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At least 379 records · Page 21

Mapping Rare Earths and Toxics in E-Waste via Hyperspectral Imaging and Machine Learning

Electronic waste (e-waste) presents a mounting challenge to environmental sustainability due to its complex composition, which includes high-value rare earth elements, hazardous organic compounds, and non-recyclable plastics. Accurate and scalable material classification is essential for enabling efficient resource recovery and safe recycling practices. This study introduces a confidence-aware classification pipeline that combines mid-infrared hyperspectral imaging (HSI), spectral angle mapping (SAM), and iterative machine learning to perform pixel-level material identification across e-waste devices. A curated spectral library encompassing artificial materials (e.g., plastic iron oxide, galvanized metals), minerals (e.g., allanite, hematite), and organic compounds (e.g., benzanthracene, toluene) was used to generate pseudo-labels, each assigned a confidence score based on SAM-derived spectral similarity. High-confidence samples from seven consumer electronics—digital cameras, keyboards, laptop fans, modems, motherboards, TV remotes, and speakers—were iteratively expanded and classified using models such as Support Vector Machine (SVM), Random Forest, Gradient Boosting Classifier, Partial Least Squares Discriminant Analysis (PLSDA) and Logistic Regression. The best-performing classifiers achieved macro F1 scores approaching 1.0. Results revealed widespread plastic content (dominated by plastic iron oxide), the presence of rare earth-bearing minerals like cerium-containing allanite, and pervasive detection of hazardous organics such as benzanthracene. Principal Component Analysis (PCA) visualizations and confusion matrices confirmed high separability and robust classification performance. This methodology enables precise, non-destructive, and scalable classification of heterogeneous e-waste streams. It supports automated, hazard-aware sorting in recycling workflows, facilitating selective recovery of critical materials and compliance with circular economy goals. The confidence-aware framework provides a foundation for real-time deployment in industrial settings, offering significant implications for smart e-recycling infrastructure and policy-driven material stewardship.

Circular economy↗

Improved Crystal Quality by Detached Solidification in Microgravity

The goals of our work on detached solidification have been to: Develop a complete understanding of all of the phenomena of detached solidification; Make it possible to achieve detached solidification reproducibly; Increase crystallographic perfection through detached solidification. Specifically, we aimed in this project to: Identify a system and develop methods that would allow viewing of the melt surface and convection in the melt during detached solidification in microgravity; Improve understanding of the origination and evolution of detachment through experiments and theoretical treatments; Achieve detachment on earth. The project resulted in 14 publications, 15 presentations, completion of 2 Ph.D. theses, and completion of 2 M.S. theses. Two additional papers are currently being reviewed for publication. Copies of most of the papers are attached as appendices. Among the accomplishments are: Achievement of detached solidification of InSb on earth and determination of the conditions favoring detachment on earth. Development of a new method for coating the interior of silica growth ampoules with transparent boron nitride, which yields the high contact angles for semiconductor melts that favor detachment. Development of a new coating for the interior of Pyrex ampoules yielding very high contact angles for water and molten organic compounds. Development of a material-balance model for steady detached solidification that provides greatly improved insight into the process, both in microgravity and on earth. Dimensionless parameters were found that clarify the role of operating conditions and physical properties. The reason for the occurrence of two steady states was clarified, along with their relative stability. Observation of periodic gas tubes during directional solidification of water and organic compounds. Gas bubbles did not propagate around the periphery to yield full detachment. Failure to obtain detachment is attributed to the ready plastic deformation of these materials, so that the frozen material continues to adhere to the ampoule wall during cooling.

Regel, Liya L.↗

Contribution of Speciated Monoterpenes to Secondary Aerosol in the Eastern North Atlantic

Extension of laboratory results suggests that monoterpenes, a subset of marine biogenic volatile organic compounds, might play a competitive role in secondary aerosol formation in the remote marine atmosphere, where the oxidation of dimethyl sulfide has traditionally been thought to dominate. However, the current assessment of the role of monoterpenes in secondary aerosol formation in the remote marine atmosphere is limited by the scarcity of speciated monoterpene measurements and the complete absence of collocated measurements of particle chemical composition and monoterpene speciation. Here, in this paper, we present measurements of gas-phase volatile organic compounds, with particular focus on speciated monoterpenes, and commensurate measurements of aerosol chemical composition in the Eastern North Atlantic. The average monoterpene concentration in periods of marine air was 14 ± 10 ppt, and the dominant isomer was β-pinene (46 ± 10%), with other contributions from α-pinene, limonene, and β-ocimene. The total monoterpene concentration in marine air was greater than that of isoprene by a factor of 3.9 on average, in contrast to prior research and potentially due to the large β-pinene contribution. Monoterpenes were significantly smaller in concentration than dimethyl sulfide, which was also highlighted by the substantial contribution of sulfate to non-refractory submicron aerosol. The mean and interquartile range of the sulfate to organic aerosol mass ratio in clean marine air were 2.7 (0.7–3.4). Finally, a simple box model analysis showed that the BVOC precursors, dimethyl sulfide, methanethiol, monoterpenes, and isoprene, could sustain the measured sulfate to organic aerosol ratio in clean marine air.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbonaceous Components in the Comet Halley Dust

Cometary grains containing large amounts of carbon and/or organic matter (CHON) were discovered by in situ measurements of comet Halley dust composition during VEGA and GIOTTO flyby missions. In this paper, we report the classification of these cometary, grains by means of cluster analysis, discuss the resulting compositional groups, and compare them with substances observed or hypothesized in meteorites, interplanetary dust particles, and the interstellar medium. Grains dominated by carbon and/or organic matter (CHON grains) represent approx. 22% of the total population of measured cometary dust particles. They, usually contain a minor abundance of rock-forming elements as well. Grains having organic material are relatively more abundant in the vicinity of the nucleus than in the outer regions of the coma, which suggests decomposition of the organics in the coma environment. The majority of comet Halley organic particles are multicomponent mixtures of carbon phases and organic compounds. Possibly, the cometary CHON grains may be related to kerogen material of an interstellar origin in carbonaceous meteorites. Pure carbon grains, hydrocarbons and polymers of cyanopolyynes, and multi-carbon monoxides are present in cometary dust as compositionally simple and distinctive components among a variety of others. There is no clear evidence of significant presence of pure formaldehyde or HCN polymers in Halley dust particles. The diversity of types of cometary organic compounds is consistent with the inter-stellar dust model of comets and probably reflects differences in composition of precursor dust. Preservation of this heterogeneity among submicron particles suggest the gentle formation of cometary, nucleus by aggregation of interstellar dust in the protosolar nebula without complete mixing or chemical homogenization at the submicron level.

Fomenkova, M. N.↗

Intercomparison of the representations of the atmospheric chemistry of pre-industrial methane and ozone in earth system and other global chemistry-transport models

An intercomparison has been set up to study the representation of the atmospheric chemistry of the pre-industrial troposphere in earth system and other global tropospheric chemistry-transport models. The intercomparison employed a constrained box model and utilised tropospheric trace gas composition data for the pre-industrial times at ninety mid-latitude surface locations. Incremental additions of four organic compounds: methane, ethane, acetone and propane, were used to perturb the constrained box model and generate responses in hydroxyl radicals and tropospheric ozone at each location and with each chemical mechanism. Although the responses agreed well across the chemical mechanisms from the selected earth system and other global tropospheric chemistry-transport models, there were differences in the detailed responses between the chemical mechanisms that could be tracked down by sensitivity analysis to differences in the representation of C1–C3 chemistry. Inter-mechanism ranges in NOx compensation points were about 0.17 ± 0.12 when expressed relative to the inter-mechanism average. Monte Carlo uncertainty analysis carried out with a single chemical mechanism put the intra-mechanism range a factor of three higher at 0.50 ± 0.12. Similar differences between inter-mechanism and intra-mechanism ranges were found for hydroxyl radical depletion but were up to a factor of six wider for ozone formation from incremental additions of organic compounds. The cause of the discrepancies between the inter- and intra-mechanism ranges was found to be the large uncertainties that are present in the laboratory determinations of the rate coefficients and product channel branching ratios of some key chemical reactions involving organic peroxy radicals and hydroperoxides. Whilst these large uncertainties are present in the laboratory determinations, there will be irreducible uncertainties in the predictions from the earth system and other chemistry-transport models of methane and tropospheric ozone trends since pre-industrial times and hence their contributions to the radiative forcing of climate change. Further definitive laboratory studies of the reaction rates and product yields of the reactions of the simple organic peroxy radicals and hydroperoxides are required to resolve and reduce current uncertainties in earth system and chemistry-transport model predictions.

atmospheric chemistry↗

Organic Synthesis via Irradiation and Warming of Ice Grains in the Solar Nebula

Complex organic compounds, including many important to life on Earth, are commonly found in meteoritic and cometary samples, though their origins remain a mystery. We examined whether such molecules could be produced within the solar nebula by tracking the dynamical evolution of ice grains in the nebula and recording the environments they were exposed to. We found that icy grains originating in the outer disk, where temperatures were less than 30 K, experienced UV irradiation exposures and thermal warming similar to that which has been shown to produce complex organics in laboratory experiments. These results imply that organic compounds are natural byproducts of protoplanetary disk evolution and should be important ingredients in the formation of all planetary systems, including our own.

Ciesla, Fred J.↗

Possible Mechanism(s) in the Photo-Magnetic Production of Enantiomer Excesses.

Among the multitude of organic compounds identified in carbonaceous chondrites are sugar acids ((HO-R)xCOOH), i.e., oxidized counterparts of the common aldehyde sugars (e.g., glyceraldehyde, erythrose, ribose, glucose, etc.). In the historical study of extraterrestrial compounds chiral analyses are particularly significant in origins-of-life studies. Chiral compounds are composed of two non-superposable mirror images or "enantiomers", analogous to a left and right hand. Such molecules are important in contemporary life because biological polymers (proteins, nucleic acids, etc.) are homochiral, i.e., their chiral monomers usually consist of only one of the two enantiomers. It has been shown, at least in one lab setting, that abiotic syntheses of significantly sized RNA polymers do not proceed if the monomers are present in racemic (50:50) amounts. The latter results may argue for, at least, significant enantiomer excesses in organic compounds before the origin of nucleic acids and life. Therefore, the finding that amino acids and sugar acids in carbonaceous chondrites possess enantiomeric excesses may aid in understanding one source of precursors to homochirality. Note: Attachment contains full abstract.

G. Cooper↗

EPCAPE-PT-LANL Measurements: Soot Particle Aerosol Mass Spectrometer

Coastal cities offer a unique environment for studying aerosol-cloud interactions and the effects of urban emissions on cloud properties. As part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), the Partitioning Thrust by Los Alamos National Laboratory (EPCAPE-PT-LANL) was conducted. Our campaign focused on measuring the optical and chemical properties of aerosols and their interactions within marine stratocumulus clouds in La Jolla, California. EPCAPE-PT-LANL enhances the primary goals of EPCAPE through innovative observations of vapor-phase transitions between aerosols and cloud droplets, the impact of black carbon on aerosol-cloud dynamics, and the effects of cloud processing on aerosol optical properties. Instrument: Soot particle-Aerosol Mass Spectrometer. (Aerodyne Inc.) Header: - Organic_GCVIoff[ug/m3]: Concentration of organic compounds measured via the Main Inlet (out-of-cloud) in micrograms per cubic meter. - Nitrate_GCVIoff[ug/m3]: Concentration of nitrate measured via the Main Inlet (out-of-cloud) in micrograms per cubic meter. - Sulfate_GCVIoff[ug/m3]: Concentration of sulfate measured via the Main Inlet (out-of-cloud) in micrograms per cubic meter. - Chloride_GCVIoff[ug/m3]: Concentration of chloride measured via the Main Inlet (out-of-cloud) in micrograms per cubic meter. - Ammonium_GCVIoff[ug/m3]: Concentration of ammonium via the Main Inlet (out-of-cloud) in micrograms per cubic meter. - Organic_GCVIon[ug/m3]: Concentration of organic compounds measured in-cloud via CVI in micrograms per cubic meter. - Nitrate_GCVIon[ug/m3]: Concentration of nitrate measured in-cloud via CVI in micrograms per cubic meter. - Sulfate_GCVIon[ug/m3]: Concentration of sulfate measured in-cloud via CVI in micrograms per cubic meter. - Chloride_GCVIon[ug/m3]: Concentration of chloride measured in-cloud via CVI in micrograms per cubic meter. - Ammonium_GCVIon[ug/m3]: Concentration of ammonium measured in-cloud via CVI in micrograms per cubic meter. - CVI_Flag[bool]: A boolean flag indicating whether the CVI was active (true) or inactive (false) during the measurement.

54 ENVIRONMENTAL SCIENCES↗

Regenerable Incinerator Exhaust Purification and Trace Contaminant Control System

In this novel approach to air purification, contaminants removed from a process air stream by a high-capacity adsorbent are displaced periodically by a warm, high-humidity, reverse-flow air stream. Displaced contaminants flow into a closed regeneration loop, in which organic compounds are oxidized catalytically and acid gases are removed by a gas- water contactor (which also serves as the source of the water vapor). These features are expected to result in a design that has few expendables and lower energy consumption than alternative regenerable techniques. The joint project between NASA Ames Research Center and Vanderbilt University has completed its third year. Breadboard development continues at NASA Ames, while Vanderbilt has completed most of its adsorption equilibria development. Vanderbilt has completed its fixed-bed apparatus for investigation of dynamic adsorption and desorption processes for trace organic compounds and water vapor, and is continuing its development of the mathematical model describing the column dynamics.

Finn, John E.↗

Electrocatalytic benchmarking of ruthenium-based bimetallic anodes for the electrocatalytic oxidation of biomass-derived wastewater

In this paper, we report on the synthesis, characterization, and use of ruthenium oxide (RuO 2 ) doped with a secondary metal (M2) to enhance electrochemical activity and stability for the electrocatalytic oxidation (ECO) of biomass-derived wastewaters. We used different electrochemical methods such as cyclic voltammetry (CV), electrochemical surface area (ECSA), and Tafel analysis as well as physical characterization such as grazing incidence X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy to understand how the introduction of M2 affects electrochemical performance. Our results show that including an M2 improves the ECO performance regardless of the composition of the electrolyte. Specifically, we saw increase in ECSA, which could be due to enhanced charge transfer for the pH ranges evaluated. Furthermore, the introduction of organic compounds in wastewater generated during the hydrothermal liquefaction of food waste affected the ECO performance differently, depending on M2, the electrolyte composition, and anodic half-cell potential, highlighting the need to properly control the reaction conditions when testing and characterizing the electrocatalysts under different reaction regimes. We developed an in situ electrocatalytic benchmarking protocol, Boruah – Lopez-Ruiz – Strange (BLoRS), to quickly assess if the presence of M2 improves the ECO performance; thus, saving time and resources in ex situ characterization, testing, and product analysis. This foundational work provides the basis for characterization and benchmarking of electrodes of the ECO of organic compounds.

Electrocatalysis↗

Cavitating Jet Method and System for Oxygenation of Liquids

Reclamation and re-use of water is critical for space-based life support systems. A number of functions must be performed by any such system including removal of various contaminants and oxygenation. For long-duration space missions, this must be done with a compact, reliable system that requires little or no use of expendables and minimal power. DynaJets cavitating jets can oxidize selected organic compounds with much greater energy efficiency than ultrasonic devices typically used in sonochemistry. The focus of this work was to develop cavitating jets to simultaneously accomplish the functions of oxygenation and removal of contaminants of importance to space-structured water reclamation systems. The innovation is a method to increase the concentration of dissolved oxygen or other gasses in a liquid. It utilizes a particular form of novel cavitating jet operating at low to moderate pressures to achieve a high-efficiency means of transporting and mixing the gas into the liquid. When such a jet is utilized to simultaneously oxygenate the liquid and to oxidize organic compounds within the liquid, such as those in waste water, the rates of contaminant removal are increased. The invention is directed toward an increase in the dissolved gas content of a liquid, in general, and the dissolved oxygen content of a liquid in particular.

Chahine, Georges L.↗

Unraveling the ecological success of Iodidimonas in a bioreactor treating oil and gas produced water

Iodidimonas sp., a bacterium found in bioreactors treating oil and gas produced water as well as iodide-rich brines, has garnered attention for its unique ability to oxidize iodine. However, little is known about the metabolic capabilities that enable Iodidimonas sp. to thrive in certain unique ecological niches. In this study, we isolated, characterized, and sequenced three strains belonging to the Iodidimonas genus from the sludge of a membrane bioreactor used for produced water treatment. We investigated the genomic features of these isolates and compared them with the four publicly available isolate genomes from this genus, as well as a metagenome-assembled genome from the source bioreactor. Our Iodidimonas isolates had several genes associated with mitigating salinity, heavy metal, and organic compound stress, which likely help these bacteria to survive in produced water. Phenotyping tests revealed that while the isolates could utilize a wide variety of simple carbon substrates, they failed to degrade aliphatic or aromatic hydrocarbons, consistent with the lack of genes associated with common hydrocarbon degradation pathways in their genomes. We hypothesize that these microbes may lead a scavenging lifestyle in the bioreactor and similar iodide-rich brines. IMPORTANCE: Occupying a niche habitat and having few representative isolates, the genus Iodidimonas is a relatively understudied alphaproteobacterial group. Its ability to corrode pipes in iodine production facilities has economic implications, and its ability to generate potentially carcinogenic iodinated organic compounds during treatment of oil and gas produced water may cause environmental and health concerns with the recycling of treated water. Therefore, detailed characterization of the metabolic potential of the Iodidimonas isolates in this study both sheds light on their adaptation to the environmental conditions they inhabit and has environmental and economic significance.

Acharya, Shwetha M↗

Progress Report on the Spacecraft Atmosphere Monitor’s Development Model

The Spacecraft Atmosphere Monitor (S.A.M.) is a miniature gas chromatograph (GC) mass spectrometer (MS) intended for assessing trace volatile organic compounds and the major constituents in the atmosphere of present (the International Space Station) and future crewed spacecraft. As such, S.A.M. will continuously sample concentrations of major air constituents (CH4, H2O, N2, O2, and CO2) and report results in two-second intervals. The S.A.M. is a technology demonstration planned to launch in 2018 and we report here on recent developments taking place in building a testbed and development model of the instrument. The S.A.M. is mechanically designed to operate under hi-G loads present during launch events and can operate at sub-atmospheric pressures relevant to extra-vehicular activities. Total instrument mass is projected at 9.5 kg with power consumption estimated at 35 W. The S.A.M. instrument will provide on-demand reporting on trace volatile organic compounds (VOC) at ppm to ppb levels of 40+ species relevant for astronaut health.

Darrach, M.↗

Analytical Methods and Testbeds for Characterizing Adsorbents and Catalysts for Atmosphere Revitalization of Crewed Spacecraft

Spacecraft environmental control and life support systems (ECLSS) include a number of air revitalization (AR) technologies to provide breathable air and a comfortable living environment to the crew. Crew health and comfort is ensured by controlling human produced CO2 (1 kg person-1 day-1) and water vapor (~2 kg person-1 day-1), and by removing trace contaminants (TCs) from cabin air. These life support functions on-board the International Space Station (ISS) are carried out by the Carbon Dioxide Removal Assembly (CDRA), the Water Processor Assembly (WPA), and the trace contaminant control system (TCCS). During the development of the TCCS, new analytical and theoretical methods were developed in the 1970s for characterizing adsorption and desorption characteristics of activated carbons for the purpose of designing suitable AR technologies required for controlling airborne trace contaminants within spacecraft cabins during long exploration missions. The TCCS removes harmful volatile organic compounds and other trace contaminants from the circulating air. It consists of a granular activated carbon (GAC) bed for the removal of high molecular weight contaminants and ammonia followed by a heated catalytic bed for low molecular weight hydrocarbons. The high temperature catalytic oxidizer (HTCO) of the TCCS, which operates at 400°C and requires 120W average power, removes low molecular weight compounds such as carbon monoxide (CO), formaldehyde (CH2O), and methane (CH4), that pass through the GAC bed. The Air Revitalization Laboratory at the Kennedy Space Center (KSC) was established to develop new analytical methods for evaluating emerging ECLSS technologies for use in future AR architectures. General properties of adsorbents and catalysts are required for trace contaminant control system design calculations and vendor-supplied data are seldom available at relevant process conditions of interest to spacecraft cabin applications. To address this shortcoming, appropriate testbeds were developed to measure the desired properties of AR technologies being considered for use in ECLS architectures. Generally, the testbeds developed at KSC challenge the test media (activated carbon, impregnated activated carbon, catalysts, zeolites, solid amines, or pleated filters) with simulated spacecraft gas streams containing representative mixtures of trace contaminants (volatile organic compounds, ammonia, CO, CO2, or siloxanes) at the flow rates, temperatures, and relative humidity that will be encountered within manned spacecraft. Work performed at KSC funded by NASA’s Advanced Exploration (AES) Program has included: Identifying candidate sorbents to replace commercially obsolete impregnated carbons for NH3 control within the TCCS, characterizing their adsorptive capacities using simulated spacecraft gas streams, and ranking their appropriateness in various AR applications; evaluating novel low temperature catalysts for controlling CO and formaldehyde by traditional and photocatalytic methods for trace contaminant control; development of analytical methods to assess regenerable solid amine performance for CO2 control via pressure swing adsorption. The Air Revitalization lab was also funded to study trace contaminant control by other NASA programs. These include: screening of candidate sorbents for the design of new Charcoal HEPA Integrated Particle Scrubber (CHIPS) filters for removing siloxanes from cabin air; characterizing the performance of an impregnated activated carbon at low humidity for use in ORION ECLS; screening of sorbents for protecting the Sabatier 2.0 catalyst from DMSO2, siloxanes, NH3, and solid amine byproducts.

Monje, Oscar↗

Carbon isotope evidence for the substrates and mechanisms of prebiotic synthesis in the early solar system

Meteorites contain prebiotic, bio-relevant organic compounds including amino acids. Their syntheses could result from diverse sources and mechanisms and provide a window on the conditions and materials present in the early solar system. Here we constrain alanine’s synthetic history in the Murchison meteorite using site-specific 13C/12C measurements, reported relative to the VPDB standard. The δ13CVPDB values of −29 ± 10‰, 142 ± 20‰, and −36 ± 20‰ for the carboxyl, amine-bound, and methyl carbons, respectively, are consistent with Strecker synthesis of interstellar-medium-derived aldehydes, ammonia, and low-δ13C nebular or interstellar-medium-derived CN. We report experimentally measured isotope effects associated with Strecker synthesis, and use them to constrain the δ13C values of the alanine precursors, which we then use to construct a model that predicts the molecular-average δ13C values of 19 other organic compounds of prebiotic significance found in Murchison if they were made by our proposed synthetic network. Most of these predictions agree with previous measurements, suggesting that interstellar-medium-derived aldehydes and nebular and/or pre-solar CN could have served as substrates for synthesis of a wide range of prebiotic compounds in the early solar system.

L.Chimiak↗

Water Ice and Life's Roots in Space

Nearly three decades ago as Voyager 2 spacecraft raced out of the Solar System. NASA engineers turned its camera arm around (at the request of the American astronomer Carl Sagan) to take a parting snapshot of Earth. Earth's image was a single pale blue pixel, its color caused by the Rayleigh scattering of sunlight in the water of our oceans. Earth is a water planet, and this is the color of life. No matter how far we travel on our planet, no matter how high or deep, if we find liquid water, we find some form of life that manages to survive there. And yet there is a cruel irony. Water in its solid crystalline form is hostile to life. Organisms can roost in geysers, wallow in brine and gulp down acid, but they cowered from ice. The rigid ordering of water molecules in ice crystals expels impurities and tears organic tissue beyond repair. In fact, about the only good thing you can say about ice is that it gets out of the way: Its low density ensures that it floats and leaves the water dwelling creatures in peace. Recent discoveries have caused us to rethink this basic premise. New lines of evidence both observational and experimental - suggest that prebiotic organic compounds are not only comfortable in, but in fact had their origin in a peculiar form of solid water ice that is ubiquitous in interstellar space, but completely absent from Earth. Only recently have we been able to create even submicroscopic quantities of this ice in terrestrial laboratories, yet it constitutes the most abundant form of water in the universe. Interstellar ice is a far cry from the ice we are so familiar with on Earth. This interstellar ice has no crystalline structure, and despite the fact that its temperature is a scant few degrees above absolute zero (where all molecular motion ceases), it is highly reactive and can flow like water when exposed to radiation. It is in fact this ice's similarity to liquid water that allows it to participate in the creation of the very first organic compounds.

Blake, David↗

Electron Spin Resonance (ESR) detection of active oxygen species and organic phases in Martian soils

The presence of active oxygen species (O(-), O2(-), O3(-)) and other strong oxidants (Fe2O3 and Fe3O4) was invoked in interpretations of the Viking biological experiments and a model was also suggested for Martian surface chemistry. The non-biological interpretations of the biological results gain futher support as no organic compounds were detected in the Viking pyrolysis-gas chromatography mass spectrometer (GCSM) experiments at concentrations as low as 10 ppb. Electron spin resonance (ESR) measures the absorption of microwaves by a paramagnetic and/or ferromagnetic center in the presence of an external field. In many instances, ESR has the advantage of detailed submicroscopic identification of the transient species and/or unstable reaction intermediates in their environments. Since the higly active oxygen species (O(-), O2(-), O3(-), and R-O-O(-)) are all paramagnetic in nature, they can be readily detected in native form by the ESR method. Active oxygen species likely to occur in the Martian surface samples were detected by ESR in UV-irradiated samples containing MgO. A miniaturized ESR spectrometer system can be developed for the Mars Rover Sample Return Mission. The instrument can perform the following in situ Martian samples analyses: detection of active oxygen species; characterization of Martian surface chemistry and photooxidation processes; and searching for organic compounds in the form of free radicals preserved in subsoils, and detection of microfossils with Martian carbonate sediments.

Tsay, Fun-Dow↗

Compound-Specific Carbon Isotope Compositions of Aldehydes and Ketones in the Murchison Meteorite

Compound-specific carbon isotope analysis (delta(exp 13)C) of meteoritic organic compounds can be used to elucidate the abiotic chemical reactions involved in their synthesis. The soluble organic content of the Murchison carbonaceous chondrite has been extensively investigated over the years, with a focus on the origins of amino acids and the potential role of Strecker-cyanohydrin synthesis in the early solar system. Previous delta(exp 13)C investigations have targeted alpha-amino acid and alpha-hydroxy acid Strecker products and reactant HCN; however, delta(exp 13)C values for meteoritic aldehydes and ketones (Strecker precursors) have not yet been reported. As such, the distribution of aldehydes and ketones in the cosmos and their role in prebiotic reactions have not been fully investigated. Here, we have applied an optimized O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) derivatization procedure to the extraction, identification, and delta(exp 13)C analysis of carbonyl compounds in the Murchison meteorite. A suite of aldehydes and ketones, dominated by acetaldehyde, propionaldehyde, and acetone, were detected in the sample. delta(exp 13)C values, ranging from -10.0(0/00) to +66.4(0/00), were more (exp 13)C-depleted than would be expected for aldehydes and ketones derived from the interstellar medium, based on interstellar (exp 12)C/(exp 13)C ratios. These relatively (exp 13)C-depleted values suggest that chemical processes taking place in asteroid parent bodies (e.g., oxidation of the IOM) may provide a secondary source of aldehydes and ketones in the solar system. Comparisons between delta(exp 13)C compositions of meteoritic aldehydes and ketones and other organic compound classes were used to evaluate potential structural relationships and associated reactions, including Strecker synthesis and alteration-driven chemical pathways.

meteoritic organic compounds↗