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At least 613 records · Page 34

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Shock, Everett L.↗

BOREAS AFM-03-NCAR Electra 1994 Aircraft Sounding Data

The Boreal Ecosystem-Atmosphere Study (BOREAS) Airborne Fluxes and Meteorology (AFM)-3 team used the National Center for Atmospheric Research's (NCAR) Electra aircraft to make sounding measurements to study the planetary boundary layer using in situ and remote-sensing measurements. Measurements were made of wind speed and direction, air pressure and temperature, potential temperature, dewpoint, mixing ratio of H, O, CO, concentration, and ozone concentration. Twenty-five research missions were flown over the Northern Study Area (NSA), Southern Study Area (SSA), and the transect during BOREAS Intensive Field Campaigns (IFCs) 1, 2, and 3 during 1994. All missions had from four to ten soundings through the top of the planetary boundary layer. This sounding data set contains all of the in situ vertical profiles through the boundary layer top that were made (with the exception of 'porpoise' maneuvers). Data were recorded in one-second time intervals. These data are stored in tabular ASCII files. The NCAR Electra 1994 aircraft sounding data are available from the Earth Observing System Data and Information System (EOSDIS) Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC). The data files are available on a CD-ROM (see document number 20010000884).

Lenschow, Donald H.↗

Emissions from Miombo Woodland and Dambo Grassland Savanna Fires

Airborne measurements of trace gases and particles over and downwind of two prescribed savanna fires in Zambia are described. The measurements include profiles through the smoke plumes of condensation nucleus concentrations and normalized excess mixing ratios of particles and gases, emission factors for 42 trace gases and seven particulate species, and vertical profiles of ambient conditions. The fires were ignited in plots of miombo woodland savanna, the most prevalent savanna type in southern Africa, and dambo grassland savanna, an important enclave of miombo woodland ecosystems. Emission factors for the two fires are combined with measurements of fuel loading, combustion factors, and burned area (derived from satellite burn scar retrievals) to estimate the emissions of trace gases and particles from woodland and grassland savanna fires in Zambia and southern Africa during the dry season (May-October) of 2000. It is estimated that the emissions of CO2, CO, total hydrocarbons, nitrogen oxides (NOx as NO), sulfur dioxide (SO2), formaldehyde, methyl bromide, total particulate matter, and black carbon from woodland and grassland savanna fires during the dry season of 2000 in southern Africa contributed 12.3%, 12.6%, 5.9%, 10.3%, 7.5%, 24.2%, 2.8%, 17.5%, and 11.1%, respectively, of the average annual emissions from all types of savanna fires worldwide. In 2000 the average annual emissions of methane, ethane, ethene, acetylene, propene, formaldehyde, methanol, and acetic acid from the use of biofuels in Zambia were comparable to or exceeded dry season emissions of these species from woodland and grassland savanna fires in Zambia.

Sinha, Parikhit↗

LU-HF Age and Isotope Systematics of ALH84001

Allan Hills (ALH) 84001 is an orthopyroxenite that is unique among the Martian meteorites in having the oldest inferred crystallization age (approx..4.5 to 4.0 Gyr) [e.g., 1-6 and references therein 7]. Its ancient origin makes this stone a critical constraint on early history of Mars, in particular the evolution of different planetary crust and mantle reservoirs. However, because there is significant variability in reported crystallization ages, determination of initial isotope compositions is imprecise making assessment of planetary reservoirs difficult. Here we report a new Lu-Hf mineral isochron age, initial Hf-176/Hf-177 isotope composition, and inferred Martian mantle source compositions for ALH84001 that place constraints on longlived source reservoirs for the enriched shergottite suite of Martian meteorites including Shergotty, Zagami, NWA4468, NWA856, RBT04262, LAR06319, and Los Angeles. Sm-Nd isotope analyses are under way for the same mineral aliquots analyzed for Lu-Hf. The Lu-Hf system was utilized because Lu and Hf are both lithophile and refractory and are not easily redistributed during short-lived thermal pulses associated with shock metamorphism. Moreover, chromite has relatively modest Hf concentrations with very low Lu/Hf ratios [9] yielding tight constraints on initial Hf-176/Hf-177 isotope compositions

Righter, M.↗

Correlations Between Porosity, Spatter, and Process Metrics for Powder Bed Fusion Laser Beam Metallic Additive Manufacturing

Components fabricated using the powder bed fusion laser beam metallic (PBF-LB/M)additive manufacturing process are the result of a multitude of weld passes conducted sequentially. Qualifying components for aerospace applications requires a thorough understanding of the process-structure-properties relationships. Porosity defects are known to have a strong adverse effect on the mechanical properties of a component. In particular, porosity defects created by lack of fusion have high aspect ratio morphologies leading to stress concentrations that become crack initiation sites. In the present work, the occurrence of spatter induced lack of fusion porosity was studied using synchronized in-situ process monitoring, additive manufacturing model-based process metrics, and high-resolution X-ray computed tomography. The results show that lack of fusion porosity is statistically correlated with unremoved welding spatter ejecta of the PBF-LB/M process and process metrics related to the hatching strategy.

Qualification↗

High-Fidelity Arc-Discharge Model for Hydrogen-Plasma-Smelting-Reduction of Iron Ore

Electrification and use of renewable hydrogen is currently a necessity for decarbonizing the iron-and-steel industry. In this regard, hydrogen plasma smelting reduction (HPSR) is a novel pathway that is being explored for reduction of iron ore. HPSR provides several decarbonization merits compared to conventional blast furnaces. Firstly, the use of renewable hydrogen drastically reduces the CO2 emissions compared to the use of coke. Secondly, renewable electricity in the form of a thermal plasma for making reactive hydrogen species (radicals, ions) are more efficient at reducing iron ore compared to neutral H2. Thirdly, a molten product compatible with downstream processes is obtained from the intense heat transfer from the plasma. However, the scale-up of this technology requires fundamental exploration of hydrogen plasma dynamics and its interaction with complex solid material that include phase changing iron-ore and slag. In this work, we present a first principles continuum scale model for thermal plasmas in Ar/H2 gas mixtures typically used for HPSR. The thermal plasma governing equations for mass, momentum and energy with Lorentz force and Joule heating source terms are solved along with electromagnetic equations for electrostatic and magnetic vector potential. Our solver will be based on Pele, a suite of reacting flow solvers designed for advanced scientific computing architectures (Henry De Frahan et al., Proceedings of SIAM Parallel Processing, 13-25, 2024), and will utilize adaptive mesh generation for enhanced resolutions at locations of intense physicochemical interactions. This study will present the impact of Ar to H2 ratios on excited/dissociated hydrogen species concentrations, plasma temperature and conductivity along with the impact of outgassed species (water, metal vapor, O, OH radicals) from ore surface on gas phase chemistry. Furthermore, the heat and species flux to the surface will be quantified as a function of applied voltages in a transferred arc configuration.

hydrogen plasma↗

Influence of physical and chemical hydrology on bioremediation of a U-contaminated aquifer informed by reactive transport modeling incorporating 238 U/ 235 U ratios

Microbially-catalyzed reductive immobilization of aqueous uranium (U) as a solid phase has been proposed as a U remediation technique. Both laboratory and field experiments have demonstrated that this reduction reaction alters the 238 U/ 235 U ratio, producing a 238 U-enriched U(IV) solid. In contrast, other major U reactive transport processes fractionate these isotopes much less. This suggests the potential to quantify the extent of bioreduction occurring in groundwater containing U using the 238 U/ 235 U ratio, which would substantially improve upon current practices largely relying on U concentration measurements alone. Current reactive transport models for uranium dynamics include only concentration measurements, which are strongly influenced by highly coupled reactive transformation and aqueous transport processes. The complex physical and chemical behavior of U potentially compromises such quantitative analysis of U storage and release. Here we report the first numerical reactive transport model which explicitly incorporates variations in the 238 U/ 235 U ratio of U and demonstrates improved interpretation of the principal chemical reactions and groundwater transport processes affecting the subsurface mobility and distribution of this widespread contaminant. Recent U bioreduction studies performed in a contaminated aquifer in Rifle, Colorado, USA applied Rayleigh distillation models to interpret U stable isotope fractionation observed as a result of acetate amendment. These simplified models were unable to resolve the spatiotemporal pattern of U isotope fractionation recorded in the aqueous solutes. Here, we employ the multi-component, isotope-enabled CrunchTope reactive transport software to interpret these measured U isotope ratios, and demonstrate accurate reproduction of observed trends in both geochemistry and 238 U/ 235 U ratios for two consecutive years of field experiments. Overall, our results indicate that accurately modeling both the U concentration and isotope ratio distributions greatly constrains the parameter space of the model. We find that the transport properties of U in the Rifle aquifer are governed by the presence of low-permeability regions, which the isotopes are uniquely sensitive to. When U reduction is spatially constrained by these low-permeability regions, the shift in the 238 U/ 235 U ratio becomes more muted. Accurate modeling of observed U isotope ratios thus provides a powerful means to better understand bioremediation, and the current study serves to advance the application of this novel method.

238U/235U↗

The effect of equilibration time on Al uptake in C-S-H

Calcium silicate hydrate (C-S-H) is the main hydration product of Portland cements. The partial replacement of Portland cements by supplementary cementitious materials can result in C-S-H with lower Ca/Si ratios and more aluminum and alkalis. The effect of equilibration time on Al uptake in C-S-H was investigated using equilibration times from 7 days up to 3 years. Lower Al concentrations were measured in the solution after longer equilibration times. In addition, a higher uptake of Al in C-S-H was observed based on the decrease in the content of secondary phases. Little further decrease in Al concentrations was observed after 2 years and longer at low Ca/Si. At high Ca/Si no significant change in solution concentrations was observed after more than 3 month, while the destabilization of secondary phases continued up to 1 year, indicating that a (meta)stable equilibrium was reached faster at higher Ca/Si ratios.

36 MATERIALS SCIENCE↗

Cloud Condensation Nuclei Closure Study Using Airborne Measurements Over the Southern Great Plains

Abstract Airborne measurements of non‐refractory bulk aerosol chemical composition, aerosol size distributions, and cloud condensation nuclei (CCN) were conducted onboard a research aircraft during the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems field campaign in the spring and summer of 2016. A CCN closure study for the entire campaign period was performed where measured CCN concentrations at 0.24% and 0.46% supersaturation were compared with the predicted CCN concentrations calculated using κ ‐Köhler theory, three different assumptions of aerosol mixing state, and various assumptions about hygroscopicity, density, and the insoluble fraction of organic particles. We found that the Closure Ratio (CR), calculated as the ratio of predicted to measured CCN concentrations, was equal to one under two different aerosol mixing state assumptions: (a) all particles are composed of 100% organic particles, and (b) particles are externally mixed and composed of pure sulfates, nitrates, and organic particles assuming hygroscopicity values for organic particles ( ) between 0.04 and 0.17. The use of internal mixing state assumption often led to overprediction of CCN concentrations but the agreement within ±20% with the measured CCN concentrations was observed under certain closure permutations. A similar agreement, that is, within ±20%, was also observed using permuted parameters concerning density (1 and 1.5 g cm −3 ) and an insoluble fraction (0% and 20%) of organic particles. These findings may provide constraints on to predict CCN concentrations at a remote continental Southern Great Plains site.

54 ENVIRONMENTAL SCIENCES↗

Effects of 9.5 years warming on SOC concentration and composition in bulk soil and density fractions

Original data of whole-soil warming experiment after 9.5 years at Blodgett Forest Research Station. The Blodgett Forest is a mixed coniferous temperate forest with Mediterranean climate. The annual air temperature is 12.5℃ and the annual precipitation is 1774 mm yr-1- The soil is mesic ultic Alfisol of granitic origin, equivalent to Dystric Cambisol according to The World Reference Base for Soil Resources (WRB) system. The soil is warmed down to 1 m at + 4℃ by vertically installed heating cables. At the time of soil sampling on 1 May 2023, the whole-soil warming experiment had been running for approximately 9.5 years, from January 2014 to May 2023. The dataset includes: - Bulk_EA: C, N content, δ13C, and CN ratio of bulk soil; - Density_fractionation: organic carbon concentration, δ13C, and C/N ratio of free light fraction (fLF), occluded ligh fraction (oLF), and heavy fraction (HF); - PCA_DRIFT_AUC: original data of area under the curve (AUC) values of eight carbon bond types integrated on diffuse reflectance infrared fourier transform spectroscopy for each soil sample and soil fraction, which are consequently used for principal component analysis (PCA); - DRIFTS_stability_index: the calculation of aliphatic C–H (3000–2800 cm-1) to aromatic C=C (1670–1600 cm-1) ratios for each bulk soil sample and soil fraction. All data are provided in CSV format and can be viewed using Microsoft Excel.

Climate change↗

Microextraction–TQ–ICP–MS for the Direct Analysis of U and Pu from Cotton Swipes

Here, the microextraction sampling technique was integrated with triple quadrupole–inductively coupled plasma–mass spectrometry (TQ–ICP–MS) to directly sample and measure the isotopic compositions of uranium (U) and plutonium (Pu) from cotton swipes. Once extracted, the U/Pu were directed into the TQ–ICP–MS instrument for isotopic determination. Carbon dioxide (CO 2 ) and helium (He) gases were delivered to a collision reaction cell within the ICP–MS system for ion separation. The CO 2 reacts with the U + forming UO + which is ultimately separated from the Pu + ions of interest in the third quadrupole. This study demonstrates direct liquid extraction of U/Pu from a solid surface and subsequent measurement by TQ–ICP–MS in <60 s. Flow rates were optimized (0.3 mL min –1 CO 2 and 5 mL min –1 He) in the reaction cell of the ICP–MS system to maximize the Pu signal while minimizing U interferences (i.e., 238 U + tail and 238 UH + ) at m/z 239. Low levels of Pu (~2 pg) were deposited on a cotton swipe along with U at concentrations ranging from 20 to 200 ng. The 240 Pu/ 239 Pu ratio was measured with <7% relative difference from the certified value at all U concentrations. Major and minor U isotope ratios were also measured with <4% relative difference. This highlights that the microextraction–TQ–ICP–MS method can extract a mixed U/Pu sample directly from a cotton swipe and measure both isotopic systems without chemical separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Seasonal Characteristics of the Perennial Ice Cover of the Beaufort Sea

By definition, ice which survives the summer is classified as multiyear ice. Thus the area covered by multiyear ice during the winter should be nearly equivalent to the ice area during the previous summer's minima. This condition provides a reasonable criterion for the evaluation of ice concentration and ice type retrieval algorithms using remote-sensing data sets. From special sensor microwave imager (SSM/I) data the NASA Team algorithm estimates the multiyear, first-year, and total ice concentrations during the winter using combinations of the polarization and spectral gradient ratios. The Team algorithm provides only estimates of ice concentration in the summer. From ERS 1 synthetic aperture radar (SAR) data the remarkably stable contrast between multiyear ice and first-year ice in winter provides consistent estimates of multiyear ice concentrations. In the summer, multiyear ice concentration cannot be estimated from SAR or SSM/I data because free water on the surface effectively masks the backscatter and emissivity signature of this ice type. From SAR data a technique which takes advantage of the high backscatter of wind-roughened open water as a discrimination feature is used to estimate the total ice concentration in the summer. With a year-long (January 1992 to January 1993) data set from the Beaufort Sea we found that the multiyear ice concentration estimates from the SAR data are stable and are nearly equivalent to the ice concentration estimated at the end of the previous summer. We contrast this with the variability of the multiyear ice concentration and ice friction estimates obtained using SSM/I data. The Team algorithm produces ice concentration and multiyear ice estimates which are consistently lower than those from the SAR data. We discuss reasons for these discrepancies and the implications of the higher than previously noted multiyear ice concentrations.

Kwok, R.↗

Computational investigation on the combined effect of pore attributes on strain concentrators in metal additively manufactured materials

Metal additive manufacturing provides a pathway for creating highly optimized components. However, porosity continues to be a prevalent issue for fatigue performance despite best efforts in optimizing process parameters and postprocessing techniques. This work uses finite element analysis to conduct a parametric study to link various pore attributes (i.e., aspect ratio, orientation, and location) to strain concentration factors (SCF) under elastic/plastic deformation during uniaxial loading. Keyhole and lack-of-fusion pores are idealized by prolate and oblate ellipsoids, respectively. Each simulation of the parametric study assumes a single isolated pore in a Ti-6Al-4V material, modeled with J2-plasticity. A reduced-order model is developed to relate pore attributes to SCF, and then used to quantify the variability in SCF for a given experimentally characterized probability distribution of pore attributes. This reduced-order model can be used in a production environment to provide a first-order evaluation to rapidly screen sub-optimally performing components.

Additive Manufacturing↗

Cosmic ray records in Antarctic meteorites

The cosmogenic radionuclides Be(10), Al(26), and Mn(53) and noble gases were determined in more than 28 meteorites from Antarctica by nuclear analytical techniques and static mass spectrometry, respectively. The summarized results are listed. The concentrations of Al(26) and Mn(53) are normalized to the repective main target elements and given in dpm/kg Si sub eq and dpm/kg Fe. The errors stated include statistical as well as systematical errors. For noble gas concentrations estimated errors are 5% and for isotopic ratios 1.5%. Cosmic ray exposure ages T sub 21 were calculated by the noble gas concentrations and the terrestrial residence time (T) on the basis of the spallogenic nuclide Al(26). The suggested pairing of the LL6 chondrite RKPA 80238 and RKPA 80248 and the eucrites ALHA 76005 and ALHA 79017 is confirmed not only by the noble gas data but also by the concentrations of the spallation produced radionuclides. Futhermore, ALHA 80122, clasified as an H6 chondrite, has a noble gas pattern which suggest that this meteorite belongs to the ALHA 80111 shower.

Vogt, S.↗

Methanol Droplet Extinction in Oxygen/Carbon-dioxide/Nitrogen Mixtures in Microgravity: Results from the International Space Station Experiments

Motivated by the need to understand the flammability limits of condensed-phase fuels in microgravity, isolated single droplet combustion experiments were carried out in the Combustion Integrated Rack Facility onboard the International Space Station. Experimental observations of methanol droplet combustion and extinction in oxygen/carbon-dioxide/nitrogen mixtures at 0.7 and 1 atmospheric pressure in quiescent microgravity environment are reported for initial droplet diameters varying between 2 mm to 4 mm in this study.The ambient oxygen concentration was systematically lowered from test to test so as to approach the limiting oxygen index (LOI) at fixed ambient pressure. At one atmosphere pressure, ignition and some burning were observed for an oxygen concentration of 13% with the rest being nitrogen. In addition, measured droplet burning rates, flame stand-off ratios, and extinction diameters are presented for varying concentrations of oxygen and diluents. Simplified theoretical models are presented to explain the observed variations in extinction diameter and flame stand-off ratios.

Nayagam, Vedha↗

Optimization of Localized High Concentration Electrolytes (LHCE) for Li||LiCoO 2 and Si|| LiCoO 2 Batteries used in Consumer Electronics Applications (Final Report for I3T Project 75934)

This project will optimize localized high concentration electrolyte (LHCE) for Li/LCO and Si/LCO batteries for consumer electronics applications, including select the best solvent and diluent, optimize the ratios of the solvents and the salt concentration. Results will be demonstrated not only in both coin cells, but also in pouch cells, which is required for large-scale commercial applications. This work can provide better understanding that would also benefit other LMB projects, including Li/NMC and Li/S batteries for electric vehicle applications. In the history of rechargeable batteries, all batteries have been first used in small scale consumer electronics, then eventually penetrate to large scale applications such as electrical vehicle or grid. We believe this development route will also be true for LMBs. By developing the best electrolyte for Li/LCO and Si/LCO chemistry, we will not only get the early market entry in consumer electronics, but we can also accumulate experience on the practical application of LMBs which can be used to further develop other types of LMBs for EV and other large-scale applications pursued by DOE.

25 ENERGY STORAGE↗

Polymer degradation rate control of hybrid rocket combustion

Polymer degradation to small fragments is treated as a rate controlling step in hybrid rocket combustion. Both numerical and approximate analytical solutions of the complete energy and polymer chain bond conservation equations for the condensed phase are obtained. Comparison with inert atmosphere data is very good. It is found that the intersect of curves of pyrolysis rate versus interface temperature for hybrid combustors, with the thermal degradation theory, falls at a pyrolysis rate very close to that for which a pressure dependence begins to be observable. Since simple thermal degradation cannot give sufficient depolymerization at higher pyrolysis rates, it is suggested that oxidative catalysis of the process occurs at the surface, giving a first order dependence on reactive species concentration at the wall. Estimates of the ratio of this activation energy and interface temperature are in agreement with best fit procedures for hybrid combustion data. Requisite active species concentrations and flux are shown to be compatible with turbulent transport. Pressure dependence of hybrid rocket fuel regression rate is thus shown to be describable in a consistent manner in terms of reactive species catalysis of polymer degradation.

Stickler, D. B.↗

Orbital chemistry - Lunar surface analysis from the X-ray and gamma ray remote sensing experiments

The X-ray and gamma-ray lunar surface remote sensing experiments conducted by the Apollo 15 and 16 are discussed. The data indicate mare basins that are extensively basaltic and highlands of aluminum-rich anorthositic-type feldspar. An east-west asymmetry involving higher Al/Si ratios toward the east is noted; high concentrations of a KREEP-type component along the Imbrium-Procellarum edges and throughout the basin are also observed. Lunar K/Th ratios, lowest in areas of the Imbrium and higher in the surrounding mare and highlands, may lend support to the picture of the moon as a high-temperature condensate.

Adler, I.↗