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Analysis of Volatile Compounds From CO2 Removal Systems

One of the primary concerns when designing CO2 scrubber systems that will be integrated with a Sabatier reactor to produce water and methane is the amount of water released from the scrubber. Because the gas stream entering a Sabatier reactor must be compressed, water entering the reactor can condense and compromise the integrity of the system, thus rendering its valuable conversion capability useless. When the Johnson Space Center Environmental Chemistry Laboratory was tasked to develop an assay to quantify the water concentration in air samples from CO2 scrubbers, additional testing was also performed to see if any other compounds were being concentrated on the scrubbers. It was thought that the efficiency of the scrubber systems could be quantified by comparing the differences in samples from the ambient air on the International Space Station (ISS) to the exit gas of the scrubber. As this analysis was carried out, it became evident that the concentrations of certain volatile compounds were higher in the samples from the scrubbers than they were in nominal environmental samples. This meant these compounds were being retained and concentrated on the scrubber beds. Based on this finding, concerns were raised about their potential for these compounds to poison the Sabatier reactor. Further investigation was required to identify these compounds due to their high concentrations and unique matrix of the CO2 scrubber exhaust. This paper describes these events as well as the process that was developed to identify the volatile compounds that increased. An examination of how much the certain compounds can be concentrated by the scrubber systems is also included.

Volatiles↗
NASA NTRS1994

Summertime partitioning and budget of NO(y) compounds in the troposphere over Alaska and Canada: ABLE 3B

As part of NASA's Arctic Boundary Layer Expedition 3A and 3B field measurement programs, measurements of NO(x), HNO3, PAN, PPN, and NO(y) were made in the middle to lower troposphere over Alaska and Canada during the summers of 1988 and 1990. These measurements are used to assess the degree of closure within the reactive odd nitrogen (N(x)O(y)) budget through the comparison of the values of NO(y) measured with a catalytic convertor to the sum of individually measured NO(y) (i) compounds (i.e., sigmaNO(y)(i) = NO(x) + HNO3 + PAN + PPN). Significant differences were observed between the various study regions. In the lower 6 km of the troposphere over Alaska and the Hudson Bay lowlands of Canada a significant fraction of the NO(y) budget (30 to 60%) could not be accounted for by the measured sigmaNO(y)i. This deficit in the NO(y) budget is about 100 to 200 parts per trillion by volume (pptv) in the lower troposphere (0.15 to 3 km) and about 200 to 400 pptv in the middle free troposphere (3 to 6.2 km). Conversely, the NO(y) budget in the northern Labrador and Quebec regions of Canada is almost totally accounted for within the combined measurement uncertainties of NO(y) and the various NO(y)(i) compounds. A substantial portion of the NO(y) budget's 'missing compounds' appears to be coupled to the photochemical and/or dynamical parameters influencing the tropospheric oxidative potential over these regions. A combination of factors are suggested as the causes for the variability observed in the NO(y) budget. In addition, the apparent stability of compounds represented by the NO(y) budget deficit in the lower-altitude range questions the ability of these compounds to participate as reversible reservoirs for 'active' odd nitrogen and suggest that some portion of the NO(y) budget may consist of relatively unreactive nitrogen-containing compounds.

Sandholm, S.↗
NASA NTRS1994

Compound chondrules: An experimental investigation

Compound chondrules are considered to be the product of collisions between molten chondrules during chondrule formation Wasson, J. T. et al. (1994) have argued that some compound chondrules are formed when a chondrule with an accretional rim experienced a flash-melting event similar to a chondrule-forming event. We have designed experiments to investigate the formation of compound chondrules by both methods. Experiments were performed on a Deltech vertical muffle tube furnace to form synthetic chondrules to use as accretion rim material. For our experimental conditions, it is clear that compound chondrules can only be made by a collisional event. Our changes maintain their spherical shape and produce distinct boundaries between charges that are similar to natural compound chondrules. Furthermore, collision event(s) between chondrules will cause nucleation if they are molten and undercooled, thus producing chondrule textures. Flash melting chondrules with accretionary rims will not produce compound chondrules but will produce new chondrules with new textures.

Connolly, H. C., Jr.↗
NASA NTRS1976

Group extraction of organic compounds present in liquid samples

An extraction device is disclosed comprising a tube containing a substantially inert, chemically non-reactive packing material with a large surface area to volume ratio. A sample which consists of organic compounds dissolved in a liquid, is introduced into the tube. As the sample passes through the packing material it spreads over the material's large surface area to form a thin liquid film which is held on the packing material in a stationary state. A particular group or family of compounds is extractable from the sample by passing a particular solvent system consisting of a solvent and selected reagents through the packing material. The reagents cause optimum conditions to exist for the compounds of the particular family to pass through the phase boundary between the sample liquid and the solvent of the solvent system. Thus, the compounds of the particular family are separated from the sample liquid and become dissolved in the solvent of the solvent system. The particular family of compounds dissolved in the solvent, representing an extract, exits the tube together with the solvent through the tube's nozzle, while the rest of the sample remains on the packing material in a stationary state. Subsequently, a different solvent system may be passed through the packing material to extract another family of compounds from the remaining sample on the packing material.

Jahnsen, Vilhelm J.↗
NASA NTRS2013

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Socki, Richard A.↗
NASA NTRS2022

Responses of Compound Daytime and Nighttime Warm-Dry and Warm-H Events to Individual Anthropogenic Forcings

Daytime heat is often associated with reduced soil moisture and cloud cover, while nighttime heat is connected to high humidity and increased cloud cover. Due to these differing mechanisms, compound daytime and nighttime heat events may respond differently to major anthropogenic forcings (greenhouse gases, anthropogenic aerosols, land-use and land-cover change). Here, we use GISS ModelE2.1-G historical single-forcing runs from 1955 to 2014 to examine how individual anthropogenic forcings affect compound heat events—specifically warm daytime and nighttime temperatures compounded with dry precipitation or high humidity conditions. We show that greenhouse gases alone amplify the natural frequency of warm-dry events by 1.5–5 times and warm-humid events by 2–9 times in tropical and extratropical latitudes. Conversely, aerosols and land-use/land-cover change reduce the frequency of these events, resulting in more modest increases and in some regions, declines, in the historical 'all-forcings' scenario. Individually, aerosol effects are stronger and more widespread compared to land-use, oftentimes reducing the natural frequency of these events by 60%–100%. The responses of these compound events are primarily driven by changes in daytime and nighttime temperatures through large-scale warming via greenhouse gases and cooling from aerosols and land-use/land-cover change. However, changes in warm-dry events are amplified in regions with concurrent precipitation declines (e.g. Central America, Mediterranean regions) and warm-humid events are amplified by global concurrent humidity increases. Additionally, we find differences between daytime and nighttime compound responses in the historical experiment that can be traced back to the individual forcings. In particular, aerosols produce a greater cooling effect on daytime relative to nighttime temperatures, which notably results in a historical reduction of Northern Hemisphere daytime warm-dry events relative to natural conditions. Our analysis provides a more comprehensive understanding of the significant impacts of different anthropogenic climate forcings on daytime and nighttime warm-dry and warm-humid events, informing future risk and impact assessments.

Anthropogenic forcings↗
NASA NTRS2023

The Compound Risk of Heat and COVID-19 in New York City: Riskscapes, Physical and Social Factors, and Interventions

Climate change is disrupting the fundamental conditions of human life and exacerbating existing inequity by placing further burdens on communities that are already vulnerable. Risk exposure varies by where people live and work. In this article, we examine the spatial overlap of the compound risks of COVID-19 and extreme heat in New York City. We assess the relationship between socio-demographic and natural, built and social environmental characteristics, and the spatial correspondence of COVID-19 daily case rates across three pandemic waves. We use these data to create a compound risk index combining heat, COVID-19, density and social vulnerability. Our findings demonstrate that the compound risk of COVID-19 and heat are public health and equity challenges. Heat and COVID-19 exposure are influenced by natural, built, and social environmental factors, including access to mitigation infrastructure. Socio-demographic characteristics are significant indicators of COVID-19 and heat exposure and of where compound vulnerability exists. Using GIS mapping, we illustrate how COVID-19 risk geographies change across the three waves of the pandemic and the particular impact of vaccinations before the onset of the third wave. We, then, use our compound risk index to assess heat interventions undertaken by the City, identify neighborhoods of both adequate and inadequate coverage and provide recommendations for future interventions.

COVID-19↗
NASA NTRS1992

Material selection and evaluation of new encapsulation compounds for electric cables for launch support system

Eight urethane compounds were evaluated as possible replacement for the existing encapsulating compoounds for electrical cables for the Launch Support System at Kennedy Space Center (KSC). The existing encapsulating compound, PR-1535, contains the curative MOCA 4-4'-Methylene-BIS (2-chloroaniline), which is a suspect carcinogen and hence may be the subject of further restrictions of its use by the Occupational Safety and Health Administration (OSHA). The samples made in the configuration of cable joints and in the form of disks were evaluated for flammability and hypergolic compatibility. These also underwent accelerated weatherability tests that measured the residual hardness of the exposed samples. Three candidates and the existing compound passed the hardness test. Of these, only one candidate and the existing compound passed the flammability test. The thermal and hydrolytic stability (weatherability) of these samples was studied using thermogravimetric analysis (DSC) techniques. The TMA and DSC data correlated with the residual hardness data; whereas, the TGA data showed no correlation. A hypergolic compatibility test will be conducted on the compound V-356-HE80, which passed both the flammability and accelerated weatherability tests.

Ray, Asit K.↗
NASA NTRS1993

Elastomer Compound Developed for High Wear Applications

The U.S. Army is currently spending 300 million dollars per year replacing rubber track pads. An experimental rubber compound has been developed which exhibits 2 to 3 times greater service life than standard production pad compounds. To improve the service life of the tank track pads various aspects of rubber chemistry were explored including polymer, curing and reinforcing systems. Compounds that exhibited superior physical properties based on laboratory data were then fabricated into tank pads and field tested. This paper will discuss the compounding studies, laboratory data and field testing that led to the high wear elastomer compound.

Crawford, D.↗
NASA NTRS1999

Molecular Modeling and Experimental Investigations of Nonlinear Optical Compounds Monosubstituted Derivatives of Dicyanovinylbenzene

A search for potential nonlinear optical compounds was performed using the Cambridge Structure Database and molecular modeling. We investigated a series of monosubstituted derivatives of dicyanovinylbenzene, since the nonlinear optical (NLO) properties of such derivatives (o-methoxy-dicyanovinylbenzene, DIVA) were studied earlier. The molecular geometry of these compounds was investigated with x-ray analysis and discussed along with the results of molecular mechanics and ab initio quantum chemical calculations. The influence of crystal packing on the planarity of the molecules of this series has been revealed. Two new compounds from the series studied, ortho-F and para-Cl-dicyanovinylbenzene, according to powder measurements, were found to be NLO compounds in the crystal state about 10 times more active than urea. The peculiarities of crystal structure formation in the framework of balance between van der Waals and electrostatic interactions have been discussed. The crystal shape of DIVA and two new NLO compounds have been calculated on the basis of the known crystal structure.

Timofeeva, Tatiana V.↗
NASA NTRS1997

Field Evaluation of Anti-Biofouling Compounds on Optical Instrumentation

Biofouling has been a serious question in the stability of optical measurements in the ocean, particularly in moored and drifting buoy applications. Many investigators coat optical surfaces with various compounds to reduce the amount of fouling; to our knowledge, however, there are no objective, in-situ comparative testing of these compounds to evaluate their effectiveness with respect to optical stability relative to untreated controls. We have tested a wide range of compounds at in-situ locations in Halifax Harbour and in the Adriatic Sea on passive optical sensors. Compounds tested include a variety of TBT formulations, antifungal agents, and low-friction silicone-based compounds; time-scales of up to four months were evaluated. The results of these experiments are discussed.

McLean, Scott↗
NASA NTRS1996

The Infrared Spectra of Nitriles and Related Compounds Frozen in Ar and H2O

We present the 2320-2050/cm (4.31-4.88 micron) infrared spectra of 16 solid state nitrites, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C(is congruent to)N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile phenylcyanide) 9-anthracenecarbonitrile, dimethylcyanamide, isopropy1nitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyr-uvonitrile, dicyandiamide, cyanamide, n-butyfisocyanide, methylisocyanoacetate, dilsopropylcarbodiimide, and hydrogen cyanide. The C(is congruent to)N stretching bands of the majority of nitrites fall in the 2300-2200/cm (4.35-4.55 micron) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contest, the isonitriles and a few exceptional nitrites and related species produce bands at lower frequencies spanning the 2200-2080/cm (4.55-4.81 micron) range. These features also have similar positions in both Am and H2O matrices and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C(is congruent to)N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165/cm (4.62 micron) "XCN" interstellar feature and the 4550/cm (2.2 micron) feature of various objects in the solar system are discussed.

Bernstain, Max P.↗
NASA NTRS1999

Heats of Formation and Bond Energies in Group III Compounds

We present heats of formation and bond energies for Group-III compounds obtained from calculations of molecular ground-state I electronic energies. Data for compounds of the form MXn are presented, where M = B, Al, Ga, and In, X = He H, Cl, and CH3, and n = 1-3. Energies for the B, Al, and Ga compounds are obtained from G2 predictions, while those for the In compounds are obtained from CCSD(T)/CBS calculations; these are the most accurate calculations for indium-containing compounds published to date. In most cases, the calculated thermochemistry is in good agreement with published values derived from experiments for those species that have well-established heats of formation. Bond energies obtained from the heats of formation follow the expected trend (Cl much greater than CH3 approx. H). However, the CH3M-(CH3)2 bond energies obtained for trimethylgallium and trimethylindium are considerably stronger (greater than 15 kcal/mol) than currently accepted values.

Bauschlicher, Charles W., Jr.↗
NASA NTRS2003

Extraterrestrial Organic Compounds in Meteorites

Many organic compounds or their precursors found in meteorites originated in the interstellar or circumstellar medium and were later incorporated into planetesimals during the formation of the solar system. There they either survived intact or underwent further processing to synthesize secondary products on the meteorite parent body. The most distinct feature of CI and CM carbonaceous chondrites, two types of stony meteorites, is their high carbon content (up to 3% of weight), either in the form of carbonates or of organic compounds. The bulk of the organic carbon consists of an insoluble macromolecular material with a complex structure. Also present is a soluble organic fraction, which has been analyzed by several separation and analytical procedures. Low detection limits can be achieved by derivatization of the organic molecules with reagents that allow for analysis by gas chromatography/mass spectroscopy and high performance liquid chromatography. The CM meteorite Murchison has been found to contain more than 70 extraterrestrial amino acids and several other classes of compounds including carboxylic acids, hydroxy carboxylic acids, sulphonic and phosphonic acids, aliphatic, aromatic and polar hydrocarbons, fullerenes, heterocycles as well as carbonyl compounds, alcohols, amines and amides. The organic matter was found to be enriched in deuterium, and distinct organic compounds show isotopic enrichments of carbon and nitrogen relative to terrestrial matter.

Botta, Oliver↗
NASA NTRS2004

Enantiomeric and Isotopic Analysis of Organic Compounds in Carbonaceous Meteorites

Carbonaceous meteorites are relatively enriched in soluble organic compounds. The Murchison and Murray meteorites contain numerous compounds of interest in the study of early solar system organic chemistry and organic compounds of potential importance for the origin of life. These include: amino acids, amides, carboxylic acids, and polyols. This talk will focus on the enantiomeric and isotopic analysis of individual meteoritic compounds - primarily polyol acids. The analyses will determine if, in addition to certain amino acids from Murchison, another potentially important class of prebiotic compounds also contains enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life. Preliminary enantiomeric and isotopic (C- 13) measurements of Murchison glyceric acid show that it is indeed extraterrestrial. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) has shown that they are also indigenous to the meteorite.

Cooper, George↗
NASA NTRS2001

Carbonaceous meteorites as a source of sugar-related organic compounds for the early Earth

The much-studied Murchison meteorite is generally used as the standard reference for organic compounds in extraterrestrial material. Amino acids and other organic compounds important in contemporary biochemistry are thought to have been delivered to the early Earth by asteroids and comets, where they may have played a role in the origin of life. Polyhydroxylated compounds (polyols) such as sugars, sugar alcohols and sugar acids are vital to all known lifeforms-they are components of nucleic acids (RNA, DNA), cell membranes and also act as energy sources. But there has hitherto been no conclusive evidence for the existence of polyols in meteorites, leaving a gap in our understanding of the origins of biologically important organic compounds on Earth. Here we report that a variety of polyols are present in, and indigenous to, the Murchison and Murray meteorites in amounts comparable to amino acids. Analyses of water extracts indicate that extraterrestrial processes including photolysis and formaldehyde chemistry could account for the observed compounds. We conclude from this that polyols were present on the early Earth and therefore at least available for incorporation into the first forms of life.

Biogenesis↗
NASA NTRS1997

The infrared spectra of nitriles and related compounds frozen in Ar and H2O

We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.

NASA Center ARC↗
NASA NTRS1996

Transmembrane transport of peptide type compounds: prospects for oral delivery

Synthesis and delivery of potential therapeutic peptides and peptidomimetic compounds has been the focus of intense research over the last 10 years. While it is widely recognized that numerous limitations apply to oral delivery of peptides, some of the limiting factors have been addressed and their mechanisms elucidated, which has lead to promising strategies. This article will briefly summarize the challenges, results and current approaches of oral peptide delivery and give some insight on future strategies. The barriers determining peptide bioavailability after oral administration are intestinal membrane permability, size limitations, intestinal and hepatic metabolism and in some cases solubility limitations. Poor membrane permeabilities of hydrophilic peptides might be overcome by structurally modifying the compounds, thus increasing their membrane partition characteristics and/or their affinity to carrier proteins. Another approach is the site-specific delivery of the peptide to the most permeable parts of the intestine. The current view on size limitation for oral drug delivery has neglected partition considerations. Recent studies suggest that compounds with a molecular weight up to 4000 might be significantly absorbed, assuming appropriate partition behavior and stability. Metabolism, probably the most significant factor in the absorption fate of peptides, might be controlled by coadministration of competitive enzyme inhibitors, structural modifications and administration of the compound as a well absorbed prodrug that is converted into the therapeutically active agent after its absorption. For some peptides poor solubility might present a limitation to oral absorption, an issue that has been addressed by mechanistically defining and therefore improving formulation parameters. Effective oral peptide delivery requires further development in understanding these complex mechanisms in order to maximize the therapeutic potential of this class of compounds.

NASA Discipline Regulatory Physiology↗