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All sourcesNASA NTRSDOE OSTI
NASA NTRS2026

Molecular Inventory and Comparative Organic Profiling of A Homogenized Aggregate Sample From Asteroid (101955) Bennu

Evaluating the distribution and diversity of solvent-soluble organic molecules in extraterrestrial materials provide information about the physicochemical environments where prebiotic chemistry occurred and is essential for assessing the inventory of prebiotic compounds available to the early Earth. In this work, we conducted a comprehensive molecular characterization of solvent-soluble organic compounds in a homogenized aggregate sample (ID: OREX-800107-128) of unsorted regolith from asteroid (101955) Bennu returned by NASA’s OSIRIS-REx mission. Using two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC×GC-HRMS), we identified 87 organic compounds across several molecular classes, including alkanes, polycyclic aromatic hydrocarbons, and nitrogen-, oxygen-, and sulfur-bearing species. Comparison with the organic inventory of CI (Orgueil), C2-ungrouped (Tagish Lake and Tarda), and CM2 (Murchison) carbonaceous chondrites revealed that Bennu sample OREX-800107-128 is most similar to Tagish Lake and Tarda yet compositionally distinct from all of these meteorites. This Bennu sample exhibits a relatively high abundance of low-molecular-weight aromatics (e.g., toluene), pyridine derivatives, and sulfur species such as dimethyl sulfite, consistent with episodic low-temperature aqueous alteration. The presence of these organic compounds suggests that this material experienced chemically diverse processes in the parent body conducive to complex organic synthesis, including aldol condensation reactions responsible for N- and O-bearing compounds. We also compared the molecular distributions of this Bennu sample and previously analyzed samples from (162173) Ryugu to assess potential common origins between these two carbonaceous asteroids. Bennu shows more chemically diverse and nitrogen-rich organic materials than Ryugu. While both asteroids share broadly similar primitive compositions, the observed chemical differences indicate distinct evolutionary histories within a likely common formation environment though whether Bennu and Ryugu derive from a single compositionally heterogeneous parent body or from multiple closely related progenitors remains unresolved. Further detailed comparative analyses of material from Bennu, Ryugu, and specific carbonaceous meteorites (e.g., Tagish Lake and Tarda) will provide new insights into how the N-rich molecular profile observed in Bennu samples was formed and evolved in the outer Solar System.

sample return↗
NASA NTRS1990

Carbon-rich aggregates in type 3 ordinary chondrites - Characterization, origins, and thermal history

Carbon-rich aggregates from three type 3.4-3.6 ordinary chondrites and two chondritic clasts have been characterized in detail, using TEM techniques. The aggregates in all the meteorites studied range in size from 5-1000 microns and consist of a fine scale intergrowth of poorly graphitized carbon, amorphous carbon, Fe,Ni metal, and minor chromite. Contrary to previous reports, well-crystallized graphite and magnetite are absent. The association of Fe,Ni metal and carbonaceous material suggests that the original carbonaceous material may have formed by Fischer-Tropsch (FT) type reactions at low temperatures (less than 400 K), possibly in the solar nebula. This carbonaceous material probably consisted of a complex mixture of hydrocarbons, kerogen-like material, and other complex organic molecules. The aggregates were subsequently accreted onto the ordinary chondrite parent bodies and underwent planetary thermal processing which resulted in the catalytic graphitization of hydrocarbons, in the presence of Fe,Ni metal, to produce poorly graphitized carbon. None of the meteorites studied experienced temperatures sufficiently high to produce crystalline, ordered graphite. Using the empirical geothermometer of Rietmeijer and Mackinnon (1985), the measured d(002) spacings of poorly graphitized carbon show that graphitization occurred at temperatures between 300 and 450 C. This range of temperatures is significantly lower than the generally quoted metamorphic temperatures for type 3.4-3.6 ordinary chondrites (about 450-500 C).

Brearley, Adrian J.↗
NASA NTRS2001

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗
NASA NTRS2012

Burning Questions in Gravity-Dependent Combustion Science

Building upon a long history of spaceflight and ground based research, NASA's Combustion Science program has accumulated a significant body of accomplishments on the ISS. Historically, NASAs low-gravity combustion research program has sought: to provide a more complete understanding of the fundamental controlling processes in combustion by identifying simpler one-dimensional systems to eliminate the complex interactions between the buoyant flow and the energy feedback to the reaction zone to provide realistic simulation of the fire risk in manned spacecraft and to enable practical simulation of the gravitational environment experienced by reacting systems in future spacecraft. Over the past two decades, low-gravity combustion research has focused primarily on increasing our understanding of fundamental combustion processes (e.g. droplet combustion, soot, flame spread, smoldering, and gas-jet flames). This research program was highly successful and was aided by synergistic programs in Europe and in Japan. Overall improvements were made in our ability to model droplet combustion in spray combustors (e.g. jet engines), predict flame spread, predict soot production, and detect and prevent spacecraft fires. These results provided a unique dataset that supports both an active research discipline and also spacecraft fire safety for current and future spacecraft. These experiments have been conducted using the Combustion Integrated Rack (CIR), the Microgravity Science Glovebox and the Express Rack. In this paper, we provide an overview of the earlier space shuttle experiments, the recent ISS combustion experiments in addition to the studies planned for the future. Experiments in combustion include topics such as droplet combustion, gaseous diffusion flames, solid fuels, premixed flame studies, fire safety, and super critical oxidation processes.

Urban, David↗
NASA NTRS1994

Situational reaction and planning

One problem faced in designing an autonomous mobile robot system is that there are many parameters of the system to define and optimize. While these parameters can be obtained for any given situation determining what the parameters should be in all situations is difficult. The usual solution is to give the system general parameters that work in all situations, but this does not help the robot to perform its best in a dynamic environment. Our approach is to develop a higher level situation analysis module that adjusts the parameters by analyzing the goals and history of sensor readings. By allowing the robot to change the system parameters based on its judgement of the situation, the robot will be able to better adapt to a wider set of possible situations. We use fuzzy logic in our implementation to reduce the number of basic situations the controller has to recognize. For example, a situation may be 60 percent open and 40 percent corridor, causing the optimal parameters to be somewhere between the optimal settings for the two extreme situations.

Yen, John↗
DOE OSTI2023

Control of Cement Timing, Mineralogy, and Texture on Hydro-chemo-mechanical Coupling from CO2 Injection into Sandstone: A Synthesis

Carbon capture, utilization, and storage (CCUS) has been widely applied to enhance oil recovery (CO2-EOR). A thorough investigation of the impact of injecting CO2 into a heterogeneous reservoir is critical to understanding the overall reservoir robustness and storage performance. We conducted fifteen flow-through tests on Morrow B sandstone that allowed for chemical reactions between a CO2-rich brackish solution and the sandstones, and four creep/flow-through tests that simultaneously allowed for chemical reactions and stress monitoring. From fluid chemistry and X-ray computed tomography, we found that the dissolution of disseminated cements and the precipitation of iron-rich clays did not significantly affect the permeability and geomechanical properties. Minor changes in mechanical properties from Brazilian and creep tests indicated that the matrix structure was well-supported by early diagenetic quartz overgrowth cement and the reservoir’s compaction history at deep burial depths. However, one sample experienced a dissolution of poikilotopic calcite, leading to a permeability increase and significant tensile strength degradation due to pore opening, which overcame the effect of the early diagenetic cements. We concluded that the Morrow B sandstone reservoir is robust for CO2 injection. Most importantly, cement timing, the abundance and texture of reactive minerals, and the reservoir’s burial history are critical in predicting reservoir robustness and storage capacity for CO2 injection.

Wu, Zhidi (ORCID:0000000338869492)↗
DOE OSTI2020

Influence of the double bond position in combustion chemistry of methyl butene isomers: A shock tube and laser absorption study

Shock tube experiments have been carried out on 2–methyl–1–butene (2M1B), 2–methyl–2–butene (2M2B), and 3–methyl–1–butene (3M1B)—the three isomers of methyl butene compound. Here, carbon monoxide (CO) time–histories and ignition delay times are obtained behind reflected shockwaves over the temperature range of 1350–1630 K and pressures of 8.3–10.5 atm with stoichiometric mixtures of 0.075% fuel in O 2 /Ar. Comparative ignition study reveals that 3M1B ignites significantly faster than the other two isomers, while 2M1B dissociates earlier but ignites later than 2M2B. Possible mechanisms for this behavior are discussed with ignition delay time sensitivity and reaction path analysis. In addition, time–resolved CO measurements are compared with three different reaction mechanisms from the literature. Sensitivity analyses have been carried out to identify important reactions that need attention to accurately predict the chemistry of these isomers. Further investigation into the rates of unimolecular fuel decomposition reactions and C 3 H 3 + O 2 = CH 2 CO + HCO reaction are suggested based on the current investigation.

09 BIOMASS FUELS↗
DOE OSTI2021

Correcting the PFNS for more consistent fission modeling

For FY20, we had a deliverable to write a report detailing efforts to simultaneously evaluate both the prompt neutron multiplicity, $\overline{ν}$, and the prompt neutron fission neutron spectrum, PFNS, using CGMF. CGMF is the LANL-developed fission fragment decay code that consistently evaporates prompt neutrons and γ rays using the Hauser-Feshbach statistical theory of compound reactions. The decay begins by constructing the initial conditions of the fission fragments, then decaying each one from the excited state by neutrons and γ rays, conserving energy, momentum, spin, and parity in each step of the emission. The initial conditions of the fragments, along with the multiplicity, energy, and direction of each emitted neutron or γ ray, are recorded, allowing for the full reconstruction of the fission event. These event histories allow us to reconstruct average quantities, as well as correlations between observables, that can be compared with experimental or evaluated data. In that initial report, although there was already a favorable comparison between $\overline{ν}$ from CGMF, experiment, and the current ENDF/B-VIII.0 evaluation, we showed that there was still significant work to be done to improve the PFNS from CGMF. Historically, the PFNS is calculated too soft by Hauser-Feshbach fission models, and CGMF is no exception. The incorrect shape presents a significant challenge in fission modeling, including for our understanding of the fission process and for our ability to consistently calculate and predict a variety of prompt fission observables (such as fission fragment initial conditions, neutron and γ-ray multiplicities and energies, and the correlations between all observables). In our companion report, we detail our success in using CGMF to evaluate $\overline{ν}$. Although not included in the optimization explicitly, we also keep the initial conditions of the fission fragments physical, along with reproducing reasonably well the neutron multiplicity distribution. As we would expect from the sensitivities calculations from, the average neutron energies change very little from the $\overline{ν}$ optimization along with the PFNS (as will be shown in Sec. 2.6). The conclusion was that the global and statistical models would have to be investigated instead of just the fission fragment initial conditions (as is sufficient for $\overline{ν}$). This report details those efforts.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1985

Willy: A prize noble Ur-Fremdling - Its history and implications for the formation of Fremdlinge and CAI

The structure and composition of Willy, a 150-micron-diameter Fremdling in CAI 5241 from the Allende meteorite, are investigated using optical, secondary-electron, and electron-backscatter microscopy and electron-microprobe analysis. The results are presented in diagrams, maps, tables, graphs, and micrographs and compared with those for other Allende Fremdlinge. Willy is found to have a concentric-zone structure comprising a complex porous core of magnetite, metal, sulfide, scheelite, and other minor phases; a compact magnetite-apatite mantle; a thin (20 microns or less) reaction-assemblage zone; and a dense outer rim of fassaite with minor spinel. A multistage formation sequence involving changes in T and fO2 and preceding the introduction of Willy into the CAI (which itself preceded CAI spinel and silicate formation) is postulated, and it is inferred from the apparent lack of post-capture recrystallization that Willy has not been subjected to temperatures in excess of 600 C and may represent the precursor material for many other Fremdlinge.

Armstrong, J. T.↗
DOE OSTI2021

Surface Dynamics of Charge Transport in LaAlO 3 /SrTiO 3 with Time-Resolved Kelvin Probe Force Microscopy

Time-resolved Kelvin probe force microscopy (tr-KPFM) was used to map surface potential dynamics in LAO/STO under its critical thickness, where it acts as an insulator, as polarizing and depolarizing electric fields were applied to planar electrodes in ambient conditions. Two time constants, for polarization and relaxation (i.e., depolarization) each, were derived and were shown to be independent of the direction of electrical field, revealing the reproducibility and recovery of the surfaces. Ambient aging or recent electrical history did not change the surface kinetics as determined by tr-KPFM. During polarization, the faster time constant (~3–6 s) is likely associated with the transport of H+ ions through the full length of the channel. The slower time constant (~40–50 s), on the other hand, is observed across only half the channel width near the higher-potential–more positive–electrode, which is likely associated with an electrochemical reaction such as the dissociation of water. This slower time constant drops to ~10–20 s toward the middle of the channel which could represent the transport of OH– ions. Furthermore, during relaxation, the fast time constant is consistent with polarization and is correlated to the same mechanism while the slower time constant is higher than it was during polarization and may represent the reabsorption of moisture from the atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A critical review of molybdenum sequestration mechanisms under euxinic conditions: Implications for the precision of molybdenum paleoredox proxies

The observed difference in molybdenum (Mo) mobility and isotopic fractionation under oxic versus euxinic (i.e., anoxic and sulfidic) aqueous conditions provides a sound operational basis for the use of Mo geochemical signatures in ancient sedimentary records to infer palaeoceanographic redox conditions. While Mo is known to exist predominantly as molybdate (MoO 4 2– ) in oxic waters and convert into thiomolybdate species (MoO x S 4-x 2– ) under euxinic conditions, the pathways that lead to Mo sequestration are highly debated. As mechanistic understanding of Mo sequestration is crucial for accurately reconstructing the chemistry of ancient oceans and constraining the timing and intensity of oxygenation events through Earth's history using Mo paleoproxies, we have closely examined the current proposed mechanisms for Mo sequestration across a wide range of euxinic conditions. Through compilation and comparison of such information, we aim to provide an integrated view of Mo sequestration processes, to identify the current controversies as well as the roots of such controversies, and importantly, to propose avenues for future research. Here, sequestration of Mo may occur through complexation with organic matter (OM), reactions with oxyhydroxide and sulfide mineral surfaces, incorporation into iron sulfide crystal structures, formation of Mo-sulfide, and cellular assimilation. However, several major questions remains unresolved, including whether OM complexation plays a significant role in overall sedimentary Mo accumulation, whether the reduction of Mo(VI) occurs during interaction with Fe-S clusters/precipitates and/or with OM, whether microbial enzymatic reduction of Mo(VI) is important in Mo sequestration, whether synergistic effects exist between the biological and abiotic processes in Mo sequestration, and whether differences in reactivity among the various thiomolybdate intermediate species and tetrathiomolybdate influence the Mo sequestration process. At the end of the review, the reliability of Mo paleoproxies is discussed and reevaluated.

58 GEOSCIENCES↗
NASA NTRS1974

Study of recrystallization and devitrification of lunar glass

The technique of differential thermal analysis (DTA) was applied to the study of the Apollo 17 orange soil (74220,63) and the Apollo 16 glass coated anorthite (64455,21). These glasses show accentuated exotherms of strain relief in the annealing range which is indicative of rapid cooling. These are amenable to interpretation by comparison to the known history of synthetic glasses. Synthetic glasses were prepared whose similarity in behavior between the lunar glasses and their synthetic analogs is striking. Approximate rates of cooling of the lunar glasses were determined from comparative DTA of lunar and synthetic glasses and from the determination of the relation of strain relief in the annealing range to quench rate. At higher temperatures the glasses show exotherms of crystallization. The crystallization products associated with the exothermic reactions have been identified by X-ray diffraction and the surface morphologies developed by strain relief and crystallization have been characterized with scanning electron microscopy.

Ulrich, D. R.↗
NASA NTRS1989

Shuttle tethered operations: The effect on orbital trajectory and inertial navigation

The first full scale test of a large tethered satellite system is planned. The Orbiter will be linked to a 500 kg payload by a 20 km tether, an action with a profound effect on the trajectory of the Orbiter. For the first time in the history of the Shuttle program, the vehicle will conduct prolonged operations with the center of mass of the orbiting system a significant distance from the center of mass of the Space Shuttle Orbiter, a violation of the fundamental assumption made in both the Orbiter ground-based and onboard navigation software. Inertial navigation of tethered operations with the Shuttle is further complicated by the presence of non-conservative forces in the system: Reaction Control System (RCS) translational effects, atmospheric drag, and electro-magnetic dynamics. These can couple with the conservative tether dynamics effects, and degrade the navigation software performance. The primary effects are examined on the Orbiter's trajectory, coupling by conservative forces during tethered operations, and the impact of both on the ability to meet inertial navigation constraints. The impact of electrodynamics, different RCS control modes, commanded attitudes, and attitude deadbands are presented. Operational guidelines which optimize successful mission navigation, and necessary navigation constraints are discussed.

Lardas, Mark N.↗
NASA NTRS2004

Chemical Reaction and Flow Modeling in Fullerene and Nanotube Production

The development of processes to produce fullerenes and carbon nanotubes has largely been empirical. Fullerenes were first discovered in the soot produced by laser ablation of graphite [1]and then in the soot of electric arc evaporated carbon. Techniques and conditions for producing larger and larger quantities of fullerenes depended mainly on trial and error empirical variations of these processes, with attempts to scale them up by using larger electrodes and targets and higher power. Various concepts of how fullerenes and carbon nanotubes were formed were put forth, but very little was done based on chemical kinetics of the reactions. This was mainly due to the complex mixture of species and complex nature of conditions in the reactors. Temperatures in the reactors varied from several thousand degrees Kelvin down to near room temperature. There are hundreds of species possible, ranging from atomic carbon to large clusters of carbonaceous soot, and metallic catalyst atoms to metal clusters, to complexes of metals and carbon. Most of the chemical kinetics of the reactions and the thermodynamic properties of clusters and complexes have only been approximated. In addition, flow conditions in the reactors are transient or unsteady, and three dimensional, with steep spatial gradients of temperature and species concentrations. All these factors make computational simulations of reactors very complex and challenging. This article addresses the development of the chemical reaction involved in fullerene production and extends this to production of carbon nanotubes by the laser ablation/oven process and by the electric arc evaporation process. In addition, the high-pressure carbon monoxide (HiPco) process is discussed. The article is in several parts. The first one addresses the thermochemical aspects of modeling; and considers the development of chemical rate equations, estimates of reaction rates, and thermodynamic properties where they are available. The second part addresses modeling of the arc process for fullerene and carbon nanotube production using O-D, 1-D and 2-D fluid flow models. The third part addresses simulations of the pulsed laser ablation process using time-dependent techniques in 2-D, and a steady state 2-D simulation of a continuous laser ablation process. The fourth part addresses steady state modeling in O-D and 2-D of the HiPco process. In each of the simulations, there is a variety of simplifications that are made that enable one to concentrate on one aspect or another of the process. There are simplifications that can be made to the chemical reaction models , e.g. reduction in number of species by lumping some of them together in a representative species. Other simulations are carried out by eliminating the chemistry altogether in order to concentrate on the fluid dynamics. When solving problems with a large number of species in more than one spatial dimension, it is almost imperative that the problem be decoupled by solving for the fluid dynamics to find the fluid motion and temperature history of "particles" of fluid moving through a reactor. Then one can solve the chemical rate equations with complex chemistry following the temperature and pressure history. One difficulty is that often mixing with an ambient gas is involved. Therefore, one needs to take dilution and mixing into account. This changes the ratio of carbon species to background gas. Commercially available codes may have no provision for including dilution as part of the input. One must the write special solvers for including dilution in decoupled problems. The article addresses both ful1erene production and single-walled carbon nanotube (SWNT) production. There are at least two schemes or concepts of SWNT growth. This article will only address growth in the gas phase by carbon and catalyst cluster growth and SW T formation by the addition of carbon. There are other models that conceive of SWNT growth as a phase separation process from clusters me up carbon and metal catalyst, with the carbon precipitating from the cluster as it cools. We will not deal with that concept in this article. Further research is needed to determine the rates at which these composite clusters form, evaporate, and segregate.

Scott, Carl D.↗
DOE OSTI2021

Upscaling Reactive Transport and Clogging in Shale Microcracks by Deep Learning

Fracture networks in shales exhibit multiscale features. A rock system may contain a few main fractures and thousands of microcracks, whose length and aperture are orders of magnitude smaller than the former. It is computationally prohibitive to resolve all the fractures explicitly for such multiscale fracture networks. One traditional approach is to model the small-scale features (e.g., microcracks in shales) as an effective medium. Although this fracture-matrix conceptualization significantly reduces the problem complexity, there are classes of physical processes that cannot be accurately upscaled by effective medium approximations, e.g., microcrack clogging during mineral reactions. Here, we employ deep learning in place of effective medium theory to upscale physical processes in small-scale features. Specifically, we consider reactive transport in a fracture-microcrack network where microcracks can be clogged by precipitation. A deep learning multiscale algorithm is developed, in which the microcracks are upscaled as a wall boundary condition of the main fractures. The wall boundary condition is constructed by recurrent neural networks, which take concentration histories as input and predict the solute transport from main fractures to microcracks. The deep learning multiscale algorithm is firstly employed in specific scenarios, then a general model is developed which can work under various conditions. The new approach is validated against fully resolved simulations and an analytical solution, providing a reliable and efficient solution for problems that cannot be upscaled by effective medium models.

58 GEOSCIENCES↗
NASA NTRS2004

Earth's Early Biosphere and the Biogeochemical Carbon Cycle

Our biosphere has altered the global environment principally by influencing the chemistry of those elements most important for life, e g., C, N, S, O, P and transition metals (e.g., Fe and Mn). The coupling of oxygenic photosynthesis with the burial in sediments of photosynthetic organic matter, and with the escape of H2 to space, has increased the state of oxidation of the Oceans and atmosphere. It has also created highly reduced conditions within sedimentary rocks that have also extensively affected the geochemistry of several elements. The decline of volcanism during Earth's history reduced the flow of reduced chemical species that reacted with photosynthetically produced O2. The long-term net accumulation of photosynthetic O2 via biogeochemical processes has profoundly influenced our atmosphere and biosphere, as evidenced by the O2 levels required for algae, multicellular life and certain modem aerobic bacteria to exist. When our biosphere developed photosynthesis, it tapped into an energy resource that was much larger than the energy available from oxidation-reduction reactions associated with weathering and hydrothermal activity. Today, hydrothermal sources deliver globally (0.13-1.1)x10(exp l2) mol yr(sup -1) of reduced S, Fe(2+), Mn(2+), H2 and CH4; this is estimated to sustain at most about (0.2-2)xl0(exp 12)mol C yr(sup -1) of organic carbon production by chemautotrophic microorganisms. In contrast, global photosynthetic productivity is estimated to be 9000x10(exp 12) mol C yr(sup -1). Thus, even though global thermal fluxes were greater in the distant geologic past than today, the onset of oxygenic photosynthesis probably increased global organic productivity by some two or more orders of magnitude. This enormous productivity materialized principally because oxygenic photosynthesizers unleashed a virtually unlimited supply of reduced H that forever freed life from its sole dependence upon abiotic sources of reducing power such as hydrothermal emanations and weathering. Communities sustained by oxygenic photosynthesis apparently thrived wherever supplies of sunlight, moisture and nutrients were sufficient. Prior to the development of oxygenic photosynthesis, the net global effect of the ancient global biosphere was to facilitate chemical equilibrium between reduced species from thermal activity and weathering and more oxidized constituents in the surface environment. But even this ancient biosphere might have been globally pervasive. The global geothermal heat flow was substantially higher during Earth's first billion years, and thus reduced chemical species might have persisted in sunlit aquatic environments. Perhaps the substantial decline in thermal activity between 4000 and 3000 Ma created a driver for oxygenic photosynthesis to develop.

DesMarais, David↗
DOE OSTI2025

Time-resolved measurements of OH during auto-ignition of syngas with trimethylsilanol and hexamethyldisiloxane

The effects of trimethylsilanol (TMSO) and hexamethyldisiloxane (HMDSO) addition on OH time histories during syngas (H 2 and CO) ignition were investigated using the University of Michigan rapid compression facility. Experiments spanned temperatures of 1010–1080 K, at a pressure of approximately 5 atm. Syngas mixtures of 1.2 % H 2 /2.8 % CO/20 % O 2 by volume (balance N 2 and Ar) provided a baseline for comparison with mixtures that included 100, 200, and 1000 ppm of the TMSO and 100 ppm of HMDSO. Narrow-line ultraviolet laser-absorption was used to measure OH mole-fraction during ignition. The addition of TMSO and HMDSO significantly shifted the OH time-histories earlier in time, by up to 51 %, compared with the baseline syngas mixture. The value of the maximum OH mole fraction was consistent between the 100 and 200 ppm TMSO mixtures and the 100 ppm HMDSO mixtures, but the maximum OH increased significantly with the 1000 ppm TMSO mixtures. Here, the OH data indicate TMSO and HMDSO were not direct sources of OH radicals. Analysis further indicates the TMSO and HMDSO decompose rapidly followed by reactions that enhance the production of H atoms, and the increased reactivity observed is via the H + O 2 = OH + O reaction.

Hexamethyldisiloxane↗
NASA NTRS2023

Early Fluid Activity on Ryugu Inferred By Oxygen, Carbon, and 53Mn-53Cr Isotopic Analyses of Carbonates and Magnetite

Samples from asteroid Ryugu returned by the Hayabusa2 mission contain evidence of extensive alteration by aqueous fluids and appear related to the CI chondrites. To understand the sources of the fluid and the timing of chemical reactions occurring during the alteration processes, we investigated the oxygen, carbon, and 53Mn-53Cr systematics of carbonate and magnetite in two Ryugu particles. We find that the fluid was initially between 0−20 °C and enriched in 13C, and 17O and 18O, and subsequently evolved towards lighter carbon and oxygen isotopic compositions as alteration proceeded. Carbonate ages show that this fluid-rock interaction took place within the first ~1.8 million years of solar system history, requiring early accretion either in a planetesimal less than ~20 km in diameter or within a larger body which was disrupted and reassembled.

Astromaterials↗