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NASA NTRS2004

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

Tyson, Daniel S.↗

NASA NTRS2004

Soyuz 7 Return Samples: Assessment of Air Quality Aboard the International Space Station

The toxicological assessments of one grab sample canister (GSC), 6 dual sorbent tubes (DSTs), and 20 formaldehyde badges returned aboard Soyuz 7 are reported. Analytical methods have not changed from earlier reports. Surrogate standard recoveries from the GSC were 84-89%. The recoveries of the less volatile surrogates from the DSTs were 87 to 112%; however, 13C-acetone was only recovered at 53-59%. Formaldehyde recoveries from 2 lab controls were 87 and 95%; trip controls were not returned to ground.

James, John T.↗

NASA NTRS2007

Genesis Concentrator Target Particle Contamination Mapping and Material Identification

The majority of surface particles were found to be < 5 microns in diameter with increasing numbers close to the optical resolution limit of 0.3 microns. Acceleration grid EDS results show that the majority of materials appear to be from the SRC shell and SLA materials which include carbon-carbon fibers and Si-rich microspheres in a possible silicone binder. Other major debris material from the SRC included white paint, kapton, collector array fragments, and Al. Image analysis also revealed that SRC materials were also found mixed with the Utah mud and salt deposits. The EDS analysis of the acceleration grid showed that particles < 1 m where generally carbon based particles. Chemical cleaning techniques with Xylene and HF in an ultrasonic bath are currently being investigated for removal of small particles by the Genesis science team as well as ultra-pure water megasonic cleaning by the JSC team [4]. Removal of organic contamination from target materials is also being investigated by the science team with the use of UV-ozone cleaning devices at JSC and Open University [5]. In preparation for solar wind oxygen analyses at UCLA and Open University [1, 2], surface particle contamination on three Genesis concentrator targets was closely examined to evaluate cleaning strategies. Two silicon carbide (Genesis sample # 60001 and 60003) and one chemical vapor deposited (CVD) 13C concentrator target (60002) were imaged and mosaic mapped with optical microscopes. The resulting full target mosaic images and particle feature maps were subsequently compared with non-flight, but flight-like, concentrator targets and sample return capsule (SRC) materials. Contamination found on the flown concentrator acceleration grid was further examined using a scanning electron microscope (SEM). Energy dispersive X-ray spectroscopy (EDS) for particle identification was subsequently compared with the optical images from the flown targets. Figure 1 show that all three targets imaged in this report are fully intact and do not show any signs of material fractures. However, previous ellipsometry results and overview imaging of both flown SiC targets show a solar wind irradiation gradient from the center focal point to the outer edge [3]. In addition, due to the hard landing, each target has experienced varying degrees of impacts, scratches, and particle debris from the spacecraft and Utah impact site.

Calaway, Michael J.↗

NASA NTRS2008

NanoSIMS Sheds Light on the Origin and Significance of Early Archean Organic Microstructures from the Pilbara of Australia

NanoSIMS was used to characterize sub-micron scale morphology and elemental composition (C, N, S, Si, O) of organic microstructures in Early Archean (3 - 3.4 Ga) charts from the Pilbara of Western Australia. Three categories of structures were analyzed: small spheroids in clusters; spindle-shaped remains; and large spheroids. All are relatively poorly preserved and occur within the chert matrix of the samples. Carbonaceous material in a secondary hydrothermal vein also was analyzed, as an example of non-indigenous organic matter. Comparisons were made of NanoSIMS characteristics of the Archean samples and those from well-preserved, biogenic microfossils in the 0.8 Ga Bitter Springs Formation. The comparisons show that the Pilbara microstructures are generally distinct from material in the hydrothermal vein but similar in morphology and elemental composition to the Bitter Springs microfossils. In addition, the Pilbara structures exhibit a spatial relationship to silicon and oxygen that seemingly reflects silica nucleation on organic surfaces; this argues that the organic frameworks of the Archean structures were present in the sediment during crystallization of the silica matrix. The structures are thus interpreted as being indigenous to the enclosing sediment. While these results are suggestive of Early Archean biogenicity and are consistent with a growing body of data suggesting that life on Earth was well established by 3 to 3.4 Ga, work is continuing to determine the N/C and 13C ratios of individual forms, and this should provide additional insight into the derivation and significance of these ancient organic remains.

Oehler, Dorothy Z.↗

NASA NTRS2009

Status of Reconstruction of Fragmented Diamond-on-Silicon Collector From Genesis Spacecraft Solar Wind Concentrator

In addition to passive solar wind collector surfaces, the Genesis Discovery Mission science canister had on board an electrostatic concave mirror for concentrating the solar wind ions, known as the concentrator . The 30-mm-radius collector focal point (the target) was comprised of 4 quadrants: two of single crystal SiC, one of polycrystalline 13C diamond and one of diamond-like-carbon (DLC) on a silicon substrate. [DLC-on-silicon is also sometimes referenced as Diamond-on-silicon, DOS.] Three of target quadrants survived the hard landing intact, but the DLC-on-silicon quadrant fractured into numerous pieces (Fig. 1). This abstract reports the status of identifying the DLC target fragments and reconstructing their original orientation.

Rodriquez, Melissa C.↗

NASA NTRS2009

A First Look at Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric C02 by the Phoenix Lander

Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars. The isotopic composition of the martian atmosphere has been measured using a number of different methods (Table 1), however a precise value (<1%) has yet to be achieved. Given the elevated 13C values measured in carbonates in martian meteorites it has been supposed that the martian atmosphere was enriched in delta(sup 13)C. This was supported by measurements of trapped CO2 gas in EETA 79001[2] which showed elevated delta(sup 13)C values (Table 1). More recently, Earth-based spectroscopic measurements of the martian atmosphere have measured the martian CO2 to be depleted in delta(sup 13)C relative to CO2 in the terrestrial atmosphere. The spectroscopic measurements performed by Krasnopolsky et al. were reported with approx.2% uncertainties which are much smaller than the Viking measurements, but still remain very large in comparison to the magnitude of carbon and oxygen isotope fractionations under martian surface conditions. The Thermal Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander included a magnetic sector mass spectrometer (EGA) which had the goal of measuring the isotopic composition of martian atmospheric CO2 to within 0.5%. The mass spectrometer is a miniature magnetic sector instrument intended to measure both the martian atmosphere as well as gases evolved from heating martian soils. Ions produced in the ion source are drawn out by a high voltage and focused by a magnetic field onto a set of collector slits. Four specific trajectories are selected to cover the mass ranges, 0.7 - 4, 7 - 35, 14 - 70, and 28 - 140 Da. Using four channels reduces the magnitude of the mass scan and provides simultaneous coverage of the mass ranges. Channel electron multiplier (CEM) detectors that operate in the pulse counting mode detect the ion beams.

Niles, P.B.↗

NASA NTRS2008

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Reddy, V. Prakash↗

NASA NTRS2009

Ethane's 12C/13C Ratio in Titan: Implications for Methane Replenishment

As the .main destination of carbon in the destruction of methane in the atmosphere of Titan, ethane provides information about the carbon isotopic composition of the reservoir from which methane is replenished. If the amount of methane entering the atmosphere is presently equal to the amount converted to ethane, the 12C/13C ratio in ethane should be close to the ratio in the reservoir. We have measured the 12C/13C ratio in ethane both with Cassini CIRS(exp 1) and from the ground and find that it is very close to the telluric standard and outer planet values (89), consistent with a primordial origin for the methane reservoir. The lower 12C/13C ratio measured for methane by Huygens GCMS (82.3) can be explained if the conversion of CH4 to CH3 (and C2H6) favors 12C over 13C with a carbon kinetic isotope effect of 1.08. The time required for the atmospheric methane to reach equilibrium, i.e., for replenishment to equal destruction, is approximately 5 methane atmospheric lifetimes.

Jennings, Donald E.↗

NASA NTRS2010

Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric CO2 by the Phoenix Lander

Niles, Paul B.↗

NASA NTRS2010

STS 130 Return Samples: Assessment of Air Quality Aboard the Shuttle (STS-130) and International Space Station (20A)

The toxicological assessments of 3 grab sample canisters (GSCs) from the Shuttle are reported in Table 1. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates ( 13C-acetone, fluorobenzene, and chlorobenzene) from the 3 Shuttle GSCs averaged 96, 90, and 85 %, respectively. Based on the end-of-mission sample, the Shuttle atmosphere was acceptable for human respiration.

James, John T.↗

NASA NTRS2010

STS 132 Return Samples: Assessment of Air Quality Aboard the Shuttle (STS-132) and International Space Station (ULF4)

The toxicological assessments of 2 grab sample canisters (GSCs) from the Shuttle are reported. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates (13C-acetone, fluorobenzene, and chlorobenzene) from the 2 Shuttle GSCs averaged 93, 85%, and 88%, respectively. Based on the end-of-mission sample, the Shuttle atmosphere was acceptable for human respiration. The toxicological assessment of 7 GSCs from the ISS is also shown. The recoveries of the 3 standards (as listed above) from the GSCs averaged 78, 96 and 90%, respectively. Recovery from formaldehyde control badges ranged from 90 to 112%.

James. John T.↗

NASA NTRS2010

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Fu, Qi↗

NASA NTRS2007

Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of 13C CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

Meador, Mary Ann B.↗

NASA NTRS2011

Soyuz 23 Return Samples: Assessment of Air Quality Aboard the International Space Station

Six mini-grab sample containers (m-GSCs) were returned aboard Soyuz 23 because of concerns that new air pollutants had been present in the air and these were getting into the water recovery system. The Total Organic Carbon Analyzer had been giving increasing readings of total organic carbon (TOC) in the potable water, and it was postulated that an increased load into the system was responsible. The TOC began to decline in late October, 2010. The toxicological assessment of 6 m-GSCs from the ISS is shown in Table 1. The recoveries of 13C-acetone, fluorobenzene, and chlorobenzene from the GSCs averaged 73, 82, and 59%, respectively. We are working to understand the sub-optimal recovery of chlorobenzene.

James, John T.↗

NASA NTRS2004

6S Return Samples: Assessment of Air Quality in the International Space Station (ISS) Based on Solid Sorbent Air Sampler (SSAS) and Formaldehyde Monitoring Kit (FMK) Analyses

The toxicological assessments of SSAS and FMK analytical results are reported. Analytical methods have not changed from earlier reports. Surrogate standard recoveries from the SSAS tubes were 66-76% for 13C-acetone, 85-96% for fluorobenzene, and 73-89% for chlorobenzene. Post-flight flows were far below pre-flight flows and an investigation of the problem revealed that the reduced flow was caused by a leak at the interface of the pump inlet tube and the pump head. This resulted in degradation of pump efficiency. Further investigation showed that the problem occurred before the SSAS was operated on orbit and that use of the post-flight flows yielded consistent and useful results. Recoveries from formaldehyde control badges were 86 to 104%. The two general criteria used to assess air quality are the total-non-methane-volatile organic hydrocarbons (NMVOCs) and the total T-value (minus the CO2 and formaldehyde contributions). The T values will not be reported for these data due to the flow anomaly. Control of atmospheric alcohols is important to the water recovery system engineers, hence total alcohols (including acetone) are also shown for each sample. Octafluoropropane (OFP) is not efficiently trapped by the sorbents used in the SSAS. Because formaldehyde is quantified from sorbent badges, its concentration is also listed separately. These five indices of air quality are summarized.

James, John T.↗

NASA NTRS2011

Distinct Purine Distribution in Carbonaceous Chondrites

Carbonaceous chondrite meteorites are known to contain a diverse suite of organic compounds, many of which are essential components of biochemistry. Amino acids, which are the monomers of proteins, have been extensively studied in such meteorites (e.g. Botta and Bada 2002; Pizzarello et aI., 2006). The origin of amino acids in meteorites has been firmly established as extraterrestrial based on their detection typically as racemic mixtures of amino acids, the presence of many non-protein amino acids, and non-terrestrial values for compound-specific deuterium, carbon, and nitrogen isotopic measurements. In contrast to amino acids, nucleobases in meteorites have been far less studied. Nucleobases are substituted one-ring (pyrimidine) or two-ring (purine) nitrogen heterocyclic compounds and serve as the information carriers of nucleic acids and in numerous coenzymes. All of the purines (adenine, guanine, hypoxanthine, and xanthine) and pyrimidines (uracil) previously reported in meteorites are biologically common and could be interpreted as the result of terrestrial contamination (e.g. van del' Velden and Schwartz, 1974.) Unlike other meteoritic organics, there have been no observations of stochastic molecular diversity of purines and pyrimidines in meteorites, which has been a criterion for establishing extraterrestrial origin. Maltins et al. (2008) performed compound-specific stable carbon isotope measurements for uracil and xanthine in the Murchison meteorite. They assigned a non-terrestrial origin for these nucleobases; however, the possibility that interfering indigenous molecules (e.g. carboxylic acids) contributed to the 13C-enriched isotope values for these nucleobases cannot be completely ruled out. Thus, the origin of these meteoritic nucleobases has never been established unequivocally. Here we report on our investigation of extracts of II different carbonaceous chondrites covering various petrographic types (Cl, CM, and CR) and degrees of aqueous alteration (l, 2, and 3) and one ureilite. Analysis via liquid chromatography coupled with electrospray triple-stage mass spectrometry or orbitrap mass spectrometry employed a targeted approach for analysis focused on the five canonical RNA/DNA nucleobases as well as 14 non-canonical pyrimidines and purines, which have bcen observed under plausible prebiotic reactions.

Callahan, Michael P.↗

NASA NTRS2012

Calibration and Sequence Development Status for the Sample Analysis at Mars Investigation on the Mars Science Laboratory

The measurement goals of the Sample Analysis at Mars (SAM) instrument suite on the "Curiosity" Rover of the Mars Science Laboratory (MSL) include chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples [1,2]. SAM directly supports the ambitious goals of the MSL mission to provide a quantitative assessment of habitability and preservation in Gale crater by means of a range of chemical and geological measurements [3]. The SAM FM combined calibration and environmental testing took place primarily in 2010 with a limited set of tests implemented after integration into the rover in January 2011. The scope of SAM FM testing was limited both to preserve SAM consumables such as life time of its electromechanical elements and to minimize the level of terrestrial contamination in the SAM instrument. A more comprehensive calibration of a SAM-like suite of instruments will be implemented in 2012 with calibration runs planned for the SAM testbed. The SAM Testbed is nearly identical to the SAM FM and operates in a ambient pressure chamber. The SAM Instrument Suite: SAM's instruments are a Quadrupole Mass Spectrometer (QMS), a 6-column Gas Chromatograph (GC), and a 2-channel Tunable Laser Spectrometer (TLS). Gas Chromatography Mass Spectrometry is designed for identification of even trace organic compounds. The TLS [5] secures the C, H, and O isotopic composition in carbon dioxide, water, and methane. Sieved materials are delivered from the MSL sample acquisition and processing system to one of68 cups of the Sample Manipulation System (SMS). 59 of these cups are fabricated from inert quartz. After sample delivery, a cup is inserted into one of 2 ovens for evolved gas analysis (EGA ambient to >9500C) by the QMS and TLS. A portion of the gas released can be trapped and subsequently analyzed by GCMS. Nine sealed cups contain liquid solvents and chemical derivatization or thermochemolysis agents to extract and transform polar molecules such as amino acids, nucleobases, and carboxylic acids into compounds that are sufficiently volatile to transmit through the GC columns. The remaining 6 cups contain calibrants. SAM FM Calibration Overview: The SAM FM calibration in the Mars chamber employed a variety of pure gases, gas mixtures, and solid materials. Isotope calibration runs for the TLS utilized 13C enriched C02 standards and 0 enriched CH4. A variety of fluorocarbon compounds that spanned the entire mass range of the QMS as well as C3-C6 hydrocarbons were utilized for calibration of the GCMS. Solid samples consisting of a mixture of calcite, melanterite, and inert silica glass either doped or not with fluorocarbons were introduced into the SAM FM cups through the SAM inlet funnel/tube system.

Mahaffy, Paul R.↗

NASA NTRS2013

Toxicological Assessment of ISS Air Quality: SpaceX-2 First Ingress

One mini-grab sample container (M-GSC) was collected by crew members onboard ISS during first ingress into SpaceX-2 on March 3, 2013, three days after late cargo loading and a pre-launch clean air purge. Recoveries of the three surrogate standards from the m-GSC were: 13C-acetone, 97%; fluorobenzene, 95%; and chlorobenzene, 68%.

Meyers, Valerie↗