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Observing System Simulations for the NASA ASCENDS Lidar CO2 Mission Concept: Substantiating Science Measurement Requirements

The NASA ASCENDS mission (Active Sensing of Carbon Emissions, Nights, Days, and Seasons) is envisioned as the next generation of dedicated, space-based CO2 observing systems, currently planned for launch in about the year 2022. Recommended by the US National Academy of Sciences Decadal Survey, active (lidar) sensing of CO2 from space has several potentially significant advantages, in comparison to current and planned passive CO2 instruments, that promise to advance CO2 measurement capability and carbon cycle understanding into the next decade. Assessment and testing of possible lidar instrument technologies indicates that such sensors are more than feasible, however, the measurement precision and accuracy requirements remain at unprecedented levels of stringency. It is, therefore, important to quantitatively and consistently evaluate the measurement capabilities and requirements for the prospective active system in the context of advancing our knowledge of carbon flux distributions and their dependence on underlying physical processes. This amounts to establishing minimum requirements for precision, relative accuracy, spatial/temporal coverage and resolution, vertical information content, interferences, and possibly the tradeoffs among these parameters, while at the same time framing a mission that can be implemented within a constrained budget. Here, we present results of observing system simulation studies, commissioned by the ASCENDS Science Requirements Definition Team, for a range of possible mission implementation options that are intended to substantiate science measurement requirements for a laser-based CO2 space instrument.

Kawa, Stephan R.↗

Photochemical consequences of enhanced CO2 levels in earth's early atmosphere

Greatly enhanced atmospheric CO2 concentrations are the most likely mechanism for offsetting the effects of reduced solar luminosity early in the earth's history. CO2 levels of 80 to 600 times the present value could have maintained a mean surface temperature of 0 C to 15 C, given a 25 percent decrease in solar output. Such high CO2 levels are at least qualitatively consistent with the present understanding of the carbonate-silicate geochemical cycle. The presence of large amounts of CO2 has important implications for the composition of the earth's prebiotic atmosphere. The hydrogen budget of a high-CO2 primitive atmosphere would have been strongly influenced by rainout of H2O2 and H2CO. The reaction of H2O2 with dissolved ferrous iron in the early oceans could have been a major sink for atmospheric oxygen. The requirement that this loss of oxygen be balanced by a corresponding loss of hydrogen (by escape to space and rainout of H2CO) implies that the atmospheric H2 mixing ratio was greater than 2 x 10 to the -5th and the ground level O2 mixing ratio was below 10 to the -12th, even if other surface sources of H2 were small. These results are only weakly dependent on changes in solar UV flux, rainout rates, and vertical mixing rates in the primitive atmosphere.

Kasting, J. F.↗

Greenhouse Gas Impact of Algal Bio-Crude Production for a Range of CO2 Supply Scenarios

Refined bio-crude production from hydrothermal liquefaction of algae holds the potential to replace fossil-based conventional liquid fuels. The microalgae act as natural carbon sequestrators by consuming CO2. However, this absorbed CO2 is released to the atmosphere during the combustion of the bio-crude. Thus, the life-cycle greenhouse gas (GHG) emissions of refined bio-crude are linked to the production and supply of the materials involved and the process energy demands. One prominent raw material is CO2, which is the main source of carbon for algae and the subsequent products. The emissions associated with the supply of CO2 can have a considerable impact on the sustainability of the algae-based refined bio-crude production process. Furthermore, the diurnal algae growth cycle complicates the CO2 supply scenarios. Traditionally, studies have relied on CO2 supplied from existing power plants. However, there is potential for building natural gas or biomass-based power plants with the primary aim of supplying CO2 to the biorefinery. Alternately, a direct air capture (DAC) process can extract CO2 directly from the air. The life-cycle GHG emissions associated with the production of refined bio-crude through hydrothermal liquefaction of algae are presented in this study. Different CO2 supply scenarios, including existing fossil fuel power plants and purpose-built CO2 sources, are compared. The integration of the CO2 sources with the algal biorefinery is also presented. The CO2 supply from biomass-based power plants has the highest potential for GHG reduction, with a GHG footprint of −57 g CO2 eq./MJ refined bio-crude. The CO2 supply from the DAC process has a GHG footprint of 49 CO2 eq./MJ refined bio-crude, which is very similar to the scenario that considers the supply of CO2 from an existing conventional natural gas-based plant and takes credit for the carbon utilization.

36 MATERIALS SCIENCE↗

Ambient-temperature co-oxidation catalysts

Oxidation catalysts which operate at ambient temperature were developed for the recombination of carbon monoxide (CO) and oxygen (O2) dissociation products which are formed during carbon dioxide (CO2) laser operation. Recombination of these products to regenerate CO2 allows continuous operation of CO2 lasers in a closed cycle mode. Development of these catalyst materials provides enabling technology for the operation of such lasers from space platforms or in ground based facilities without constant gas consumption required for continuous open cycle operation. Such catalysts also have other applications in various areas outside the laser community for removal of CO from other closed environments such as indoor air and as an ambient temperature catalytic converter for control of auto emissions.

Upchurch, Billy T.↗

Atmospheric Science Experiment for Mars: ATMIS for the Netlander 2005 Mission

ATMIS (Atmospheric and Meteorological Instrumentation System) is a versatile suite of atmospheric instrumentation to be accommodated onboard the Netlander Mission slated for launch in 2005. Four Netlanders are planned to form a geophysical measurement network on the surface of Mars. The atmospheric sciences are among the scientific disciplines benefiting most of the network concept. The goal of the ATMIS instrument is to provide new data on the atmospheric vertical structure, regional and global circulation phenomena, the Martian Planetary Boundary Layer (PBL) and atmosphere-surface interactions, dust storm triggering mechanisms, as well as the climatological cycles of H2O, dust and CO2. To reach the goal of characterization of a number of phenomena exhibiting both spatial and temporal variations, simultaneous observations of multiple variables at spatially displaced sites Deforming a network D are required. The in situ observations made by the ATMIS sensors will be supported by extensive modeling efforts. Additional information is contained in the original extended abstract.

Harri, A.-M.↗

Autotrophy of green non-sulphur bacteria in hot spring microbial mats: biological explanations for isotopically heavy organic carbon in the geological record

Inferences about the evidence of life recorded in organic compounds within the Earth's ancient rocks have depended on 13C contents low enough to be characteristic of biological debris produced by the well-known CO2 fixation pathway, the Calvin cycle. 'Atypically' high values have been attributed to isotopic alteration of sedimentary organic carbon by thermal metamorphism. We examined the possibility that organic carbon characterized by a relatively high 13C content could have arisen biologically from recently discovered autotrophic pathways. We focused on the green non-sulphur bacterium Chloroflexus aurantiacus that uses the 3-hydroxypropionate pathway for inorganic carbon fixation and is geologically significant as it forms modern mat communities analogous to stromatolites. Organic matter in mats constructed by Chloroflexus spp. alone had relatively high 13C contents (-14.9%) and lipids diagnostic of Chloroflexus that were also isotopically heavy (-8.9% to -18.5%). Organic matter in mats constructed by Chloroflexus in conjunction with cyanobacteria had a more typical Calvin cycle signature (-23.5%). However, lipids diagnostic of Chloroflexus were isotopically enriched (-15.1% to -24.1%) relative to lipids typical of cyanobacteria (-33.9% to -36.3%). This suggests that, in mats formed by both cyanobacteria and Chloroflexus, autotrophy must have a greater effect on Chloroflexus carbon metabolism than the photoheterotrophic consumption of cyanobacterial photosynthate. Chloroflexus cell components were also selectively preserved. Hence, Chloroflexus autotrophy and selective preservation of its products constitute one purely biological mechanism by which isotopically heavy organic carbon could have been introduced into important Precambrian geological features.

NASA Discipline Exobiology↗

Simulation and Optimization of Vacuum Swing Adsorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and humidity levels in a spacesuit is critical to ensuring both the safety and comfort of an astronaut during extra-vehicular activity (EVA). Traditionally, this has been accomplished utilizing non-regenerative lithium hydroxide (LiOH) or regenerative metal oxide (MetOx) canisters which pose a significant weight burden. Although such technology enables air revitalization, the volume requirements to store the waste canisters as well as the mass to transport multiple units become prohibitive as mission durations increase. Consequently, motivation exists toward developing a fully regenerative technology for environmental control. The application of solid amine materials with vacuum swing adsorption technology has shown the capacity to control CO2 and concomitantly manage humidity levels through a fully regenerative cycle eliminating mission constraints imposed with non-regenerative technologies. Experimental results for full-size and sub-scale test articles have been collected and are described herein. In order to accelerate the developmental efforts, an axially-dispersed plug ow model with an accompanying energy balance has been established and correlated with the experimental data. The experimental and simulation results display good agreement for a variety of ow rates (110-170 SLM), replicated metabolic challenges (100-590 Watts), and atmosphere pressures under consideration for the spacesuit (248 and 760 mm Hg). The relationship between swing adsorption cycles for an outlet criterion of 6.0 mm Hg of CO2 partial pressure has been established for each metabolic challenge. In addition, variable metabolic profiles were imposed on the test articles in order to assess the ability of the technology to transition to new operational constraints. The advent of the model provides the capacity to apply computer-aided engineering practices to support the ongoing efforts to optimize and mature this technology for future application to space exploration.

Swickrath, Michael J.↗

Continued Development of the Rapid Cycle Amine (RCA) System for Advanced Extravehicular Activity Systems

Development activities related to the Rapid Cycle Amine (RCA) Carbon Dioxide (CO2) and Humidity control system have progressed to the point of integrating the RCA into an advanced Primary Life Support System (PLSS 2.0) to evaluate the interaction of the RCA among other PLSS components in a ground test environment. The RCA 2.0 assembly (integrated into PLSS 2.0) consists of a valve assembly with commercial actuator motor, a sorbent canister, and a field-programmable gate array (FPGA)-based process node controller. Continued design and development activities for RCA 3.0 have been aimed at optimizing the canister size and incorporating greater fidelity in the valve actuator motor and valve position feedback design. Further, the RCA process node controller is envisioned to incorporate a higher degree of functionality to support a distributed PLSS control architecture. This paper will describe the progression of technology readiness levels of RCA 1.0, 2.0 and 3.0 along with a review of the design and manufacturing successes and challenges for 2.0 and 3.0 units. The anticipated interfaces and interactions with the PLSS 2.0/2.5/3.0 assemblies will also be discussed.

Papale, William↗

Continued Development of the Rapid Cycle Amine (RCA) System for Advanced Extravehicular Activity Systems

Development activities related to the Rapid Cycle Amine (RCA) Carbon Dioxide (CO2) and Humidity control system have progressed to the point of integrating the RCA into an advanced Primary Life Support System (PLSS 2.0) to evaluate the interaction of the RCA among other PLSS components in a ground test environment. The RCA 2.0 assembly (integrated into PLSS 2.0) consists of a valve assembly with commercial actuator motor, a sorbent canister, and a field-programmable gate array (FPGA)-based process node controller. Continued design and development activities for RCA 3.0 have been aimed at optimizing the canister size and incorporating greater fidelity in the valve actuator motor and valve position feedback design. Further, the RCA process node controller is envisioned to incorporate a higher degree of functionality to support a distributed PLSS control architecture. This paper will describe the progression of technology readiness levels of RCA 1.0, 2.0 and 3.0 along with a review of the design and manufacturing successes and challenges for 2.0 and 3.0 units. The anticipated interfaces and interactions with the PLSS 2.0/2.5/3.0 assemblies will also be discussed.

Papale, William↗

The Orbiting Carbon Observatory: Mission Overview

OCO will acquire the space-based data needed to identify CO2 sources and sinks and quantify their variability over the seasonal cycle. Approach: a) Collect spatially resolved, high resolution spectroscopic observations of CO2 and O2 absorption in reflected sunlight; b) Use these data to resolve spatial and temporal variations in the column averaged CO2 dry air mole fraction, X cub CO2) over the sunlit hemisphere; and c) Employ independent calibration and validation approaches to produce X(sub CO2) estimates with random errors and biases no larger than 1-2 ppm (0.3-0.5%) on regional scales at monthly intervals.

CO2↗

Perspectives on improving photosynthesis to increase crop yield

Abstract Improving photosynthesis, the fundamental process by which plants convert light energy into chemical energy, is a key area of research with great potential for enhancing sustainable agricultural productivity and addressing global food security challenges. This perspective delves into the latest advancements and approaches aimed at optimizing photosynthetic efficiency. Our discussion encompasses the entire process, beginning with light harvesting and its regulation and progressing through the bottleneck of electron transfer. We then delve into the carbon reactions of photosynthesis, focusing on strategies targeting the enzymes of the Calvin–Benson–Bassham (CBB) cycle. Additionally, we explore methods to increase carbon dioxide (CO2) concentration near the Rubisco, the enzyme responsible for the first step of CBB cycle, drawing inspiration from various photosynthetic organisms, and conclude this section by examining ways to enhance CO2 delivery into leaves. Moving beyond individual processes, we discuss two approaches to identifying key targets for photosynthesis improvement: systems modeling and the study of natural variation. Finally, we revisit some of the strategies mentioned above to provide a holistic view of the improvements, analyzing their impact on nitrogen use efficiency and on canopy photosynthesis.

59 BASIC BIOLOGICAL SCIENCES↗

Simulation Studies for a Space-Based CO2 Lidar Mission

We report results of initial space mission simulation studies for a laser-based, atmospheric CO2 sounder, which are based on real-time carbon cycle process modelling and data analysis. The mission concept corresponds to the Active Sensing of CO2 Emissions over Nights, Days and Seasons (ASCENDS) recommended by the US National Academy of Sciences' Decadal Survey. As a pre-requisite for meaningful quantitative evaluation, we employ a CO2 model that has representative spatial and temporal gradients across a wide range of scales. In addition, a relatively complete description of the atmospheric and surface state is obtained from meteorological data assimilation and satellite measurements. We use radiative transfer calculations, an instrument model with representative errors and a simple retrieval approach to quantify errors in 'measured' CO2 distributions, which are a function of mission and instrument design specifications along with the atmospheric/surface state. Uncertainty estimates based on the current instrument design point indicate that a CO2 laser sounder can provide data consistent with ASCENDS requirements and will significantly enhance our ability to address carbon cycle science questions. Test of a dawn/dusk orbit deployment, however, shows that diurnal differences in CO2 column abundance, indicative of plant photosynthesis and respiration fluxes, will be difficult to detect

Kawa, S. R.↗

Energy Arbitrage: Comparison of Options for use with LWR Nuclear Power Plants

Arbitrage is the opportunistic buying and selling of a commodity during local pricing valleys and peaks respectively to maximize economic value. This report evaluates options for energy arbitrage integrated with existing light water reactor (LWR) nuclear power plants (NPPs) where nuclear energy could be stored in a variety of forms and later recovered to generate electrical power during periods when grid electricity demand and pricing are high. The forms of energy storage examined in this report include the potential value of batteries, hydrogen, and thermal energy storage for coupling with nuclear power. Various large demand response options are also analyzed, including the production of liquid nitrogen via air separation and liquefaction, liquefaction of hydrogen, compressed hydrogen, and the cryogenic capture of CO2. Demand response refers to dispatchable loads that can cycle up or down depending on-grid electricity demand to aid in balancing the grid. Large demand response options could dispatch to aid nuclear power stations in avoiding power turndowns by providing an alternate disposition for electrical energy by producing marketable products (e.g., liquid nitrogen, hydrogen, or captured CO2). Static conditions were chosen and analyzed in this report for each option. Dynamic operation or optimization of energy arbitrage or demand response are out of scope for this report. The analysis is based on storage systems with discharge capacities of 500 MW for which various durations of storage and costs of charging (electricity cost) are examined. While the value of thermal energy to an industrial user for flexible plant operations has been previously proven as a business case, this report evaluates costs of hydrogen energy storage and leading thermal energy storage options, and large demand response loads that could be integrated with LWRs in comparison to utility-scale battery storage for use of off-peak nuclear energy. Compilation of this information will be used by the Idaho National Laboratory (INL) RAVEN/HERON systems integration and economics tool to evaluate thermal energy dispatch to industrial users. Relative ranking of energy storage options was done using a levelized cost of storage (LCOS) metric which calculates a rough breakeven cost for the system, taking into account the capital and operating costs as well as the revenue from arbitrage. Table ES1 below shows the LCOS for each of the energy storage options considered. First, in the table, lithium iron (Fe) phosphate batteries are listed as the base case for comparison against the other options. Next is hydrogen storage where most of the hydrogen analyses assumed the hydrogen to be produced using solid oxide electrolytic cell (SOEC) high temperature steam electrolysis (HTSE). The others used existing models of polymer electrolyte membrane (PEM) low temperature electrolysis to produce hydrogen. HTSE performance parameters and costs were taken from existing INL models. Various means were assumed to convert the hydrogen to electricity, including PEM fuel cells (FCs) and a gas turbine mixed in a 30 vol% mixture with natural gas. Physical storage (pressure vessels) and geological storage (natural underground features) were used to store the hydrogen as noted. Geological storage is more economical, but the locations are limited because of the requirement for pre-existing geological formations that will support storage. Thermal energy storage (TES) options were also analyzed including electro-thermal energy storage (ETES) and four different liquid sensible heat TES storage media as noted (Hitec, Hitec XL, Therminol-66, and Dowtherm A). The ETES process considered was modified using existing public documentation on an Echogen process and uses a separate supercritical CO2 charge and discharge cycle with sand as the heat storage media.

25 ENERGY STORAGE↗

Measuring Atmospheric Carbon Dioxide from the NASA Orbiting Carbon Observatory-2 (OCO-2)

Fossil fuel combustion, deforestation, and other human activities are now adding almost 40 billion tons of carbon dioxide (CO2) to the atmosphere each year. These emissions are superimposed on an active natural carbon cycle that adds about 20 times as much CO2 to the atmosphere annually, and then reabsorbs a comparable amount, along with over half of the CO2 contributed by human activities. Interestingly, the identity and location of the natural “sinks” in the land biosphere and ocean that are responsible for absorbing this anthropogenic CO2 are still poorly understood. Because of this, it is impossible to accurately predict how these sinks will respond to a warming climate. Space based remote sensing provides new tools for studying the sources and sinks of CO2. The NASA Orbiting Carbon Observatory-2 (OCO-2) was launched in July 2014 and was inserted at the head of the 705-km Afternoon Constellation (A-Train) a month later.

Crisp, David↗

Effect of Initial Water Saturation on The Performance of Fracturing Fluids With and Without Polyallylamine under Simulated EGS Conditions

Objectives/Scope: StimuFrac (US Patents 9,873,828 B2 and 9,447,315 B2), a CO2-reactive polymer aqueous solution [polyallylamine (PAA) 1wt% in water] combined with CO2, can be used as a less water-intensive fracturing fluid for enhanced geothermal systems (EGS). Our previous results show that in hot dry rock (HDR), PAA/CO2 fracturing fluids outperformed other fluids such as water, CO2, and CO2/water in generating large fractures with less fluid consumed. The objective of this work is to study the effect of initial water saturation of rock on the performance of StimuFrac fluid in ½ foot cubic rock samples and under representative EGS pressure/temperature conditions using cyclic and constant flow rate injection strategies. The fracturing results are compared with results using different fracturing fluids in terms of controlling fracture propagation rates, fracture hydraulic conductivity, breakdown pressures and volumes of fluids required. Methods/Procedures/Process: In all tests, water was initially injected into the rock to increase the water saturation before the fracturing processes to simulate actual geothermal reservoir conditions. For the cyclic injection, one complete cycle consisted of (1) a PAA slug (or water slug) injection followed by (2) CO2 injection to initiate the fracture. In the second step of the first cycle, the pressure of CO2 is increased until a maximum pressure is reached (fracture is initiated at this moment), and then the injection of CO2 is allowed for another 30 seconds to propagate the fracture. Then, the two-step cycle of PAA followed by CO2 injection (up to 2-4 mL/min) was continued. For the constant flow rate injection strategies, the initial water saturation was increased by injecting water at 1000 psi and 200°C for three days. After that, an initial slug of water, CO2, or PAA was injected and then fracturing was initiated and propagated by injecting CO2 at a constant flow rate. Applications/Significance/Novelty: The results of this study suggest that water saturation, especially near the wellbore region, will significantly affect the fracturing fluid transmission into the rock porous media by changing the relative permeability of CO2 or water, thus affecting the fracture initiation and propagation. In this study, fracturing with cyclic injection or constant flow rate injection methods were performed using three different kinds of fluids systems. These fluids are water, CO2, or CO2 with PAA. Splitting the rock samples in half after fracturing reveals that the fracture propagation is significantly limited under these high water saturated conditions compared to dry initial conditions: The fractures propagate less than 1/3 length of the distance from the wellbore to rock surface, and in some cases no fracture is generated. This may be caused by the fact that leak-off is dominating the fracturing process and the injected fluid flow rate is not high enough to overcome the leak-off even under high flow rate injection conditions. Additionally, CO2 could be leaking off into the wellbore annulus and this may be making it more difficult to generate pressure gradients away from the near-wellbore region.

Jian, Guoqing↗

Monitoring Ocean CO2 Fluxes from Space: GOSAT and OCO-2

The ocean is a major component of the global carbon cycle, emitting over 330 billion tons of carbon dioxide (CO2) into the atmosphere each year, or about 10 times that emitted fossil fuel combustion and all other human activities [1, 2]. The ocean reabsorbs a comparable amount of CO2 each year, along with ~25% of the CO2 emitted by these human activities. The nature and geographic distribution of the processes controlling these ocean CO2 fluxes are still poorly constrained by observations. A better understanding of these processes is essential to predict how this important CO2 sink may evolve as the climate changes.While in situ measurements of ocean CO2 fluxes can be very precise, the sampling density is far too sparse to quantify ocean CO2 sources and sinks over much of the globe. One way to improve the spatial resolution, coverage, and sampling frequency is to make observations of the column averaged CO2 dry air mole fraction, XCO2, from space [4, 5, 6]. Such measurements could provide global coverage at high resolution (< 100 km) on monthly time scales. High precision (< 1 part per million, ppm) is essential to resolve the small, near-surface CO2 variations associated with ocean fluxes and to better constrain the CO2 transport over the ocean. The Japanese Greenhouse gases Observing Satellite (GOSAT) and the NASA Orbiting Carbon Observatory (OCO) were first two space based sensors designed specifically for this task. GOSAT was successfully launched on January 23, 2009, and has been returning measurements of XCO2 since April 2009. The OCO mission was lost in February 2009, when its launch vehicle malfunctioned and failed to reach orbit. In early 2010, NASA authorized a re-flight of OCO, called OCO-2, which is currently under development.

GOSAT↗

Performance Characterization and Simulation of Amine-Based Vacuum Swing Adsorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and water (H2O) concentrations in the vapor phase of a space suit is critical to ensuring an astronauts safety, comfortability, and capability to perform extra-vehicular activity (EVA) tasks. Historically, this has been accomplished using lithium hydroxide (LiOH) and metal oxides (MetOx). Lithium hydroxide is a consumable material and requires priming with water before it becomes effective at removing carbon dioxide. MetOx is regenerable through a power-intensive thermal cycle but is significantly heavier on a volume basis than LiOH. As an alternative, amine-based vacuum swing beds are under aggressive development for EVA applications which control atmospheric concentrations of both CO2 and H2O through a fully-regenerative process. The current concept, referred to as the rapid cycle amine (RCA), has resulted in numerous laboratory prototypes. Performance of these prototypes have been assessed and documented from experimental and theoretical perspectives. To support developmental efforts, a first principles model has also been established for the vacuum swing adsorption technology. The efforts documented herein summarize performance characterization and simulation results for several variable metabolic profiles subjected to the RCA. Furthermore, a variety of control methods are explored including timed swing cycles, instantaneous CO2 feedback control, and time-averaged CO2 feedback control. A variety of off-nominal tests are also explored including high/low suit temperatures, increasingly high humidity cases, and dynamic pressure cases simulating the suit pre-breathe protocol. Consequently, this work builds on efforts previous efforts to fully bound the performance of the rapid cycle amine under a variety of nominal and off-nominal conditions.

Swickrath, Michael J.↗