring 2018 campaign, ASCENDS CarbonHawk Experiment Simulator (ACES), an intensity modulated continuous wave (IMCW) lidar system funded by NASA’s Science Mission Directorate, measured differential optical depths leading to partial-column CO2 lidar retrievals while flying aboard the C-130 aircraft across North America striving to advance technology critical to measuring column carbon dioxide mixing ratios (XCO2) remotely. ACES was developed by NASA Langley Research Center in the aims to have an active remote sensing system able to accurately measure XCO2 from space independent of the presence of sunlight, land surface type, and even through thin clouds. Differential absorption optical depth measurements made during the fourth campaign of ACT-America in Spring of 2018 were processed, analyzed and compared to on board in situ derived differential optical depth CO2 measurements.
This study presents an approach for quantifying when injected carbon dioxide (CO 2 ) stabilizes pursuant to carbon capture and storage (CCS) project permitting and site closure requirements. The distribution of mobile-phase CO 2 (CO 2 plume) will evolve within the storage reservoir during and after injection through both physical and chemical trapping mechanisms. CCS policies generally agree that the CO 2 plume’s migratory behavior in post-injection should demonstrate nonendangerment to the environment but do not provide specific guidance on how to meet the definition of plume stabilization, generating some uncertainty for operators. Plume stability herein means the CO 2 plume 1) changes size minimally and predictably in the storage reservoir such that it will not cross key boundaries identified in the permit and 2) does not pose a threat to human health, underground sources of drinking water (USDWs), and the environment because of lateral migration to areas where leakage pathways may exist. Published literature on plume metrics was reviewed to determine which metric(s) may be most appropriate for determining CO 2 plume stability. A technical approach that defines plume stabilization by estimating the rate of change in the geographic footprint of the CO 2 plume with respect to time was developed and illustrated using a case study from North Dakota, USA, as a proposed solution for CCS operators to apply at the project permitting stage. Any prospective CCS operator may benefit from using the same approach to inform the selection of pore space lease and monitoring areas and develop post-injection site care plans.
This research effort will develop a novel nanodischarge reactor loaded with nanotemplated catalysts to achieve high-efficiency plasma-enhanced conversion of CO2 and methane for the production of chemicals or fuels. The primary objective of this study is to demonstrate low temperature operation of a novel nanoplasma catalysis reactor that is characterized by a uniform discharge. Another objective is to address the most significant challenge in the plasma-catalysis hybrid system, which is to achieve the strongest synergistic interaction between the plasma and catalyst and to increase the selectivity for producing methanol and alkanes/alkenes. This enhanced synergy will be enabled by using bimetallic nanoparticles synthesized on nanorods present on surfaces of a nanotemplated oxide support.