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NASA NTRSDate not supplied

One-Carbon Metabolism and SANS 2022 Update

Spaceflight Associated Neuro-ocular Syndrome, or SANS, affects a subset of astronauts (1, 2), and biochemical evidence has documented differences in those astronauts (3). Specifically, they had higher circulating concentrations of metabolites of the one-carbon metabolic pathway (1C), including homocysteine, and these concentrations were higher before flight (3). After ruling out many potential confounding factors in these otherwise healthy individuals (e.g., sex, kidney function, vitamin status, coffee consumption), a study of genetics was warranted. In an initial pilot effort, we documented a genetic predisposition to develop ophthalmic changes after long-duration space flight (4). That is, from a limited study of 5 single-nucleotide polymorphisms (SNPs), we found that the G allele for the MTRR A66G SNP was associated with a greater risk of choroidal folds and cotton-wool spots after flight, and the C allele for SHMT1 C1420T was protective against optic disc edema (4). These data provide a potential pathway for understanding why some individuals develop SANS, while others do not. The initial pilot study of 5 SNPs yielded striking findings, but the 1C pathway is far more complex. An effort was undertaken to examine more than 500 1C SNPs to see if a broader examination could help illuminate this association. That work is ongoing. The astronaut findings led us to advocate for the inclusion of 1C pathway genetic and biochemistry testing on other SANS-related projects, noting that genetics might help identify responders, non-responders, or outliers. The first such effort yielded evidence of an association of specific forms of the MTRR and SHMT-1 SNPs and vitamin B12 status with end-tidal CO2 after acute carbon dioxide exposure (5). The second such effort led to the identification that individuals exposed to strict head-down tilt and CO2 for 30-d who developed optic disc edema also had risk alleles for the two SNPs described above (6). Additionally, we identified a clinical population with many characteristics either attributed or purported to be involved in the ocular changes seen in affected astronauts: women with polycystic ovary syndrome (PCOS). PCOS is a condition of androgen excess and anovulatory menstrual cycles. The shared characteristics and clinical findings between SANS and PCOS generally include higher circulating homocysteine concentrations, increased retinal nerve fiber layer thickness, increased androgen concentrations (or responses), and altered carbohydrate metabolism. To our knowledge, no study has examined whether women with PCOS have asymptomatic ophthalmic anomalies observed in astronauts with SANS. While researchers have evaluated the one-carbon metabolism pathway polymorphisms of PCOS patients, and initial studies show an association with certain one-carbon polymorphisms, none have looked at the set of SNPs identified in our studies that are associated with ophthalmic changes in astronauts. Accordingly, we designed a study to evaluate the association of one-carbon pathway SNPs and ophthalmic findings in patients with PCOS and/or IIH compared to controls. Subjects provided blood samples for vitamin and one carbon biochemistry analyses, an extensive analysis of >500 SNPs associated with one carbon metabolism and had eye examinations and ocular imaging. Data analysis are underway. The data collected to date have shown associations between one carbon pathway biochemistry and genetics and incidence of SANS. The mechanisms for SANS has yet to be identified, although many hypotheses exist. Based on our data, we have developed (8, 9) and expanded (6) a multi-hit hypothesis for how these seemingly disparate findings could be linked. While intriguing, the hypothesis represents the starting point for further research. We aim to clarify the relationship between B-vitamin status and genetics with regard to the risk of SANS. Ultimately, understanding the mechanism(s) behind this will provide a means to predict, prevent, or treat these ophthalmologic pathologies in astronauts, and terrestrial populations.

S M Smith↗
NASA NTRS2010

Discovery and Identification of Dimethylsilanediol as a Contaminant in ISS Potable Water

In September of 2010, analysis of ISS potable water samples was undertaken to determine the contaminant responsible for a rise in total organic carbon (TOC). As analysis of the routine target list of organic compounds did not reveal the contaminant, efforts to look for unknown compounds was initiated, resulting in an unknown peak being discovered in the gas chromatography/mass spectrometry (GC/MS) analysis for glycols. A mass spectrum of the contaminant was then generated by concentrating one of the samples by evaporation and analyzing by GC/MS in full-scan mode. Although a computer match of the compound s identity could not be obtained with the instrument s database, a search with a more up to date mass spectral library yielded a good match with dimethylsilanediol (DMSD). Inductively Coupled Plasma/Mass Spectrometry (ICP/MS) analyses showed abnormally high silicon levels in the samples, confirming that the unknown contained silicon. DMSD was then synthesized to confirm the identification and provide a standard to develop a calibration curve. Further confirmation was provided by external Direct Analysis in Real Time (DART) GC/MS analysis. A preliminary GC/MS method was then developed and archived samples from various locations on ISS were analyzed to determine the extent of the contamination and provide data for troubleshooting. This paper describes these events in more detail as well as problems encountered in routine GC/MS analyses and the subsequent development of high performance liquid chromatography and LC/MS/MS methods for quantitation of DMSD.

Rutz, Jeffrey A.↗
NASA NTRS2007

Stress Rupture Testing and Analysis of the NASA WSTF-JPL Carbon Overwrapped Pressure Vessels

Carbon composite overwrapped pressure vessels (COPVs) are widely used in applications from spacecraft to life support. COPV technology provides a pressurized media storage advantage over amorphous technology with weight savings on the order of 30 percent. The National Aeronautics and Space Administration (NASA) has been supporting the development of this technology since the early 1970's with an interest in safe application of these components to reduce mass to orbit. NASA White Sands Test Facility (WSTF) has been testing components in support of this objective since the 1980s and has been involved in test development and analysis to address affects of impact, propellant and cryogenic fluids exposure on Kevlar and carbon epoxy. The focus of this paper is to present results of a recent joint WSTF-Jet Propulsion Laboratories (JPL) effort to assess safe life of these components. The WSTF-JPL test articles consisted of an aluminum liner and a carbon fiber overwrap in an industry standard epoxy resin system. The vessels were specifically designed with one plus-minus helical wrap and one hoop wrap over the helical and they measured 4.23 x 11.4 in. long. 120 test articles were manufactured in August of 1998 of one lot fiber and resin and the 110 test articles were delivered to WSTF for test. Ten of the 120 test articles were burst tested at the manufacturer to establish the delivered fiber stress. Figure 1 shows a test article in a pre burst condition and with a hoop fiber failure (no leak of pressurized media) and post burst (failure of liner and loss of pressurized media).

Greene, Nathanael↗
NASA NTRS2010

Evolved Gas Analysis and X-Ray Diffraction of Carbonate Samples from the 2009 Arctic Mars Analog Svalbard Expedition: Implications for Mineralogical Inferences from the Mars Science Laboratory

The 2009 Arctic Mars Analog Svalbard Expedition (AMASE) investigated several geologic settings using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL), ExoMars, and Mars Sample Return (MSR). AMASE-related research comprises both analyses conducted during the expedition and further analyses of collected samples using laboratory facilities at a variety of institutions. The Sample Analysis at Mars (SAM) instrument suite, which will be part of the Analytical Laboratory on MSL, consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser spectrometer (TLS). An Evolved Gas Analysis Mass Spectrometer (EGA-MS) was used during AMASE to represent part of the capabilities of SAM. The other instrument included in the MSL Analytical Laboratory is CheMin, which uses X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF) to perform quantitative mineralogical characterization of samples. Field-portable versions of CheMin were used during the AMASE 2009. Here, we discuss the preliminary interpretation of EGA and XRD analyses of selected AMASE carbonate samples and implications for mineralogical interpretations from MSL. Though CheMin will be the primary mineralogical tool on MSL, SAM EGA could be used to support XRD identifications or indicate the presence of volatile-bearing minerals which may be near or below XRD detection limits. Data collected with instruments in the field and in comparable laboratory setups (e.g., the SAM breadboard) will be discussed.

McAdam, A. C.↗
NASA NTRS1972

The carbon chemistry of the moon.

The analysis of lunar samples has shown that the carbon chemistry of the moon is entirely different from the carbon chemistry of the earth. Lunar carbon chemistry is more closely related to cosmic physics than to conventional organic chemistry. Sources of carbon on the moon are considered, giving attention to meteorites and the solar wind. The approaches used in the analysis of the samples are discussed, taking into account the method of gas chromatography employed and procedures used by bioscience investigators in the study of the lunar fines. The presence of indigenous methane and carbide in the lunar fines was established. Reactions and processes taking place on the lunar surface are discussed.

Eglinton, G.↗
NASA NTRS2005

Test and Analysis of a Hyper-X Carbon-Carbon Leading Edge Chine

During parts production for the X43A Mach 10 hypersonic vehicle nondestructive evaluation (NDE) of a leading edge chine detected on imbedded delamination near the lower surface of the part. An ultimate proof test was conducted to verify the ultimate strength of this leading edge chine part. The ultimate proof test setup used a pressure bladder design to impose a uniform distributed pressure field over the bi-planar surface of the chine test article. A detailed description of the chine test article and experimental test setup is presented. Analysis results from a linear status model of the test article are also presented and discussed. Post-test inspection of the specimen revealed no visible failures or areas of delamination.

Smith, Russell W.↗
NASA NTRS1993

Infrared laser spectroscopy of jet-cooled carbon clusters - The bending dynamics of linear C9

We report improved measurements for the nu6 antisymmetric stretch fundamental and observation of the (nu6 + nu15) - nu15 and (nu6 + 2nu15) - 2nu15 hot bands of the linear C9 carbon cluster by direct absorption diode laser spectroscopy of a supersonic carbon cluster beam. Analysis of these bands characterizes C9 as a semirigid molecule with a bending potential similar to that of C5 and further evidences the alternation in degree of rigidity of linear carbon clusters with the g-u symmetry of the HOMO.

Van Orden, A.↗
NASA NTRS2013

Detection of Evolved Carbon Dioxide in the Rocknest Eolian Bedform by the Sample Analysis at Mars(SAM) Instrument at the Mars Curiosity Landing Site

The Sample Analysis at Mars (SAM) instrument detected four releases of carbon dioxide (CO2) that ranged from 100 to 700 C from the Rocknest eolian bedform material (Fig. 1). Candidate sources of CO2 include adsorbed CO2, carbonate(s), combusted organics that are either derived from terrestrial contamination and/or of martian origin, occluded or trapped CO2, and other sources that have yet to be determined. The Phoenix Lander s Thermal Evolved Gas Analyzer (TEGA) detected two CO2 releases (400-600, 700-840 C) [1,2]. The low temperature release was attributed to Fe- and/or Mg carbonates [1,2], per-chlorate interactions with carbonates [3], nanophase carbonates [4] and/or combusted organics [1]. The high temperature CO2 release was attributed to a calcium bearing carbonate [1,2]. No evidence of a high temperature CO2 release similar to the Phoenix material was detected in the Rocknest materials by SAM. The objectives of this work are to evaluate the temperature and total contribution of each Rocknest CO2 release and their possible sources. Four CO2 releases from the Rocknest material were detected by SAM. Potential sources of CO2 are adsorbed CO2, (peak 1) and Fe/Mg carbonates (peak 4). Only a fraction of peaks 2 and 3 (0.01 C wt.%) may be partially attributed to combustion of organic contamination. Meteoritic organics mixed in the Rocknest bedform could be present, but the peak 2 and 3 C concentration (approx.0.21 C wt. %) is likely too high to be attributed solely to meteoritic organic C. Other inorganic sources of C such as interactions of perchlorates and carbonates and sources yet to be identified will be evaluated to account for CO2 released from the thermal decomposition of Rocknest material.

Sutter, B.↗
NASA NTRSDate not supplied

A Ground-Based Network for Improved Validation of Satellite Carbon Dioxide and Methane Observations Over the Eastern United States

Satellite observations of greenhouse gases (GHGs), notably carbon dioxide and methane, over the Eastern United States, are currently only validated indirectly and/or sporadically. There are only four existing routine, ground-based remote sensing locations in the United States suitable for validation of satellite GHG observations: Edwards and Pasadena, CA, Lamont, OK, and Park Falls, WI as part of the Total Carbon Column Observing Network (TCCON). Among other efforts, e.g. the Network for the Detection of Atmospheric Composition Change (NDACC) and EM27/SUN deployments led by the University of Toronto, the only sites west of the Mississippi River are Park Falls, WI and Toronto, ON. The only remaining validation tools, vicarious calibration and airborne campaigns, are sporadic in space and/or time and thus coincide with only a small subsample of available soundings and conditions. As a result, satellite GHG observations over the east coast of the United States, home to more than half of its population, lack a consistent, widespread means of validation. We describe an ongoing effort to position 8 EM27/SUN spectrometers along the Eastern Seaboard over the next two years. The goals of this effort are to improve both satellite validation and our understanding of human and natural influences on the carbon cycle of the Eastern US, the former enabling the latter. This work is intended to augment past, ongoing, and future inter-agency programs, e.g., the NIST Urban Testbed, routine aircraft and aircore sampling by NOAA, and NASA’s Atmospheric Carbon and Transport (ACT)-America sub-orbital campaign, in particular by offering information on broader time and spatial scales than what is already available while maintaining the high-accuracy constraints of in situ data. We will present early analysis including siting considerations to capture local and/or background conditions and comparison to NASA’s Goddard Earth Observing System (GEOS) modeling and assimilation systems. This includes a 40-day, 3-km horizontal resolution global simulation of early 2020 and a 50-km retrospective analysis of Orbiting Carbon Observatory 2 (OCO-2) observations over 2015-present. Both are valuable tools for analyzing expected and observed signals and are useful boundary conditions for yet higher-resolution studies.

Brad Weir↗
NASA NTRS1994

Analysis of the Shuttle Orbiter reinforced carbon-carbon oxidation protection system

Reusable, oxidation-protected reinforced carbon-carbon (RCC) has been successfully flown on all Shuttle Orbiter flights. Thermal testing of the silicon carbide-coated RCC to determine its oxidation characteristics has been performed in convective (plasma Arc-Jet) heating facilities. Surface sealant mass loss was characterized as a function of temperature and pressure. High-temperature testing was performed to develop coating recession correlations for predicting performance at the over-temperature flight conditions associated with abort trajectories. Methods for using these test data to establish multi-mission re-use (i.e., mission life) and single mission limits are presented.

Williams, S. D.↗
NASA NTRS2008

Assimilation of SCIAMACHY Total Column CO Observations: Regional Analysis of Data Impact

Carbon monoxide (CO) total column observations from the SCanning Imaging Absorption SpectroMeter for Atmospheric CHartography (SCIAMACHY) on board ENVISAT are assimilated into the Global Modeling and Assimilation Office (GMAO) constituent assimilation system for the period July 18-October 31, 2004. This is the first assimilation of CO observations from a near infrared sounder. The impact of the assimilation on CO distribution is evaluated using independent Measurement of Ozone and Water vapor by Airbus In-service Aircraft (MOZAIC) in-situ CO profiles. Assimilation of satellite data improves agreement with MOZAIC CO globally, especially in the upper troposphere.

Tangborn, Andrew↗
NASA NTRS2012

Use of Statistical Analysis of Acoustic Emission Data on Carbon-Epoxy COPV Materials-of-Construction for Enhanced Felicity Ratio Onset Determination

Broadband modal acoustic emission (AE) data were acquired during intermittent load hold tensile test profiles on Toray T1000G carbon fiber-reinforced epoxy (C/Ep) single tow specimens. A novel trend seeking statistical method to determine the onset of significant AE was developed, resulting in more linear decreases in the Felicity ratio (FR) with load, potentially leading to more accurate failure prediction. The method developed uses an exponentially weighted moving average (EWMA) control chart. Comparison of the EWMA with previously used FR onset methods, namely the discrete (n), mean (n (raised bar)), normalized (n%) and normalized mean (n(raised bar)%) methods, revealed the EWMA method yields more consistently linear FR versus load relationships between specimens. Other findings include a correlation between AE data richness and FR linearity based on the FR methods discussed in this paper, and evidence of premature failure at lower than expected loads. Application of the EWMA method should be extended to other composite materials and, eventually, composite components such as composite overwrapped pressure vessels. Furthermore, future experiments should attempt to uncover the factors responsible for infant mortality in C/Ep strands.

Abraham, Arick Reed A.↗
NASA NTRS2013

Evaluation of Nanomaterial Approaches to Damping in Epoxy Resin and Carbon Fiber/Epoxy Composite Structures by Dynamic Mechanical Analysis

Vibration mitigation in composite structures has been demonstrated through widely varying methods which include both active and passive damping. Recently, nanomaterials have been investigated as a viable approach to composite vibration damping due to the large surface available to generate energy dissipation through friction. This work evaluates the influence of dispersed nanoparticles on the damping ratio of an epoxy matrix. Limited benefit was observed through dispersion methods, however nanoparticle application as a coating resulting in up to a three-fold increase in damping.

Miller, G.↗
NASA NTRS2016

P21C-2113: Constraining Hesperian Martian PCO2 from Mineral Analysis at Gale Crater

Carbon dioxide is an essential atmospheric component in martian climate models that attempt to reconcile a faint young sun with widespread evidence of liquid water at the planet's surface in the Noachian and Early Hesperian. Current estimates of ancient martian CO levels, derived from global inventories of carbon, and orbital detections of Noachian and Early Hesperian clay mineralbearing terrains indicate CO levels that are unable to support warm and wet conditions. These estimates are subject to various sources of uncertainty however. Mineral and contextual sedimentary environmental data collected by the Mars Science Laboratory rover Curiosity in Gale Crater provide a more direct means of estimating the atmospheric partial pressure of CO (P ) coinciding with a long-lived lake system in Gale crater at approximately 3.5 Ga. Results from a reaction transport model, which simulates mineralogy observed within the Sheepbed member at Yellowknife Bay by coupling mineral equilibria with carbonate precipitation kinetics and rates of sedimentation, indicate atmospheric levels in the 10's mbar range. At such low P levels, climate models are unable to warm Hesperian Mars anywhere near the freezing point of water and other gases are required to raise atmospheric pressure to prevent lakes from boiling away. Thus, lacustrine features of Gale formed in a cold environment by a mechanism yet to be determined, or the climate models lack an essential component that would serve to elevate surface temperatures, at least temporally and/or locally, on Hesperian Mars. Our results also impose restrictions on the potential role of atmospheric CO in inferred warmer conditions of the Noachian.

Bristow, Thomas↗
NASA NTRS2016

Constraining Hesperian martian PCO2 from mineral analysis at Gale crater

Carbon dioxide is an essential atmospheric component in martian climate models that attempt to reconcile a faint young sun with planet-wide evidence of liquid water at the planets surface in the Noachian and Early Hesperian. Current estimates of ancient martian CO2 levels, derived from global inventories of carbon, and orbital detections of Noachian and Early Hesperian clay mineral-bearing terrains indicate CO2 levels that are unable to support warm and wet conditions. These estimates are subject to various sources of uncertainty however. Mineral and contextual sedimentary environmental data collected by the Mars Science Laboratory rover Curiosity in Gale Crater provide a more direct means of estimating the atmospheric partial pressure of CO2 (PCO2) coinciding with a long-lived lake system in Gale crater at ~3.5 Ga. Results from a reaction-transport model, which simulates mineralogy observed within the Sheepbed member at Yellowknife Bay by coupling mineral equilibria with carbonate precipitation kinetics and rates of sedimentation, indicate atmospheric PCO2 levels in the 10’s mbar range. At such low PCO2 levels, climate models are unable to warm Hesperian Mars anywhere near the freezing point of water and other gases are required to raise atmospheric pressure to prevent lakes from boiling away. Thus, lacustrine features of Gale formed in a cold environment by a mechanism yet to be determined, or the climate models still lack an essential component that would serve to elevate surface temperatures, at least temporally and/or locally, on Hesperian Mars. Our results also impose restrictions on the potential role of atmospheric CO2 in inferred warmer conditions of the Noachian.

Bristow, T. F.↗
NASA NTRS1986

Far-ultraviolet fluorescence of carbon monoxide in the red giant Arcturus. II - Analysis of high-dispersion IUE spectra

Faint, diffuse emissions near 1380 A in deeply exposed IUE spectrograms of the red giant Arcturus very likely are associated with bands of the A-X fourth-positive system of carbon monoxide, fluoresced by multiplet UV2 of neutral oxygen near 1305 A. Numerical simulations indicate that the strength of the CO bands is exceedingly sensitive, in the best available one-dimensional model of the chromosphere of Arcturus, to a delicate balance between the rapid inward attenuation of the oxygen radiation field and the rapid outward decline of the molecular absorptivity. The fortuitous character of the overlap region in the single-component model argues that one should also consider the possibility that the pumping occurs in a highly inhomogeneous chromosphere, of the type proposed in previous studies of Arcturus based on observations of the infrared absorption bands of CO.

Ayres, T. R.↗