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At least 325 records · Page 18

Kinetics of Carbon Condensation in Detonation of High Explosives: First-Order Phase Transition Theory Perspective

We report the kinetics of carbon condensation, or carbon clustering, in detonation of carbon-rich high explosives is modeled by solving a system of rate equations for concentrations of carbon particles. Unlike previous efforts, the rate equations account not only for the aggregation of particles but also for their fragmentation in a thermodynamically consistent manner. Numerical simulations are performed, yielding the distribution of particle concentrations as a function of time. In addition to that, analytical expressions are obtained for all the distinct steps and regimes of the condensation kinetics, which facilitates the analysis of the numerical results and allows one to study the sensitivity of the kinetic behavior to the variation of system parameters. The latter is important because the numerical values of many parameters are not reliably known at present. The theory of the kinetics of first-order phase transitions is found adequate to describe the general kinetic trends of carbon condensation, as described by the rate equations. Such physical phenomena and processes as the coagulation, nucleation, growth, and Ostwald ripening are observed, and their dependence on various system parameters is studied and reported. It is believed that the present work will become useful when analyzing the present and future results for the kinetics of carbon condensation, obtained from experiments or atomistic simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evidence for multi-decadal fuel buildup in a large California wildfire from smoke radiocarbon measurements

In recent decades, there has been a significant increase in annual area burned in California's Sierra Nevada mountains. This rise in fire activity has prompted the need to understand how historical forest management practices affect fuel composition and emissions. Here we examined the total carbon (TC) concentration and radiocarbon abundance (Δ 14 C) of particulate matter (PM) emitted by the KNP Complex Fire, which occurred during California's 2021 wildfire season and affected several groves of giant sequoia trees in the southern Sierra Nevada. During a 26 h sampling period, we measured concentrations of fine airborne PM (PM 2.5 ), as well as dry air mole fractions of carbon monoxide (CO) and methane (CH 4 ), using a ground-based mobile laboratory. We also collected filter samples of PM 2.5 for analysis of TC concentration and Δ 14 C. High correlation among PM 2.5 , CO, and CH 4 time series confirmed that our PM 2.5 measurements captured variability in wildfire emissions. Using a Keeling plot approach, we determined that the mean Δ 14 C of PM 2.5 was 111.6 ± 7.7‰ (n = 12), which was considerably enriched relative to atmospheric carbon dioxide in the northern hemisphere in 2021 (-3.2 ± 1.4‰). Combining these Δ 14 C data with a steady-state one-box ecosystem model, we estimated that the mean age of fuels combusted in the KNP Complex Fire was 40 years, with a range of 29–57 years. These results provide evidence for emissions originating from woody biomass, larger-diameter fine fuels, and coarse woody debris that have accumulated over multiple decades. This is consistent with independent field observations that indicate high fire intensity contributed to widespread giant sequoia mortality. With the expanded use of prescribed fires planned over the next decade in California to mitigate wildfire impacts, our measurement approach has the potential to provide regionally-integrated estimates of the effectiveness of fuel treatment programs.

54 ENVIRONMENTAL SCIENCES↗

Sabatier Methanation Reactor for Space Exploration

The Sabatier Methanation Reactor technology is of vital importance to the success of the human and robotic exploration program. In order to achieve an affordable program, the logistics supply to support the mission must be minimized to the fullest extent possible. One area of potential reduction with high return on investment is the closure of life support loops, particularly oxygen and water. The Sabatier system accomplishes this by utilizing hydrogen and carbon dioxide, waste products from the life support system, to produce water and methane. The recovered water is then recycled back into the life support system to provide oxygen; while the methane can be used for propulsion, or can be broken down further to recover the hydrogen. This technology is applicable not only to transit phases of exploration, but surface habitats as well as in-situ propellant production. The Sabatier Reactor system has been developed for ground based demonstration experiments extensively over the past 30 years. Over the past three years, NASA has funded development of the Sabatier Carbon Dioxide Reduction Assembly (CRA) for use on the ISS. Currently this system is at TRL 5 and it is expected that the system will be flown on the ISS as a flight experiment, The purpose of the flight experiment is to integrate the Sabatier CRA into a synchronized system with the oxygen generation system and the carbon dioxide concentrator. The flight experiment will verify the integration of the different systems working together plus it will verify the capability of the system to operate, and effectively separate its products in a micro-gravity environment. Subsequent to design validation, the flight experiment can remain onboard the ISS providing valuable water to offset logistics re-supply requirements. Some of the challenges facing the development of the Sabatier system include handling vibration induced particulates, microgravity phase separation and containment of hazardous gases. Plans for adequately addressing these issues will be presented. The Sabatier carbon dioxide reduction process will greatly benefit any of the extended duration human exploration missions because of the tremendous savings of consumables realized. Any of these mission scenarios, be they transit or surface based, must consider closing the life support loops in order to make the mission achievable, let alone affordable. Carbon dioxide reduction technology will be necessary for future outpost habitats, and the technology needs to be proven viable in a space application. The Sabatier methanation reaction is also a desirable method for producing propellant from the Mars atmosphere. The common system could be designed to accept carbon dioxide from an indoor air revitalization loop concentrator, or from an outdoor atmosphere compressor. Carbon dioxide reduction validation is but one step in the spiral development of the in-situ propellant production system desired for future planetary exploration.

Murdoch, Karen↗

Desiccant humidity control system

A regenerable sorbent system was investigated for controlling the humidity and carbon dioxide concentration of the space shuttle cabin atmosphere. The sorbents considered for water and carbon dioxide removal were silica gel and molecular sieves. Bed optimization and preliminary system design are discussed along with system optimization studies and weight penalites.

Amazeen, J.↗

Photosynthesis-dependent Isoprene Emission from Leaf to Planet in a Global Carbon-chemistry-climate Model

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the FarquharBallBerry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50 of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 6496) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr1 that increases by 30 in the artificial absence of plant water stress and by 55 for potential natural vegetation.

photosynthesis↗

System and method for synthesis of dialkyl carbonates using carbon dioxide reaction with methanol and ammonia

A method and system for membrane-assisted production of high purity concentrated dimethyl carbonate by the reaction of carbon dioxide and methanol is provided. Carbon dioxide is recovered from flue gas or other dilute streams from industrial processes by a membrane and subsequent conversion takes place to an intermediate methyl carbamate by reacting of carbon dioxide with ammonia and methanol. For high-purity carbon dioxide obtained by one of the carbon capture technologies or by a process (such as, for example, ethanol fermentation process) the membrane reactor is replaced with a catalytic reactor for direct conversion of carbon dioxide to methyl carbamate by reacting with ammonia and methanol. The methyl carbamate is further reacted with methanol for conversion to dimethyl carbonate. An integrated reactive distillation process using side reactors is used for facilitating the catalytic reaction in the subject method for producing high purity dimethyl carbonate.

Panchal, Chandrakant B.↗

Plant-Soil Relationships Influence Observed Trends Between Manganese and Carbon Across Biomes

Manganese (Mn) is an essential plant micronutrient that plays a critical role in the litter decomposition by oxidizing and degrading complex organic molecules. Previous studies report a negative correlation between Mn concentrations and carbon (C) storage in organic horizons and suggest that high Mn concentrations in leaf litter reduce soil C storage in forest ecosystems, presumably by stimulating the oxidation of lignin by fungal enzymes. Yet, the relationship between Mn and C in the litter layer and organic soil remains poorly understood and restricted to a few biomes, hampering our ability to improve mechanistic understanding of soil C accumulation. Here, to examine plant-soil interactions that underlie observed relationships between Mn and C across a wide range of biomes, we extracted biogeochemical data reported for plants and soils from the National Ecological Observatory Network (NEON) database. We found that increased C and nitrogen (N) storage in organic horizons were associated with declines in Mn concentrations across diverse ecosystems at the continental scale, and this relationship was associated with the degree of organic matter decomposition (i.e., O i , O e , and O a ). Carbon and N stocks were more strongly correlated with Mn than with climatic variables (i.e., temperature and precipitation). Foliar Mn was strongly correlated with foliar lignin, and both these parameters increased with a decrease in soil pH, indicating links between soil pH, foliar chemistry, and litter decomposability. Our observations suggest that increased Mn bioavailability and accumulation in foliage under moderately acidic soil conditions support fungal decomposition of lignin-rich litter and contributes to lower soil C stocks.

54 ENVIRONMENTAL SCIENCES↗

Arctic Permafrost Thawing Enhances Sulfide Oxidation

Permafrost degradation is altering biogeochemical processes throughout the Arctic. Thaw-induced changes in organic matter transformations and mineral weathering reactions are impacting fluxes of inorganic carbon (IC) and alkalinity (ALK) in Arctic rivers. However, the net impact of these changing fluxes on the concentration of carbon dioxide in the atmosphere (pCO 2 ) is relatively unconstrained. Resolving this uncertainty is important as thaw-driven changes in the fluxes of IC and ALK could produce feedbacks in the global carbon cycle. Enhanced production of sulfuric acid through sulfide oxidation is particularly poorly quantified despite its potential to remove ALK from the ocean-atmosphere system and increase pCO 2 , producing a positive feedback leading to more warming and permafrost degradation. In this work, we quantified weathering in the Koyukuk River, a major tributary of the Yukon River draining discontinuous permafrost in central Alaska, based on water and sediment samples collected near the village of Huslia in summer 2018. Using measurements of major ion abundances and sulfate (SO 4 2- ) sulfur ( 34 S/ 32 S) and oxygen ( 18 O/ 16 O) isotope ratios, we employed the MEANDIR inversion model to quantify the relative importance of a suite of weathering processes and their net impact on pCO 2 . Calculations found that approximately 80% of SO 4 2- in mainstem samples derived from sulfide oxidation with the remainder from evaporite dissolution. Moreover, 34 S/ 32 S ratios, 13 C/ 12 C ratios of dissolved IC, and sulfur X-ray absorption spectra of mainstem, secondary channel, and floodplain pore fluid and sediment samples revealed modest degrees of microbial sulfate reduction within the floodplain. Weathering fluxes of ALK and IC result in lower values of pCO 2 over timescales shorter than carbonate compensation (~10 4 yr) and, for mainstem samples, higher values of pCO 2 over timescales longer than carbonate compensation but shorter than the residence time of marine (~10 7 yr). Furthermore, the absolute concentrations of and Mg 2+ in the Koyukuk River, as well as the ratios of SO 4 2- and Mg 2+ to other dissolved weathering products, have increased over the past 50 years. Through analogy to similar trends in the Yukon River, we interpret these changes as reflecting enhanced sulfide oxidation due to ongoing exposure of previously frozen sediment and changes in the contributions of shallow and deep flow paths to the active channel. Overall, these findings confirm that sulfide oxidation is a substantial outcome of permafrost degradation and that the sulfur cycle responds to permafrost thaw with a timescale-dependent feedback on warming.

54 ENVIRONMENTAL SCIENCES↗

Controlled phosphate doping into nanoscopic SiO 2 proton conducting membranes

This article describes a method to introduce phosphate (PO 4 ) into SiO 2 atomic layer deposition (ALD) films in a self-limiting fashion. The method involves the use of a less common phosphate precursor, trimethyl phosphite [P(OMe) 3 ], to introduce PO 4 as a low-level dopant, <1 at. %, into a SiO 2 ALD process using bis(ethylmethylamino)silane and a modified O 3 conversion. P(OMe) 3 does not deposit a film with typical oxygen sources but incorporates as PO 4 in an ABC-type ALD scheme at deposition temperatures ranging from 100 to 300 °C. Addition of up to ∼1 at. % of PO 4 does not significantly impact the film density or concentrations of carbon and nitrogen impurities, which are both <0.4 at. %. Despite the relatively low dopant concentrations, PO 4 incorporation is shown to have a large impact on transport properties of the film. When explored as proton (H + )-conducting membranes, undoped SiO 2 ALD films showed H + conductivities (3 × 10 −6 –8 × 10 −5 S cm −1 ) and low H 2 permeabilities (<10 −9 cm 2 s −1 ) when measured at room temperature. The addition of PO 4 is shown to increase H + conductivity to 2 × 10 −4 S cm −1 , while maintaining low H 2 permeability of <10 −9 cm 2 s −1 . The ratio of H + conductivity to H 2 permeability, a key performance metric for H + -conducting membranes used in water electrolyzers, exceeds that of commercial Nafion-117 membranes. Here, the moderate H + conductivity and very low H 2 permeability of PO 4 -doped SiO 2 films make them promising candidates as fluorine-free replacements for Nafion in applications such as water electrolysis, hydrogen fuel cells, and redox flow batteries.

Atomic layer deposition↗

Transformative Impacts of Laser-Induced Breakdown Spectroscopy on Environmental and Biological Research at Oak Ridge National Laboratory

This manuscript will present an advancement of transformative research that has been conducted at Oak Ridge National Laboratory (ORNL) over a 25-year period (2000–2025) on a variety of environmental and biological matrices. These investigations derived a fundamental understanding of how elemental detection and analysis of these matrices led to the knowledge and discovery of natural processes in plants and the environment. Each project led to the initiation of a new research area which unearthed awesome and novel breakthroughs. Highlights are listed below: 1. The preliminary research at ORNL centered on the detection of aerosols utilizing Laser-induced Breakdown Spectroscopy (LIBS) technology. The Clean Air Act Amendment (CAAA) of 1990 highlighted the importance of identifying hazardous air pollutants (HAPs) due to their impact on environmental and human health, thereby underscoring the need to detect various toxic elements. Research in aerosol chemistry aimed to identify these harmful elements released by factories during periods of increased emissions in their manufacturing processes. LIBS emerged as the most effective method for real-time, in situ measurements of metal species in both gaseous and aerosol phases. 2. An understanding of the presence of total carbon in soils gives perspective on how to develop carbon sequestration strategies. The recognition that carbon sinks can evolve back to carbon sources to emit back to the atmosphere was an important consideration. Also, the concentration of carbon in soil indicates the health of land areas for growing crops successfully. 3. The direct detection of most of the elements in a wood sample in a single emission spectrum, without sample preparation, encouraged the research to use the LIBS technique for preservative treated wood coupled with use of multivariate statistical methodology. Additionally, it encouraged the researchers to try to differentiate natural woods from different parts of the country, and it was successfully demonstrated that LIBS coupled with MVA analysis could differentiate wood of different species from each other and of similar species grown in different environments based on their elemental spectra. This was a breakthrough since it revealed a systematic approach to connect elemental scarcity and abundance to either drought or typical rainfall conditions for the hardwood trees grown in specific areas. 4. Furthermore, the research progressed to reveal physiological and developmental processes contributing to biomass production such that the variation in leaf elemental composition increases our understanding of terrestrial nutrient cycles, as well as tracking the transfer of toxic elements from soils to living organisms. 5. Recently another breakthrough viz., ionomics initiated the correlation of elements to specific genes, uncovering the function that the element performed in the plant. More recently, this has been extended from plants to fungi as well as fungi growing in symbiotic relations with plants.

09 BIOMASS FUELS↗

Partial equilibrium model for predicting concentration of CO in combustion

A simple kinetic model, based upon the concept of partial equilibrium, is developed for predicting carbon monoxide concentrations in such steady-flow hydrocarbon-air combustion systems as gas-turbine combustors. The only two kinetic constraints used in the model are on the rate of change of the total number of gaseous particles in the system, and on the rate of change of the CO concentration. The accuracy of the model is verified by comparison with experimental results obtained by burning kerosene with air in a 130,000 Btu/hr atmospheric-pressure steady-flow burner. Burnt-gas cooling rates of 1,000,000 K/sec, about the magnitude encountered in the dilution zone of gas-turbine combustors, were obtained with a compact water-cooled heat exchanger. Good agreement between measured CO concentrations and the values predicted by the partial-equilibrium model was obtained.

Morr, A. R.↗

Laser Subdivision of the Genesis Concentrator Target Sample 60000

The Genesis Allocation Committee received a request for ~ 1 square centimeter of the diamond-like-carbon (DLC) concentrator target for the analysis of solar wind nitrogen isotopes. The target consists of a single crystal float zone (FZ) silicon substrate having a thickness on the order of 550 micrometers with a 1.5-3.0 micrometer-thick coating of DLC on the exposed surface. The solar wind is implanted shallowly in the front side DLC. The original target was a circular quadrant with a radius of 3.1 cm; however, the piece did not survive intact when the spacecraft suffered an anomalous landing upon returning to Earth on September 8, 2004. An estimated 75% of the DLC target was recovered in at least 18 fragments. The largest fragment, Genesis sample 60000, has been designated for this allocation and is the first sample to be subdivided using our laser scribing system Laser subdivision has associated risks including thermal diffusion of the implant if heating occurs and unintended breakage during cleavage. A careful detailed study and considerable subdividing practice using non-flight FZ diamond on silicon, DOS, wafers has considerably reduced the risk of unplanned breakage during the cleaving process. In addition, backside scribing reduces the risk of possible thermal excursions affecting the implanted solar wind, implanted shallowly in the front side DLC.

Lauer, Howard V., Jr.↗

Organic geochemistry of sediments from the continental margin off southern New England, U.S.A.--Part II. Lipids

Organic geochemical measurements of the lipid fraction, comparing saturated and aromatic hydrocarbons, fatty acids, alcohols and sterols, have been carried out on six sediments cores collected from the Atlantic shelf, slope and the rise areas to evaluate the cross-shelf transport of the organic carbon. The concentration of most of the organic compound classes studied is correlated with the total organic carbon, which decreases from the shelf through slope to the rise. Terrigenous carbon is recognizable even in the slope and rise sediments, but terrestrial influx decreases relative to marine generated lipids in the slope and rise organic matter. We estimate that approximately 50% of the shelf organic matter is exported to the slope. Data of sediment trap material collected at 1200 m from 1250 m water depth are discussed and compared with that of surface sediment from 1280 m water depth (slope). Fluxes for specific organic compound classes have been computed. The fluxes are of the same magnitude as for equatorial North Atlantic trap particulates at comparable water depth, studied by other investigations.

NASA Discipline Exobiology↗

Plant growth modeling at the JSC variable pressure growth chamber - An application of experimental design

This paper describes the approach and results of an effort to characterize plant growth under various environmental conditions at the Johnson Space Center variable pressure growth chamber. Using a field of applied mathematics and statistics known as design of experiments (DOE), we developed a test plan for varying environmental parameters during a lettuce growth experiment. The test plan was developed using a Box-Behnken approach to DOE. As a result of the experimental runs, we have developed empirical models of both the transpiration process and carbon dioxide assimilation for Waldman's Green lettuce over specified ranges of environmental parameters including carbon dioxide concentration, light intensity, dew-point temperature, and air velocity. This model also predicts transpiration and carbon dioxide assimilation for different ages of the plant canopy.

Miller, Adam M.↗

Implications of Climate Mitigation for Future Agricultural Production

Climate change is projected to negatively impact biophysical agricultural productivity in much of the world. Actions taken to reduce greenhouse gas emissions and mitigate future climate changes, are thus of central importance for agricultural production. Climate impacts are, however, not unidirectional; some crops in some regions (primarily higher latitudes) are projected to benefit, particularly if increased atmospheric carbon dioxide is assumed to strongly increase crop productivity at large spatial and temporal scales. Climate mitigation measures that are implemented by reducing atmospheric carbon dioxide concentrations lead to reductions both in the strength of climate change and in the benefits of carbon dioxide fertilization. Consequently, analysis of the effects of climate mitigation on agricultural productivity must address not only regions for which mitigation is likely to reduce or even reverse climate damages. There are also regions that are likely to see increased crop yields due to climate change, which may lose these added potentials under mitigation action. Comparing data from the most comprehensive archive of crop yield projections publicly available, we find that climate mitigation leads to overall benefits from avoided damages at the global scale and especially in many regions that are already at risk of food insecurity today. Ignoring controversial carbon dioxide fertilization effects on crop productivity, we find that for the median projection aggressive mitigation could eliminate approximately 81% of the negative impacts of climate change on biophysical agricultural productivity globally by the end of the century. In this case, the benefits of mitigation typically extend well into temperate regions, but vary by crop and underlying climate model projections. Should large benefits to crop yields from carbon dioxide fertilization be realized, the effects of mitigation become much more mixed, though still positive globally and beneficial in many food insecure countries.

Mueller, Christoph↗

Effects of Low-Carbon Energy Adoption on Airborne Particulate Matter Concentrations With Feedbacks to Future Climate Over California

California plans to reduce emissions of long-lived greenhouse gases (GHGs) through adoption of new energy systems that will also lower concentrations of short-lived absorbing soot contained in airborne particulate matter (PM). Here we examine the direct and indirect effects of reduced PM concentrations under a low-carbon energy (GHG-Step) scenario on radiative forcing in California. Simulations were carried out using the source-oriented WRF/Chem (SOWC) model with 12 km spatial resolution for the year 2054. Furthermore, the avoided aerosol emissions due to technology advances in the GHG-Step scenario reduce ground level PM concentrations by ~8.85% over land compared to the Business-as-Usual (BAU) scenario, but changes to meteorological parameters are more modest. Top-of-atmospheric forcing predicted by the SOWC model increased by 0.15 W m -2 , surface temperature warmed by 0.001 K, and planetary boundary layer height (PBLH) increased by 2.20 cm in the GHG-Step scenario compared to the BAU scenario. PM climate feedbacks are small because the significant changes in ground level PM concentrations associated with the GHG-Step scenario are limited to the first few hundred meters of the atmosphere, with little change for the majority of the vertical column above that level. As an order-of-magnitude comparison, the long-term effects of global reductions in GHG emissions (RCP8.5–RCP4.5) lowered average surface temperature over the California study domain by approximately 0.76 K. The effects of long-lived climate pollutants such as CO 2 are much stronger than the effects of short-lived climate pollutants such as PM soot over California in the year 2054.

54 ENVIRONMENTAL SCIENCES↗