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At least 19 records

Selective and Stable In-Promoted Fe Catalyst for Syngas Conversion to Light Olefins

A selective and stable alumina-supported In-promoted Fe catalyst (10 mol % In based on Fe) was discovered for converting syngas (2:1 H 2 /CO ratio) to olefins with high selectivity (45% with CO 2 included) and a remarkable stability (72 h run) at a CO conversion of 10% at 400 °C and 5 bar. The X-ray photoelectron spectroscopy results indicated that incorporating In into Fe catalysts changed the chemical bonding state of Fe and Fe/In composition near the surface layers, which affected the catalytic reactivity. Steady-state isotopic transient kinetic analysis showed that more stable CHx fragments are present on the catalyst surface when incorporating In into Fe, which can promote C–C coupling reaction toward olefins. Our study demonstrates that introducing In into Fe catalysts on Al 2 O 3 support can lower CO activation abilities. It has more impacts on lowering hydrogenation activity, which permits more C–C couplings and like of “ene” hydrogenation. Furthermore, weakening CO adsorption both in terms of sites and strength encouraged CO toward hydrocarbons rather than CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Limitation of C4 photosynthesis by low carbonic anhydrase activity increases with temperature but does not influence mesophyll CO2 conductance

The CO2-concentrating mechanism (CCM) in C4 plants is initiated by the uptake of bicarbonate (HCO3…) via phosphoenolpyruvate carboxylase (PEPC). Generation of HCO3– for PEPC is determined by the interaction between mesophyll CO2 conductance and the hydration of CO2 to HCO3– by carbonic anhydrase (CA). Genetic reduction of CA was previously shown not to limit C4 photosynthesis under ambient atmospheric partial pressures of CO2 (pCO2). However, CA activity varies widely across C4 species and it is unknown if there are specific environmental conditions (e.g. high temperature) where CA may limit HCO3– production for C4 photosynthesis. Additionally, CA activity has been suggested to influence mesophyll conductance, but this has not been experimentally tested. We hypothesize that CA activity can limit PEPC at high temperatures, particularly at low pCO2, but does not directly influence gm. Here we tested the influence of genetically reduced CA activity on photosynthesis and gm in the C4 plant Zea mays under a range of pCO2 and temperatures. Reduced CA activity limited HCO3– production for C4 photosynthesis at low pCO2 as temperatures increased, but did not influence mesophyll conductance. Therefore, high leaf CA activity may enhance C4 photosynthesis under high temperature when stomatal conductance restricts the availability of atmospheric CO2.

Plant Sciences↗

Allowable exposure limits for carbon dioxide during extravehicular activity

The intent was to review the research pertaining to human exposure to carbon dioxide (CO2) and to recommend allowable exposure limits for extravehicular activity (EVA). Respiratory, renal, and gastrointestinal systems may be adversely affected by chronic low dose CO2 exposure. Ventilation was increased 15 percent with 1 percent CO2 and 50 percent with 2 percent CO2. Chronic exposure to less than 2 percent CO2 led to 20 day cycles of uncompensated and compensated respiratory acidosis. Acid-base changes were small. Histopathologic changes in guinea pig lungs have been noted with long term exposure to 1 percent CO2. No changes were seen with exposure to 0.5 percent CO2. Cycling of bone calcium stores with associated changes in blood and urinary calcium levels occurs with long term CO2 exposure. Histologic changes in bone have been noted in guinea pigs exposed to 1 percent CO2. Renal calcification has been noted in guinea pigs with exposure to as low as 0.5 percent CO2. An increase in gastric acidity was noted in subjects with long term exposure to 1 percent CO2. Cardiovascular and neurologic function were largely unaffected. A decrease in the incidence of respiratory, renal, and gastrointestinal disease was noted in submariners coincident with a decrease in ambient CO2 from 1.2 percent to 0.8-0.9 percent. Oxygen (O2) and CO2 stimulate respiration independently and cumulatively. The addition of CO2 to high dose O2 led to the faster onset of seizure activity in mice. Experiments evaluating the physiologic responses to intermittent, repetitive exposures to low dose CO2 and 100 percent O2 mixtures should be performed. A reduction in the current NASA standard for CO2 exposure during EVA of 1 percent (7.6 mmHg) for nominal and 2 percent (15.2 mmHg) for heavy exertion to 0.5 percent (3.8 mmHg) for nominal and 1 percent (7.6 mmHg) for heavy exertion may be prudent. At a minimum, the current NASA standard should not be liberalized.

Seter, Andrew J.↗

Development of a Pulsed 2-Micron Integrated Path Differential Absorption Lidar for CO2 Measurement

Atmospheric carbon dioxide (CO2) is an important greenhouse gas that significantly contributes to the carbon cycle and global radiation budget on Earth. Active remote sensing of CO2 is important to address several limitations that contend with passive sensors. A 2-micron double-pulsed, Integrated Path Differential Absorption (IPDA) lidar instrument for ground and airborne atmospheric CO2 concentration measurements via direct detection method is being developed at NASA Langley Research Center. This active remote sensing instrument will provide an alternate approach of measuring atmospheric CO2 concentrations with significant advantages. A high energy pulsed approach provides high-precision measurement capability by having high signal-to-noise ratio level and unambiguously eliminates the contamination from aerosols and clouds that can bias the IPDA measurement. Commercial, on the shelf, components are implemented for the detection system. Instrument integration will be presented in this paper as well as a background for CO2 measurement at NASA Langley research Center

Singh, Upendra N.↗

Catalytic Site Requirements for N2O Decomposition on Cu-, Co-, and Fe-SSZ-13 Zeolites

N2O decomposition is investigated on Cu, Co and Fe-exchanged SSZ-13 zeolite catalysts at relatively low metal loadings. The catalysts are synthesized by solution ion exchange, and subjected to X-ray diffraction (XRD), temperature-programed-reduction by H2 (H2-TPR), temperature-programed-reaction of N2O (N2O-TPR) coupled with in-situ transmission FTIR, and finally steady-state flow reaction tests. At low N2O pressures (< 0.05 kPa), all catalysts display pseudo first-order kinetics. From Arrhenius analysis, Cu and Fe-SSZ-13 display very different apparent activation energies but similar pre-exponential factors, suggesting their similar reaction mechanisms. N2O decomposition follows a dual-site mechanism, occurring on dimeric M-O-M sites in these catalysts, and O2 is formed by the combination of two O ad-atoms from two vicinal metal sites. Under low N2O pressure (0.05 kPa) and first-order kinetic regime, the reaction is limited by N-O cleavage on bare metal active sites. In comparison to Cu-SSZ-13, the much higher N2O decomposition rate over Fe-SSZ-13 is attributed to the much lower activation barriers for the N-O cleavage step. N2O decomposition occurs on isolated Co2+ ions in Co-SSZ-13. The rate-limiting step is N-O cleavage on an O-occupied Co site in the low-pressure first order kinetic regime. This single-site mechanism leads to much higher pre-exponential factors as compared to the dual-site mechanism. This beneficial factor for reaction rate enhancement, however, is compromised by the much higher activation barriers over this catalyst.

Lin, Fan↗

The Mojave Desert: A Martian Analog Site for Future Astrobiology Themed Missions

Astrobiological interest in Mars is highlighted by evidence that Mars was once warm enough to have liquid water present on its surface long enough to create geologic formations that could only exist in the presense of extended fluvial periods. These periods existed at the same time life on Earth arose. If life began on Mars as well during this period, it is reasonable to assume it may have adapted to the subsurface as environments at the surface changed into the inhospitable state we find today. If the next series of Mars missions (Mars Science Laboratory, the ExoMars Trace Gas Orbiter proposed for launch in 2016, and potential near surface sample return) fail to discover either extinct or extant life on Mars, a subsurface mission would be necessary to attempt to "close the book" on the existence of martian life. Mars is much colder and drier than Earth, with a very low pressure CO2 environment and no obvious habitats. Terrestrial regions with limited precipitation, and hence reduced active biota, are some of the best martian low to mid latitude analogs to be found on Earth, be they the Antarctic dry valleys, the Atacama or Mojave Deserts. The Mojave Desert/Death Valley region is considered a Mars analog site by the Terrestrial Analogs Panel of the NSF-sponsored decadal survey; a field guide was even developed and a workshop was held on its applicability as a Mars analog. This region has received a great deal of attention due to its accessibility and the variety of landforms and processes observed relevant to martian studies.

Mars analog sites↗

On the Ability of Space- Based Passive and Active Remote Sensing Observations of CO2 to Detect Flux Perturbations to the Carbon Cycle

Space-borne observations of CO2 are vital to gaining understanding of the carbon cycle in regions of the world that are difficult to measure directly, such as the tropical terrestrial biosphere, the high northern and southern latitudes, and in developing nations such as China. Measurements from passive instruments such as GOSAT (Greenhouse Gases Observing Satellite) and OCO-2 (Orbiting Carbon Observatory 2), however, are constrained by solar zenith angle limitations as well as sensitivity to the presence of clouds and aerosols. Active measurements such as those in development for the Active Sensing of CO2 Emissions over Nights, Days and Seasons (ASCENDS) mission show strong potential for making measurements in the high-latitude winter and in cloudy regions. In this work we examine the enhanced flux constraint provided by the improved coverage from an active measurement such as ASCENDS. The simulation studies presented here show that with sufficient precision, ASCENDS will detect permafrost thaw and fossil fuel emissions shifts at annual and seasonal time scales, even in the presence of transport errors, representativeness errors, and biogenic flux errors. While OCO-2 can detect some of these perturbations at the annual scale, the seasonal sampling provided by ASCENDS provides the stronger constraint. Plain Language Summary: Active and passive remote sensors show the potential to provide unprecedented information on the carbon cycle. With the all-season sampling, active remote sensors are more capable of constraining high-latitude emissions. The reduced sensitivity to cloud and aerosol also makes active sensors more capable of providing information in cloudy and polluted scenes with sufficient accuracy. These experiments account for errors that are fundamental to the top-down approach for constraining emissions, and even including these sources of error, we show that satellite remote sensors are critical for understanding the carbon cycle.

tropical terrestrial biosphere↗

Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS): Final Report of the ASCENDS Ad Hoc Science Definition Team

Improved remote sensing observations of atmospheric carbon dioxide (CO2) are critically needed to quantify, monitor, and understand the Earth's carbon cycle and its evolution in a changing climate. The processes governing ocean and terrestrial carbon uptake remain poorly understood,especially in dynamic regions with large carbon stocks and strong vulnerability to climate change,for example, the tropical land biosphere, the northern hemisphere high latitudes, and the Southern Ocean. Because the passive spectrometers used by GOSAT (Greenhouse gases Observing SATellite) and OCO-2 (Orbiting Carbon Observatory-2) require sunlit and cloud-free conditions,current observations over these regions remain infrequent and are subject to biases. These short comings limit our ability to understand and predict the processes controlling the carbon cycle on regional to global scales.In contrast, active CO2 remote-sensing techniques allow accurate measurements to be taken day and night, over ocean and land surfaces, in the presence of thin or scattered clouds, and at all times of year. Because of these benefits, the National Research Council recommended the National Aeronautics and Space Administration (NASA) Active Sensing of CO2 Emissions over Nights,Days, and Seasons (ASCENDS) mission in the 2007 report Earth Science and Applications from Space: National Imperatives for the Next Decade and Beyond. The ability of ASCENDS to collect low-bias observations in these key regions is expected to address important gaps in our knowledge of the contemporary carbon cycle.The ASCENDS ad hoc Science Definition Team (SDT), comprised of carbon cycle modeling and active remote sensing instrument teams throughout the United States (US), worked to develop the mission's requirements and advance its readiness from 2008 through 2018. Numerous scientific investigations were carried out to identify the benefit and feasibility of active CO2 remote sensing measurements for improving our understanding of CO2 sources and sinks. This report summarizes their findings and recommendations based on mission modeling studies, analysis of ancillary meteorological data products, development and demonstration of candidate technologies, anddesign studies of the ASCENDS mission concept.

Kawa, S. Randolph↗

Evidence-based Approach to Establish Space Suit Carbon Dioxide Limits

A literature survey was conducted to assess if published data (evidence) could help inform a space suit carbon dioxide (CO2) limit. The search identified more than 120 documents about human interaction with elevated CO2. Until now, the guiding philosophy has been to drive space suit CO2 as low as reasonably achievable. NASA’s EVA Office requested an evidencebased approach to support a new generation of exploration-class extravehicular activity (EVA) space suits. Specific literature data about CO2 are not available for EVA in microgravity because EVA is an operational activity and not a research platform. However, enough data from groundbased research are available to facilitate a consensus of expert opinion on space suit CO2 limits. The compilation of data in this report can answer many but not all concerns about the consequences of hypercapnic exercise in a space suit. Inspired partial pressure of CO2 (PICO2) and not dry-gas partial pressure of CO2 (PCO2) is the appropriate metric for hypercapnic dose to establish space suit CO2 limits. The reduction of inspired gas partial pressures by saturation of the inspired gases with water vapor at 37°C is a significant factor under conditions of hypobaric space suit operation. Otherwise healthy EVA astronauts will exhibit wide variability in responses to acute hypercapnia while at rest and during exercise. What is clear from the literature is the absence of prospective (objective) accept or reject criteria for CO2 exposure in general, and no such criteria exist for operating a space suit. There is no absolute “Gold Standard” for an acceptable acute hypercapnic limit, just a gradual decrease in performance as CO2 increases. Acceptable CO2 exposure limits are occupation, situation (learned or novel tasks), and personspecific. Investigators who measured hypercapnic physiology rarely correlated those changes to neurocognitive symptoms, and those that measured hypercapnic neurocognition rarely correlated those changes with physiology. Some answers about changes in neurocognition and functional EVA performance during hypercapnic exercise in a space suit await new research.

Conkin, Johnny↗

Calcification and photosynthesis of the coral acropora cervicornis under calcium limited conditions

Differing hypothesis about the function of calcification are based on an interesting dilemma. Is the purpose of calcification mainly a structural and protective one or does calcification serve other functions? Does photosynthesis increase carbonate ion activity and cause calcification or does calcification increase CO2 levels and stimulate photsynthesis? It is proposed that calcification in corals is not dependent upon photosynthesis but upon calcium levels in the water. Under normal ocean conditions, corals convert a certain percentage of energy to photosynthesis and respiration and another percentage to calcification. As corals become nutrient stressed, particularly calcium limited, the ratio of photosynthesis to calcification shifts towards calcification in order to generate protons. The protons generated during calcification may stimulate photosynthesis and aid in the uptake of nutrients and biocarbonates. The results of the calcification experiment show a trend towards increased calcification and decreased photosynthesis when the coral Acropora cervicornis is calcium limited, but the data are inconclusive and further research is needed.

Rathfon, Megan↗

Spring Hydrology Determines Summer Net Carbon Uptake in Northern Ecosystems

Increased photosynthetic activity and enhanced seasonal CO2 exchange of northern ecosystems have been observed from a variety of sources including satellite vegetation indices (such as the Normalized Difference Vegetation Index; NDVI) and atmospheric CO2 measurements. Most of these changes have been attributed to strong warming trends in the northern high latitudes (greater than or equal to 50N). Here we analyze the interannual variation of summer net carbon uptake derived from atmospheric CO2 measurements and satellite NDVI in relation to surface meteorology from regional observational records. We find that increases in spring precipitation and snow pack promote summer net carbon uptake of northern ecosystems independent of air temperature effects. However, satellite NDVI measurements still show an overall benefit of summer photosynthetic activity from regional warming and limited impact of spring precipitation. This discrepancy is attributed to a similar response of photosynthesis and respiration to warming and thus reduced sensitivity of net ecosystem carbon uptake to temperature. Further analysis of boreal tower eddy covariance CO2 flux measurements indicates that summer net carbon uptake is positively correlated with early growing-season surface soil moisture, which is also strongly affected by spring precipitation and snow pack based on analysis of satellite soil moisture retrievals. This is attributed to strong regulation of spring hydrology on soil respiration in relatively wet boreal and arctic ecosystems. These results document the important role of spring hydrology in determining summer net carbon uptake and contrast with prevailing assumptions of dominant cold temperature limitations to high-latitude ecosystems. Our results indicate potentially stronger coupling of boreal/arctic water and carbon cycles with continued regional warming trends.

Carbon Uptake↗

Effect of Carbon Dioxide Exposure on Physical and Cognitive Performance in A Simulated Spaceflight Contingency Scenario

INTRODUCTION: Carbon dioxide (CO2) produced by astronauts inside space suits can accumulate to levels that may affect health and performance. The human health and performance risks associated with different levels of CO2 exposure in the flight environment remain an area of debate. The purpose of this study is to characterize the limit of acceptable performance (cognitive and physical) decrements and symptom severity for mission operations when subjected to elevated inspired CO2 levels in simulated contingency lunar extravehicular activity (EVA) scenarios. METHODS: This study will create a simulation of a 1-hour, ~2km contingency EVA walk back to a habitat, incorporating a passive treadmill and a fully immersive virtual reality (VR) simulation of a lunar EVA environment. Subjects will be asked to walk on a treadmill while breathing partial pressures of CO2 of 0, 5, 10, 15, 20, 25, 30mmHg for 1 hour at a time. Cognitive performance will be quantified using validated cognitive tests and measures of functional task performance embedded within the VR environment. Test subject symptoms and self-assessment of performance will be evaluated via survey. RESULTS: This study currently has approval from NASA’s Institutional Review Board and has completed the Test Readiness Review process. Next steps for this research study include test subject recruitment, data collection, and analysis. Data collection is planned for calendar year 2023 and 2024. DISCUSSION: This study will provide valuable information regarding how various partial pressures of CO2 exposure impact acute health, as well as cognitive and physical performance during simulated contingency lunar EVA. This information will enable assessment of health and performance risk associated with spacesuit systems and operations concepts for future exploration missions as well as informing definition of future standards and requirements.

D. M. Nusbaum↗

Effect of Carbon Dioxide Exposure on Physical and Cognitive Performance in A Simulated Spaceflight Contingency Scenario

INTRODUCTION: Carbon dioxide (CO2) produced by astronauts inside space suits can accumulate to levels that may affect health and performance. The human health and performance risks associated with different levels of CO2 exposure in the flight environment remain an area of debate. The purpose of this study is to characterize the limit of acceptable performance (cognitive and physical) decrements and symptom severity for mission operations when subjected to elevated inspired CO2 levels in simulated contingency lunar extravehicular activity (EVA) scenarios. METHODS: This study will create a simulation of a 1-hour, ~2km contingency EVA walk back to a habitat, incorporating a passive treadmill and a fully immersive virtual reality (VR) simulation of a lunar EVA environment. Subjects will be asked to walk on a treadmill while breathing partial pressures of CO2 of 0, 5, 10, 15, 20, 25, 30mmHg for 1 hour at a time. Cognitive performance will be quantified using validated cognitive tests and measures of functional task performance embedded within the VR environment. Test subject symptoms and self-assessment of performance will be evaluated via survey. RESULTS: This study currently has approval from NASA’s Institutional Review Board and has completed the Test Readiness Review process. Next steps for this research study include test subject recruitment, data collection, and analysis. Data collection is planned for calendar year 2023 and 2024. DISCUSSION: This study will provide valuable information regarding how various partial pressures of CO2 exposure impact acute health, as well as cognitive and physical performance during simulated contingency lunar EVA. This information will enable assessment of health and performance risk associated with spacesuit systems and operations concepts for future exploration missions as well as informing definition of future standards and requirements.

carbon dioxide↗

REDOTHERM (Redox Countercurrent Thermodynamic Limits Model) [SWR-24-88]

REDOTHERM is an open-source, MATLAB-based thermodynamic modeling framework developed to evaluate the performance of redox-active materials for water (H2O) and carbon dioxide (CO2) splitting. It includes models of all major unit operations and supports comparative analysis of different redox-active material candidates. The model is tailored for systems of moving oxide under a parallel/cocurrent flow (PF) and countercurrent flow (CF) configurations. Unvalidated mixed flow reactor (MFR, also known as CSTR) model is also included as an optional addition.

Lidor, Alon [National Renewable Energy Laboratory ↗

The Origin of Titan's External Oxygen: Further Constraints from ALMA Upper Limits on CS and CH2NH

Titan's atmospheric inventory of oxygen compounds (H2O, CO2, CO) are thought to result from photochemistry acting on externally supplied oxygen species (O+, OH, H2O). These species potentially originate from two main sources: (1) cryogenic plumes from the active moon Enceladus and (2) micrometeoroid ablation. Enceladus is already suspected to be the major O+ source, which is required for CO creation. However, photochemical models also require H2O and OH influx to reproduce observed quantities of CO2 and H2O. Here, we exploit sulphur as a tracer to investigate the oxygen source because it has very different relative abundances in micrometeorites (S/O approx. 10(exp -2) and Enceladus' plumes (S/O approx. 10(exp -5). Photochemical models predict most sulphur is converted to CS in the upper atmosphere, so we use Atacama Large Millimeter/submillimeter Array (ALMA) observations at approx. 340 GHz to search for CS emission. We determined stringent CS 3 sigma stratospheric upper limits of 0.0074 ppb (uniform above 100 km) and 0.0256 ppb (uniform above 200 km). These upper limits are not quite stringent enough to distinguish between Enceladus and micrometeorite sources at the 3 sigma level and a contribution from micrometeorites cannot be ruled out, especially if external flux is toward the lower end of current estimates. Only the high flux micrometeorite source model of Hickson et al. can be rejected at 3 sigma. We determined a 3 sigma stratospheric upper limit for CH2NH of 0.35 ppb, which suggests cosmic rays may have a smaller influence in the lower stratosphere than predicted by some photochemical models. Disk-averaged C3H4 and C2H5CN profiles were determined and are consistent with previous ALMA and Cassini/CIRS measurements.

Teanby, N.A.↗

Gateway Integrated ECLSS Model Analysis of Intermodule Ventilation Failures

The Gateway Integrated ECLSS Model (GIEM) is a set of two independent models, made in Aspen Custom Modeler (ACM) and Thermal Desktop (TD), of the Gateway stack and each modules' associated environment control and life support system (ECLSS). The GIEM utilizes the 41-Node Metabolic Man (METMAN) to simulate crew inside the Gateway consuming O2 and producing CO2, H2O, and heat for the ECLSS to remove. The modules and visiting vehicles all have different levels of ECLSS capabilities and may rely on other modules and Intermodular Ventilation (IMV), which is used to exchange gas between the modules, to ensure the entire Gateway environment is controlled. If IMV were to fail or be turned off, some vehicles may have limited access to necessary ECLSS functions. This analysis focuses on evaluating O2, CO2, and H2O levels when crew are in vehicles without their own life support and IMV has failed to evaluate how long before the atmosphere is unsafe for the crew. This analysis uses the integrated nature of the GIEM to look at time to effect for O2 depletion and CO2 and H2O buildup when crew are working in vehicles that have been cut off from the ECLSS-active portion of the stack. This information is used to inform for how long crew can safely continue working in the ECLSS-inactive vehicles before experiencing a requirement violation or physical limitation and can be referenced when developing maintenance and emergency response concept of operations (ConOps).

Lawrence Barrett↗

Optical Breath Gas Extravehicular Activity Sensor for the Advanced Portable Life Support System

The infrared gas transducer used during extravehicular activity (EVA) in the extravehicular mobility unit (EMU) measures and reports the concentration of carbon dioxide (CO2) in the ventilation loop. It is nearing its end of life and there are a limited number remaining. Meanwhile, the next generation advanced portable life support system (PLSS) now being developed requires CO2 sensing technology with performance beyond that presently in use. A laser diode (LD) spectrometer based on wavelength modulation spectroscopy (WMS) is being developed to address both applications by Vista Photonics, Inc. Accommodation within space suits demands that optical sensors meet stringent size, weight, and power requirements. Version 1.0 devices were delivered to NASA Johnson Space Center (JSC) in 2011. The sensors incorporate a laser diode based CO2 channel that also includes an incidental water vapor (humidity) measurement. The prototypes are controlled digitally with a field-programmable gate array (FPGA)/microcontroller architecture. Version 2.0 devices with improved electronics and significantly reduced wetted volumes were delivered to JSC in 2012. A version 2.5 upgrade recently implemented wavelength stabilized operation, better humidity measurement, and much faster data analysis/reporting. A wholly reconfigured version 3.0 will maintain the demonstrated performance of earlier versions while being backwards compatible with the EMU and offering a radiation tolerant architecture.

Wood, William R.↗