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At least 631 records · Page 35

Comments on the BLAG model - The carbonate-silicate geochemical cycle and its effect on atmospheric carbon dioxide over the past 100 million years

A self-consistent method of determining initial conditions for the model presented by Berner, Lasaga, and Garrels (1983) (henceforth, the BLAG model) is derived, based on the assumption that the CO2 geochemical cycle was in steady state at t = -100 m.y. (million years). This initialization procedure leads to a dissolved magnesium concentration higher than that calculated by Berner, Lasaga, and Garrels and to a low ratio of dissolved calcium to bicarbonate prior to 60 m.y. ago. The latter prediction conflicts with the geologic record of evaporite deposits, which requires that this ratio remain greater than 0.5. The contradiction is probably caused by oversimplifications in the BLAG model, such as the neglect of the cycles of organic carbon and sulfur.

Kasting, J. F.↗

Integrated CO 2 Capture and Conversion to Formate with a Molecular Platinum Bis(diphosphine) Electrocatalyst

Carbon dioxide is a potentially valuable feedstock for carbon-based fuels or commodities but is only available in dilute streams. Many studies have focused on either the capture and concentration of CO 2 or the reduction of pure CO 2 streams. The direct reduction of sorbent-captured CO 2 in an integrated process would skip the energy-intensive CO 2 concentration and sorbent regeneration step. Herein, we report the electrocatalytic reduction of 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (IPr·CO 2 ), which forms quantitatively from the reaction of sorbent 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) with 10% and 0.04% CO 2 streams, by catalyst [Pt(dmpe) 2 ](PF 6 ) 2 (dmpe = 1,2-bis(dimethylphosphino)ethane) to formate with >70% Faradaic efficiencies. Unexpectedly, experimental studies indicate that the proton source phenol facilitates rapid decarboxylation of IPr·CO 2 to release CO 2 , which is the substrate for reduction. Kinetic studies determined the rate of hydride transfer from a catalytic intermediate [HPt(dmpe) 2 ](PF 6 ) to form the C–H bond in formate to be 0.22 M –1 s –1 . Further details on the mechanism, transition state energy, and structure for hydride transfer to CO 2 , a common step in CO 2 reduction, were explored using computational methods.

Chemistry↗

CACTUS: CO 2 Aerogel Capture Towards Utilization and Sequestration

The CACTUS project aimed to develop a novel solid sorbent and sorption module prototype for direct air capture (DAC) of carbon dioxide, by a moisture-swing adsorption (MSA) mechanism. Because MSA uses changes in humidity, not temperature to switch the sorbent from capturing CO 2 to releasing concentrated CO 2 it is > 4X more energy-efficient than the thermal swing process. The goal was to develop a sorbent with a CO 2 capture capacity of 1 mmol CO 2 /g sorbent (or 0.75 mmol CO 2 /g structured sorbent), at a projected scaled cost of < $\$$15/kg sorbent and demonstration of a path to < $\$$100/ton CO 2 . At the end of the project, we achieved 0.8 mmol CO 2 /g sorbent powders, 0.37 mmol CO 2 /g structured sorbent (50% of target), at a projected cost of $\$$29/kg sorbent and an estimated cost of $\$$160/ton CO 2 . The key innovation was SRI’s patented polymer aerogel synthesis platform, which was adapted to produce a nanoporous aerogel with a high density of CO 2 -adsorbing quaternary ammonium groups. This research discovered a new ammonium polymer sorbent and identified a chemical path for its fabrication. The new process solved the monomer immiscibility challenge encountered with the initial method (ammonium is hydrophilic and the crosslinker is hydrophobic). The team fabricated structured sorbent sheets consisting of a non-woven porous substrate impregnated with ammonium polymer and demonstrated its operation in custom made breakthrough test setup MSA DAC built at SRI, and which operates similarly to the envisioned large-scale CO 2 capture plant, to provide data for techno-economic analysis (TEA). TEA sensitivity analysis indicated that ∼$\$$100/ton CO 2 can be achieved if the target capacity of 0.75 mmol CO 2 /g structured sorbent is met. Also identified routes to decrease sorbent manufacturing cost to ∼$\$$19/kg by reducing amounts and recycling the organic solvents. More work is needed on transitioning process manufacturing from powders (which showed a capacity of up to 0.8 mmol/g sorbent) to structured sheets which showed a capacity of 0.37 mmol CO 2 /g structured sorbent (or 0.44 mmol/g sorbent if one excludes the inert porous substrate). This is likely due to different micro/nano-structure of the sorbent and material processing constraints at the laboratory scale. Sorbent cycling studies (> 100 cycles) are needed to investigate its performance stability over time.

99 GENERAL AND MISCELLANEOUS↗

Direct solar self-catalyzing pyrolysis of natural gas to hydrogen and high-quality graphite (Final Technical Report)

This project, led by researchers at UCLA in partnership with Southwest Solar Technology (SST) and SolGrapH, successfully demonstrated a new method for producing clean hydrogen fuel and high-quality graphite using concentrated solar energy. The primary goal was to develop a technology that converts natural gas (primarily methane) into two valuable products—hydrogen gas and solid carbon—without releasing carbon dioxide (CO2) into the atmosphere. This process, known as solar thermal pyrolysis, uses heat from the sun to split the methane molecules directly.

03 NATURAL GAS↗

Modeling and Analysis of a Thermophotovoltaic Integrated Self-Powered Furnace

This work investigates the energy efficiency and carbon reduction potential of self-powered residential building heating equipment using a thermodynamic modeling approach. An integrated thermophotovoltaic power module and residential scale furnace system (40,000 Btu/h) were modeled and studied in detail to assess the influence of different design configurations on primary energy efficiency. Operational characteristics such as total power generation, electrical efficiency, and heat recovery were examined in a self-powered system configuration. A sensitivity analysis was conducted to determine the influence of the electric grid’s carbon dioxide footprint (carbon intensity) and the cost of electricity on the environmental, as well as the economic, benefit associated with the self-powered configuration. Compared with a traditional furnace powered by an electric grid at a carbon intensity of 0.5 kg CO 2eq /kWh EL , the self-powered furnace was shown to decrease the annual carbon dioxide emissions by approximately 550 kg (~75% reduction), while also saving more than USD 200 in utility expenses, annually. Additionally, the carbon emission reduction potential of blending different concentrations of hydrogen in natural gas fuel was also studied.

14 SOLAR ENERGY↗

Preliminary analysis of a membrane-based atmosphere-control subsystem

Controlled ecological life supprot systems will require subsystems for maintaining the consentrations of atmospheric gases within acceptable ranges in human habitat chambers and plant growth chambers. The goal of this work was to develop a membrane-based atmosphere comntrol (MBAC) subsystem that allows the controlled exchange of atmospheric componets (e.g., oxygen, carbon dioxide, and water vapor) between these chambers. The MBAC subsystem promises to offer a simple, nonenergy intensive method to separate, store and exchange atmospheric components, producing optimal concentrations of components in each chamber. In this paper, the results of a preliminary analysis of the MBAC subsystem for control of oxygen and nitrogen are presented. Additionally, the MBAC subsystem and its operation are described.

Mccray, Scott B.↗

2-Micron Laser Transmitter for Coherent CO2 DIAL Measurement

Carbon dioxide (CO2) has been recognized as one of the most important greenhouse gases. It is essential for the study of global warming to accurately measure the CO2 concentration in the atmosphere and continuously record its variation. A high repetition rate, highly efficient, Q-switched 2-micron laser system as the transmitter of a coherent differential absorption lidar for CO2 measurement has been developed in NASA Langley Research Center. This laser system is capable of making a vertical profiling of CO2 from ground and column measurement of CO2 from air and space-borne platform. The transmitter is a master-slave laser system. The master laser operates in a single frequency, either on-line or off-line of a selected CO2 absorption line. The slave laser is a Q-switched ring-cavity Ho:YLF laser which is pumped by a Tm:fiber laser. The repetition rate can be adjusted from a few hundred Hz to 10 kHz. The injection seeding success rate is from 99.4% to 99.95%. For 1 kHz operation, the output pulse energy is 5.5mJ with the pulse length of ~50 ns. The optical-to-optical efficiency is 39% when the pump power is 14.5W. A Ho:YLF laser operating in the range of 2.05 micrometers can be tuned over several characteristic lines of CO2 absorption. Experimentally, a diode pumped Ho:Tm:YLF laser has been successfully used as the transmitter of coherent differential absorption lidar for the measurement of CO2 with a repetition rate of 5 Hz and pulse energy of 75 mJ. For coherent detection, high repetition rate is required for speckle averaging to obtain highly precise measurements. However, a diode pumped Ho:Tm:YLF laser can not operate in high repetition rate due to the large heat loading and up-conversion. A Tm:fiber laser pumped Ho:YLF laser with low heat loading can operate in high repetition rate. A theoretical model has been established to simulate the performance of Tm:fiber laser pumped Ho:YLF lasers. For continuous wave (CW) operation, high pump intensity with small beam size is suitable for high efficiency. For Q-switched operation, the optimal energy extraction relies on the pump intensity, pump volume, and pump duration which is inversely proportion to the repetition rate. CW and Q-switched Ho:YLF lasers with different linear cavity configurations have been designed and demonstrated for a 30 W Tm:fiber pump laser. The CW Ho laser slope efficiency and optical-to-optical efficiencies reach 65% and 55%, respectively. The pulsed laser efficiency depends on the repetition rate. For 1 kHz operation, the optical-to-optical efficiency is 39% when the pump power is 14.5W. Currently, the injection seeding success rate is between 99.4% and 99.95%. After a ten thousand pulses, the standard deviation of the laser frequency jitter is about 3 MHz. It meets the requirements of highly precise CO2 concentration measurement. In conclusion, an injection seeded, high repetition rate, Q-switched Ho:YLF laser has been developed for a coherent CO2 differential absorption lidar. This master-slave laser system has high optical-to-optical efficiency and seeding success rate. It can potentially meet the requirements of the coherent detection of CO2 concentration by a differential absorption lidar technique.

Singh, Upendra N.↗

Laboratory IR Studies and Astrophysical Implications of C2H2-Containing Binary Ices

Studies of molecular hot cores and protostellar environments have shown that the observed abundance of gas-phase acetylene (C2H2) cannot be matched by chemical models without the inclusion of C2H2 molecules subliming from icy grain mantles. Searches for infrared (IR) spectral features of solid-phase acetylene are under way, but few laboratory reference spectra of C2H2 in icy mixtures, which are needed for spectral fits to observational data, have been published. Here, we report a systematic study of the IR spectra of condensed-phase pure acetylene and acetylene in ices dominated by carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and water (H2O). We present new spectral data for these ices, including band positions and intrinsic band strengths. For each ice mixture and concentration, we also explore the dependence of acetylene's nu5-band position (743 cm-1, 13.46 micrometers) and FWHM on temperature. Our results show that the nu5 feature is much more cleanly resolved in ices dominated by non-polar and low-polarity molecules, specifically CO, CO2, and CH4, than in mixtures dominated by H2O-ice. We compare our laboratory ice spectra with observations of a quiescent region in Serpens.

Knez, C.↗

Fiber-Based Laser Transmitter at 1.57 Micrometers for Remote Sensing of Atmospheric Carbon Dioxide from Satellites

Over the past 20 years, NASA Goddard has successfully developed space-based lidar for remote sensing studies of the Earth and planets. The lidar in all missions to date have used diode pumped Nd:YAG laser transmitters. Recently we have been concentrating work on developing integrated path differential absorption (IPDA) lidar to measure greenhouse gases, with the goal of measurements from space. Due to the absorption spectrum of CO2 a fiber-based master oscillator power amplifier (MOPA) laser with a tunable seed source is an attractive laser choice. Fiber-based lasers offer a number of potential advantages for space, but since they are relatively new, challenges exist in developing them. In order to reduce risks for new missions using fiber-based lasers, we developed a 30- month plan to mature the technology of a candidate laser transmitter for space-based CO2 measurements to TRL-6. This work is also intended to reduce development time and costs and increase confidence in future mission success.

Fiber Lasers↗

Plasma Assisted Nutrient Recovery from Inedible Biomass via Ash Leaching

Sustaining a human presence on the Moon, Mars, or deep space will require closing loops on many life support systems. Some form of agriculture will be required because plants produce the vitamins, antioxidants, and essential oils in our diets that degrade over time in stored foods. In addition, they provide dietary fiber, restore air, and purify water. Growing plants will require recycling nutrients trapped in inedible vegetation. Researchers at KSC have investigated the use of a thermal plasma with various carrier gases to thermally degrade inedible plant biomass for nutrient recovery. Previous work demonstrated a thermally degrading environment such as a muffle furnace improved nutrient recovery from inedible biomass prior to an acid leaching process. However, a muffle furnace is an inefficient process. We have explored the use of a small scale, thermal plasma for degradation of pellets to enhance the breakdown of plant stems, leaves, and debris to further close the nutrient loop. Plasma carrier gases such as carbon dioxide (CO2), nitrogen (N2), and air were used to explore variations in recovery and potential chemical by-products. Plasma processed inedible biomass was added to varying concentrations of acid solution for leaching of nutrients (e.g. potassium (K) , magnesium (Mg), calcium (Ca), and phosphorus (P)) for reuse in the crop production cycle. We also examined total N2 recovery. Results are presented showing the impact of plasma processing prior to acid leaching on recovery of plant nutrients.

Kenneth Engeling↗

An Integrative Model for Soil Biogeochemistry and Methane Processes. II: Warming and Elevated CO 2 Effects on Peatland CH 4 Emissions

Peatlands are one of the largest natural sources for atmospheric methane (CH 4 ), a potent greenhouse gas. Climate warming and elevated atmospheric carbon dioxide (CO 2 ) are two important environmental factors that have been confirmed to stimulate peatland CH 4 emissions; however, the mechanisms underlying enhanced emissions remain elusive. A data-model integration approach was applied to understand the CH 4 processes in a northern temperate peatland under a gradient of warming and doubled atmospheric CO 2 concentration. We found that warming and elevated CO 2 stimulated CH 4 emissions through different mechanisms. Warming initially stimulated but then suppressed vegetative productivity while stimulating soil organic matter (SOM) mineralization and dissolved organic carbon (DOC) fermentation, which led to higher acetate production and enhanced acetoclastic and hydrogenotrophic methanogenesis. Warming also enhanced surface CH 4 emissions, which combined with warming-caused decreases in CH 4 solubility led to slightly lower dissolved CH 4 concentrations through the soil profiles. Elevated CO 2 enhanced ecosystem productivity and SOM mineralization, resulting in higher DOC and acetate concentrations. Higher DOC and acetate concentrations increased acetoclastic and hydrogenotrophic methanogenesis and led to higher dissolved CH 4 concentrations and CH 4 emissions. Both warming and elevated CO 2 had minor impacts on CH 4 oxidation. A meta-analysis of warming and elevated CO 2 impacts on carbon cycling in wetlands agreed well with a majority of the modeled mechanisms. Finally, this mechanistic understanding of the stimulating impacts of warming and elevated CO 2 on peatland CH 4 emissions enhances our predictability on the climate-ecosystem feedback.

54 ENVIRONMENTAL SCIENCES↗

Boreal conifers maintain carbon uptake with warming despite failure to track optimal temperatures

Warming shifts the thermal optimum of net photosynthesis ( T optA ) to higher temperatures. However, our knowledge of this shift is mainly derived from seedlings grown in greenhouses under ambient atmospheric carbon dioxide (CO 2 ) conditions. It is unclear whether shifts in T optA of field-grown trees will keep pace with the temperatures predicted for the 21 st century under elevated atmospheric CO 2 concentrations. Here, using a whole-ecosystem warming controlled experiment under either ambient or elevated CO 2 levels, we show that T optA of mature boreal conifers increased with warming. However, shifts in T optA did not keep pace with warming as T optA only increased by 0.26–0.35°C per 1°C of warming. Net photosynthetic rates estimated at the mean growth temperature increased with warming in elevated CO 2 spruce, while remaining constant in ambient CO 2 spruce and in both ambient CO 2 and elevated CO 2 tamarack with warming. Although shifts in T optA of these two species are insufficient to keep pace with warming, these boreal conifers can thermally acclimate photosynthesis to maintain carbon uptake in future air temperatures.

54 ENVIRONMENTAL SCIENCES↗

Two Catalysts for Selective Oxidation of Contaminant Gases

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.

Wright, John D.↗

New calculations for photosynthesis measurement systems: what’s the impact for physiologists and modelers?

Measurement of carbon dioxide (CO 2 ) and water vapor (H 2 O) exchanged by leaves has been tremendously important for advancing understanding of plant physiology. Typically, photosynthesis measurement systems estimate the concentration of CO 2 and H 2 O in air that has passed over a leaf inside a leaf chamber. Together with additional information such as flow rate, leaf area, and measurement of environmental variables, the calculations of von Caemmerer & Farquhar (1981), hereafter vCF1981, are used to estimate CO 2 and H 2 O fluxes between the leaf and atmosphere. Furthermore, the combination of the vCF1981 calculations and photosynthesis measurement systems has enabled significant advances in the understanding and model representation of leaf-level photosynthesis and respiration.

54 ENVIRONMENTAL SCIENCES↗

Integrated Heat Pump Thermal Storage and Power Cycle for CSP (Final Technical Report)

Pumped thermal energy storage (PTES) is a storage system that stores electricity in thermal reservoirs. In this project, methods of integrating PTES with concentrating solar power (CSP) systems were investigated and their feasibility evaluated. Hybrid "solar-PTES" devices can provide both flexible renewable power generation as well as a variety of electricity storage services. Techno-economic models of PTES and solar-PTES were developed and used to assess their performance, cost, and commercial viability. Systems were optimized using multi-objective optimization techniques. The value that these storage devices provide to the grid was estimated using production cost modelling. Key advances made in this project include the development of detailed techno-economic models that improve state-of-the-art assessments of these technologies. Off-design models were developed and used in grid-analysis models. This work describes for the first time how PTES and solar-PTES behave over a range of operating points and assesses the value that these systems can provide to the electrical grid. Feedback was obtained from experts in the field, which clarified key technological and economic barriers that must be addressed to improve the feasibility of these devices.

14 SOLAR ENERGY↗

EPCAPE-PT-LANL Measurements: NO/NOx Analyzer

Coastal cities offer a unique environment for studying aerosol-cloud interactions and the effects of urban emissions on cloud properties. As part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), the Partitioning Thrust by Los Alamos National Laboratory (EPCAPE-PT-LANL) was conducted. Our campaign focused on measuring the optical and chemical properties of aerosols and their interactions within marine stratocumulus clouds in La Jolla, California. EPCAPE-PT-LANL enhances the primary goals of EPCAPE through innovative observations of vapor-phase transitions between aerosols and cloud droplets, the impact of black carbon on aerosol-cloud dynamics, and the effects of cloud processing on aerosol optical properties. Instrument: NO2/NO/NOx Monitor (2B-Technology) Header: - NO2_2B[ppb]: Concentration of nitrogen dioxide (NO2) measured at the time of the sampling, expressed in parts per billion. - NO_2B[ppb]: Concentration of nitric oxide (NO) measured at the time of the sampling, expressed in parts per billion. - NOx_2B[ppb]: Total concentration of nitrogen oxides (NOx, which includes NO and NO2) measured at the time of the sampling, expressed in parts per billion.

54 ENVIRONMENTAL SCIENCES↗

Development of a prototype regeneration carbon dioxide absorber

A prototype regenerable carbon dioxide absorber was developed to maintain the environmental quality of the portable life support system. The absorber works on the alkali metal carbonate-bicarbonate solid-gas reaction to remove carbon dioxide from the atmosphere. The prototype sorber module was designed, fabricated, and tested at simulated extravehicular activity conditions to arrive at optimum design. The unit maintains sorber outlet concentration below 5 mm Hg. An optimization study was made with respect to heat transfer, temperature control, sorbent utilization, sorber life and regenerability, and final size of the module. Important parameters influencing the capacity of the final absorber unit were identified and recommendations for improvement were made.

Patel, P. S.↗

Gas Exchange, Transpiration and Yield of Sweetpotato Grown in a Controlled Environment

Sweetpotato was grown to harvest maturity within NASA Johnson Space Center's Variable Pressure Growth Chamber (VPGC) to characterize crop performance for potential use in advanced life support systems as a contributor to food production, air revitalization and resource recovery. Stem cuttings of breeding clone "TU-82-155" were grown hydroponically at a density of 17 plants m(sup -2) using a modified pressure-plate growing system (Patent No. 4860-490, Tuskegee University). Lighting was provided by HPS lamps at a photoperiod of 12h light: 12h dark. The photosynthetic photon flux was maintained at 500, 750 and 1000 micro mol m(sup -2) s(sub -1) during days 1-15, 16-28, 29-119, respectively. Canopy temperatures were maintained at 28 C: light: 22 C:dark. During the light period, relative humidity and carbon dioxide were maintained at 70% and 1200 micro liters l(sup -1), respectively. Nutrient solution was manually adjusted 2 to 4 times per week by addition of 10X concentrated modified half-strength Hoagland nutrient salts and NaOH to return the electrical conductivity and pH to 1.2 mS cm(sup -1) and 6.0, respectively. At 17 weeks (119 days) from transplanting, a total of 56.5 kilograms fresh mass of storage roots (84.1% moisture) were harvested from the 11.2 m(sup 2) chamber, resulting in a yield 5.0 kilograms m(sup -2). Harvest index, based on fresh mass, was 38.6%. Rates of net photosynthesis, dark respiration, transpiration, and ethylene production will be reported.

Barta, Daniel J.↗