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All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

The abundances of carbon and nitrogen in I Zw 18

The first measurements of the semiforbidden C III 1909 A and forbidden N II 6583 A emission lines in I Zw 18 are reported. These data are combined with previously published spectrophotometry in order to derive the carbon and nitrogen abundances in I Zw 18 with the aid of a nebular model. The CNO abundances in I Zw 18 are found to exceed those found in the Magellanic Clouds and other well-observed oxygen-poor irregular galaxies and are more similar to those in the sun and nearby Galactic H II regions. It is argued that I Zw 18 may be older and more chemically evolved than previously believed, and that its extremely low O/H results from escape of O-rich supernova ejecta from the Galaxy or from dilution by accretion of primordial gas. Alternatively, I Zw 18 may have formed from a preenriched intergalactic medium. Spectroscopic diagnostics for composite photoionization models to fit the spectrum of I Zw 18 are discussed.

Dufour, Reginald J.↗
NASA NTRSDate not supplied

Gaseous By-Product of Thermal Vacuum Processing of Lunar Highland Simulant

Scientists at Kennedy Space Center are advancing technologies to achieve oxygen extraction on the Lunar surface. One such technology is Molten Regolith Electrolysis (MRE) in which regolith simulant is melted under high temperatures to perform oxygen extraction through electrolysis of the melt pool. A study was conducted to understand the molten formation and proper-ties of Lunar Highlands Simulants (LHS-1) under high vacuum environments ranging between 10-6 Torr. These studies include investigating the regolith melt behavior and by-product gas analysis systems to prepare for pilot plant development and operations. The off-gassing rates and pressure build-up, gaseous compounds, and material compatibility may be a risk to MRE systems. The KSC findings are reported here for inclusion into future mis-sion architecture and operational planning. The four stages of the experiment were vacuum, resistive heating, regolith melt and gas detection. The regolith mass of 70 g was melted in a 40 cm tall x 50 cm diameter vacuum chamber at temperature increase rate 47 ℃ /min and ramp rate of 1 ampere/3 min up to an 18-amp maximum. The test is conducted for about 60 minutes and the constituent gases produced during heating of regolith is monitored with a re-sidual gas analyzer. During the molten formation, primary off-gassing volatiles included water vapor (18 amu), a peak at 44 amu (FeO2 – expected), and atomic oxygen (16 amu), among a series of other compounds that could create compatibility issues such as magnesium, chlorine, and silicon oxide. These results add to the knowledge required for successful oxygen extraction on the moon.

Molten Regolith Electrolysis↗
DOE OSTI2020

Dynamic Lattice Oxygen Participation on Perovskite LaNiO 3 during Oxygen Evolution Reaction

Determining the role of lattice oxygen in the oxygen evolution reaction (OER) is pivotal to understanding reaction mechanisms and predictive design of electrocatalysts based on transition metal oxides. In this work, using well-defined, isotope ( 18 O)-enriched, epitaxial LaNiO 3 thin films as a model system, we show that dynamic lattice oxygen exchange occurs during OER. Additionally, time-of-flight secondary ion mass spectrometry studies reveal that lattice oxygen exchange can affect the top 2 nm of the LaNiO 3 films, but the surface remains crystalline and in the perovskite phase after OER. In addition, cyclic voltammetry and potentiostatic measurements show that OER kinetics are strongly pH dependent, which is different from what is expected from the typical four concerted proton-electron transfer steps, most likely due to the involvement of lattice oxygen. Our findings suggest that the roles of lattice oxygen during OER, and charge transfer mechanisms in such systems, need to be further studied in order to design more efficient and stable electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2016

Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals −7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay of (sup 26) Al. Delta (sup 25) Mg (mass-dependent fractionation) in hibonite is approximately −5 per mille per atomic mass unit relative to Madagascar hibonite, but is not well constrained for perovskite due to very large uncertainties owing to extremely low Mg contents. Similar to Mg isotopes, SHAL hibonite and perovskite show essentially the same Ti isotopic compositions, with anomalies in (sup 50) Ti of approximately 14 per mille, but the former shows greater Ti isotope fractionation than the latter (2.5 per mille per atomic mass unit versus 0 per mille). Discussion and Conclusions: The Al-Mg and Ti isotopic compositions of SHAL hibonite are consistent with those of HAL, suggesting that SHAL hibonite is a FUN inclusion and likely formed prior to homogenization of (sup 26) Al and Ti isotope variations in the solar nebula. However, the formation mechanisms for SHAL and HAL differ, given the differences in the REE patterns and degrees of oxygen mass-dependent fractionation. The Group-II to Group-III like REE patterns, the Yb depletions, and negative delta (sup 25) Mg observed in SHAL hibonite are all consistent with condensation of the hibonite precursor in a reducing environment.. The lack of large Ce depletions in SHAL hibonite implies that distillation processes that fractionated hibonite's oxygen isotopes must have taken place under a reducing condition, but the extent to which SHAL hibonite was distilled appears to be less than HAL because of the smaller degree of oxygen mass-dependent fractionation. The perovskite shares essentially the same Ti and Mg isotopic compositions as hibonite and probably formed in the same reservoir.. The ultrarefractory REE pattern seen in perovskite likely resulted from gas-solid fractionation which depleted HREEs in this reservoir. This process also explains why SHAL hibonite is generally depleted in HREEs relative to LREEs.

Liu, M.-C.↗
NASA NTRS1989

Steps toward interstellar silicate dust mineralogy

One of the most certain facts on interstellar dust is that it contains grains with silicon oxygen tetrahedra (SOT), the internal vibrations of which cause the well known silicate bands at 10 and 18 microns. The broad and almost structureless appearance of them demonstrates lack of translation symmetry in these solids that must be considered amorphous or glassy silicates. There is no direct information on the cations in these interstellar silicates and on the number of bridging oxygens per tetrahedron (NBO). Comparing experimental results gained on amorphous silicates, e.g., silicate glasses, of cosmically most abundant metals (Mg, Fe, Ca, Al) with the observations is the only way to investigate interstellar silicate dust mineralogy (cf, Dorschner and Henning, 1986). At Jena University Observatory IR spectra of submicrometer-sized grains of pyroxene glasses (SSG) were studied. Pyroxenes are common minerals in asteroids, meteorites, interplanetary, and supposedly also cometary dust particles. Pyroxenes consist of linearly connected SOT (NBO=2). In the vitreous state reached by quenching melted minerals, the SOT remain nearly undistorted (Si-O bond length unchanged); the Si-O-Si angles at the bridging oxygens of pyroxenes, however, scatter statistically. Therefore, the original cation oxygen symmetry of the crystal (octahedral and hexahedral coordination by O) is completely lost. The blended bands at 10 and 18 microns lose their diagnostic differences and become broad and structureless. This illustrates best the basic problem of interstellar silicate mineral diagnostics. Optical data of glasses of enstatite, bronzite, hypersthene, diopside, salite, and hedenbergite have been derived. Results of enstatite (E), bronzite (B), and hypersthene (H) show very good agreement with the observed silicate features in the IR spectra of evolutionarily young objects that show P-type silicate signature according to the classification by Gurtler and Henning (1986). Compositional parameters and main characteristics of experimental SSG spectra in IR for the glasses E, B, and H are shown in tabular form. Results fit excellently the relations derived by Koike and Hasegawa (1987) and suggest that the band ratio of the astronomical silicate by Draine and Lee (1984) is too low.

Dorschner, J.↗
DOE OSTI2023

Engineering Active Surface Oxygen Sites of Cubic Perovskite Cobalt Oxides toward Catalytic Oxidation Reactions

Unraveling the role of surface oxygen sites in transition metal oxides during catalytic reactions has always been the focus of environmental and energy chemistry research. For this work, active surface oxygen sites of cubic perovskite cobalt oxide were engineered to comprehend their crucial role and catalytic mechanism at the molecular level. By removing those inert Sr/La–O termination layers, active oxygen sites were exposed on the Co terminated surface of Sr 0.6 La 0.4 CoO 3–δ that furnished the dominant catalytic process of CO oxidation via the Mars–van Krevelen (MvK) mechanism. The fabrication of five-coordinate cobalt ions and the enhanced covalency of Co–O bonds not only optimize the surface electronic structure of Co 3d–O 2p, but also supply active surface oxygen sites, which effectively oxidizes CO to CO 2 with a significantly improved oxidation performance and stability as evidenced by soft/hard XAS, XPS, and O 2 -TPD. Furthermore, online isotopic 18 O 2 mass spectrometry, in situ DRIFTS, and theoretical simulation demonstrate that the activity of surface oxygen sites enhances the kinetics of the MvK reaction, while unsaturated coordination sites from five-coordinate cobalt ions primarily contribute to the activated oxygen molecules and the stable catalytic cycle. The results reported here provide a deep insight into the comprehension of the relationships among active oxygen sites, surface electronic structure, and the reaction mechanism of transition metal oxides necessary for catalytic oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Tracer Study on sCO2 Corrosion with Multiple Oxygen-Bearing Impurities

Abstract Several modern power production systems utilize supercritical CO 2 (sCO 2 ), which can contain O 2 and H 2 O as impurities. These impurities may degrade the compatibility of structural alloys through accelerated oxidation. However, it remains unclear which of these impurities plays a bigger role in high-temperature reactions taking place in sCO 2 . In this study, various model and commercial Fe‐ and Ni‐based alloys were exposed in 300 bar sCO 2 at 750 °C to low levels (50 ppm) of O 2 and H 2 O for 1,000 h. 18 O-enriched water was used to enable the identification of the oxygen source in the post-exposure characterization of the samples. However, oxygen from the water did not accumulate in the scale, which consisted of Cr 2 O 3 in the cases where a protective oxide formed. A 2wt.% Ti addition to a Ni-22%Cr model alloy resulted in the formation of thicker oxides in sCO 2 , while a 1wt.% Al addition reduced the scale thickness. A synergistic effect of both Al and Ti additions resulted in an even thicker oxide than what was formed solely by Ti, similar to observations for Ni-based alloy 282.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A P-61 Black Widow Inspired Palladium Biladiene Complex for Efficient Sensitization of Singlet Oxygen Using Visible Light

Photodynamic therapy (PDT) is a promising treatment option that ablates cancerous cells and tumors via photoinduced sensitization of singlet oxygen. Over the last few decades, much work has been devoted to the development of new photochemotherapeutic agents for PDT. A wide variety of macrocyclic tetrapyrrole based photosensitizers have been designed, synthesized and characterized as PDT agents. Many of these complexes have a variety of issues that pose a barrier to their use in humans, including biocompatibility, inherent toxicity, and synthetic hurdles. We have developed a non-traditional, non-cyclic, and non-aromatic tetrapyrrole ligand scaffold, called the biladiene (DMBil1), as an alternative to these traditional photosensitizer complexes. Upon insertion of a heavy atom such as Pd 2+ center, Pd[DMBil1] generates singlet oxygen in substantial yields (Φ Δ = 0.54, λ exc = 500 nm) when irradiated with visible light. To extend the absorption profile for Pd[DMBil1] deeper into the phototherapeutic window, the tetrapyrrole was conjugated with alkynyl phenyl groups at the 2- and 18-positions (Pd[DMBil2-PE]) resulting in a significant redshift while also increasing singlet oxygen generation (Φ Δ = 0.59, 600 nm). To further modify the dialkynyl-biladiene scaffold, we conjugated a 1,8-diethynylanthracene with to the Pd[DMBil1] tetrapyrrole in order to further extend the compound’s π-conjugation in a cyclic loop that spans the entire tetrapyrrole unit. This new compound (Pd[DMBil2-P61]) is structurally reminiscent of the P61 Black Widow aircraft and absorbs light into the phototherapeutic window (600–900 nm). In addition to detailing the solid-state structure and steady-state spectroscopic properties for this new biladiene, photochemical sensitization studies demonstrated that Pd[DMBil2-P61] can sensitize the formation of 1 O 2 with quantum yields of Φ Δ = 0.84 upon irradiation with light λ = 600 nm. These results distinguish the Pd[DMBil2-P61] platform as the most efficient biladiene-based singlet oxygen photosensitizer developed to date. When taken together, the improved absorption in the phototherapeutic window and high singlet oxygen sensitization efficiency of Pd[DMBil2-P61] mark this compound as a promising candidate for future study as an agent of photodynamic cancer therapy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

New thermal decomposition pathway for TATB

Abstract Understanding the thermal decomposition behavior of TATB (1,3,5-triamino-2,4,6-trinitrobenzene) is a major focus in energetic materials research because of safety issues. Previous research and modelling efforts have suggested benzo-monofurazan condensation producing H 2 O is the initiating decomposition step. However, early evolving CO 2 (m/z 44) along with H 2 O (m/z 18) evolution have been observed by mass spectrometric monitoring of head-space gases in both constant heating rate and isothermal decomposition studies. The source of the CO 2 has not been explained, until now. With the recent successful synthesis of 13 C 6 -TATB ( 13 C incorporated into the benzene ring), the same experiments have been used to show the source of the CO 2 is the early breakdown of the TATB ring, not adventitious C from impurities and/or adsorbed CO 2 . A shift in mass m/z 44 (CO 2 ) to m/z 45 is observed throughout the decomposition process indicating the isotopically labeled 13 C ring breakdown occurs at the onset of thermal decomposition along with furazan formation. Partially labeled (N 18 O 2 ) 3 -TATB confirms at least some of the oxygen comes from the nitro-groups. This finding has a significant bearing on decomposition computational models for prediction of energy release and deflagration to detonation transitions, with respect to conditions which currently do not recognize this oxidation step.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Crystal structure and catalytic mechanism of drimenol synthase, an unusual bifunctional terpene cyclase–phosphatase

Drimenol synthase fromAquimarina spongiae(AsDMS) is a highly unusual chimera that integrates two distinct, sequential isoprenoid processing activities within a single polypeptide chain. AsDMS catalyzes the class II cyclization of farnesyl diphosphate (FPP) to form drimenyl diphosphate, which then undergoes enzyme-catalyzed hydrolysis to yield drimenol, a bioactive sesquiterpene alcohol with antifungal and anticancer properties. Here, we report the X-ray crystal structures of AsDMS and its complex with a sesquiterpene thiol. The AsDMS structure exhibits a didomain architecture consisting of a terpene cyclase β domain and a haloacid dehalogenase-like phosphatase domain, with two distinct active sites located on opposite sides of the protein. Mechanistic studies show that dephosphorylation of the drimenyl diphosphate intermediate proceeds through stepwise hydrolysis such that two equivalents of inorganic phosphate rather than inorganic pyrophosphate are coproducts of the reaction sequence. When the AsDMS reaction is performed in H 2 18 O, 18 O is not incorporated into drimenol, indicating that the hydroxyl oxygen of drimenol originates from the prenyl oxygen of FPP rather than a water molecule from bulk solution. These results correct a mechanistic proposal previously advanced by another group. Surprisingly, AsDMS exhibits substrate promiscuity, catalyzing the conversion of the slowly reactive substrate mimic farnesyl-S-thiolodiphosphate into cyclic and linear sesquiterpene products. Structural and mechanistic insights gained from AsDMS illustrate the functional diversity of terpene biosynthetic enzymes and provide a foundation for engineering “designer cyclase” assemblies capable of generating a wide variety of terpenoid products.

Science & Technology - Other Topics↗
DOE OSTI2024

Evidence of both molecular cloud and fluid chemistry in Ryugu regolith

The sulfur chemistry of (162173) Ryugu particles can be a powerful tracer of molecular cloud chemistry and small body processes, but it has not been well explored. We report identification of organosulfurs and a sulfate grain in two Ryugu particles, A0070 and A0093. The sulfate grain shows oxygen isotope ratios (δ 17 O = -11.0 ± 4.3 per mil, δ 18 O = -7.8 ± 2.3 per mil) that are akin to silicates in Ryugu but exhibit mass-independent sulfur isotopic fractionation (Δ 33 S = +5 ± 2 per mil). A methionine-like coating on the sulfate grain is isotopically anomalous (δ 15 N = +62 ± 2 per mil). Both the sulfate and organosulfurs can simultaneously form and survive during aqueous alteration within Ryugu’s parent body, under reduced conditions, low temperature, and a pH >7 in the presence of N-rich organic molecules. This work extends the heliocentric zone where anomalous sulfur, formed by selective photodissociation of H 2 S gas in the molecular cloud, is found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Changes in the Optical Properties of Materials Are Observed After 18 Months in Low Earth Orbit

Materials located on the exterior of spacecraft in low Earth orbit are subjected to a number of environmental threats, including atomic oxygen, ultraviolet radiation, thermal cycling, and micrometeroid and debris impact. Atomic oxygen attacks materials vulnerable to oxidation. Ultraviolet radiation can break chemical bonds and cause undesirable changes in optical properties. Thermal cycling can cause cracking, and micrometeroid and debris impacts can damage protective coatings. Another threat is contamination. The outgassing of volatile chemicals can contaminate nearby surfaces, changing their thermal control properties. Contaminated surfaces may undergo further change as a result of atomic oxygen and ultraviolet radiation exposure. The Passive Optical Sample Assembly (POSA) experiment was designed as a risk mitigation experiment for the International Space Station. Samples were characterized before launch, exposed for 18 months on the exterior of Mir, and characterized upon their return. Lessons learned from POSA about the durability of material properties can be applied to the space station and other long-duration missions.

Jaworske, Donald A.↗
NASA NTRS2002

Investigation of Nebular Processes Through Oxygen Isotopic Analysis of Primitive Meteorite Materials

As a direct result of support provided by this grant, precise and accurate determination of delta(18)O and delta(17)O in silicates (and other minerals) by ion microprobe (both IMS 6f and IMS 1270) are now being carried out in several laboratories, and these analyses, combined with application of laser fluorination techniques, have led to a proliferation of oxygen isotopic data in the past approx. 3 years. The applications of these techniques in cosmochemical research have been myriad, from understanding the most refractory objects in the nebula (CAIs) to the low temperature alteration processes on meteorite parent bodies. Here, we describe our progress in understanding the oxygen isotopic microdistributions in primitive meteorite materials, as directly supported by this Origins grant.

Leshin, Laurie↗
DOE OSTI2024

Data for: Time to anoxia: Observations and predictions of oxygen drawdown following coastal flood events

This dataset contains data and code associated with the paper Patel et al. "Time to anoxia: Observations and predictions of oxygen drawdown following coastal flood events".The coastal terrestrial-aquatic interface (TAI) is a highly dynamic system characterized by strong physical, chemical, and biological gradients. In particular, shifting soil redox conditions and consumption of terminal electron acceptors, due in part to dynamic hydrologic conditions, is a strong driver of carbon availability and transformations across TAIs. However, while redox dynamics are well described, our ability to quantitatively forecast rates of oxic to anoxic shifts in soils with different characteristics and inundation regimes is limited. We integrated field measurements, laboratory incubations, and model simulations to improve mechanistic understanding of oxygen consumption dynamics in coastal soils. Continuous in situ monitoring unexpectedly revealed that flooding caused temporary spikes in subsurface dissolved oxygen followed by rapid consumption in the wetlands. To further investigate these mechanisms in a controlled setting, we performed laboratory incubations using surface and subsurface soils from a TAI gradient (defined here as upland forest to transitional forest to wetland) in Western Lake Erie to measure oxygen consumption rates in TAI soils during flood events. In our experiments, wetland soils reached anoxia the fastest, in ∼ 9 h on average, whereas upland soils turned anoxic in ∼ 18 h. Subsurface upland soils did not turn anoxic even after two weeks of saturation in the lab, and their oxygen consumption patterns suggested carbon and/or nutrient limitation. These results are consistent with in-situ groundwater redox and oxygen measurements in the field, where wetland soils exhibited the highest rates of oxygen consumption along the TAI. Model simulations of oxygen consumption suggested that oxygen consumption had stronger abiotic controls in wetland soils but stronger biotic controls in upland soils, providing a useful framework for future incubation experiments. Microbial activity is a strong driver of oxygen consumption in TAI soils, although it is constrained by the availability of dissolved carbon in subsurface soils.This dataset contains a compressed (.zip) archive of the data and R scripts used for this manuscript. The dataset includes files in .csv format, which can be accessed and processed using MS Excel or R. This archive can also be accessed on GitHub at https://github.com/COMPASS-DOE/cmps-time_to_anoxia (DOI: 10.5281/zenodo.10815374).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Organic contamination detection for isotopic analysis of water by laser spectroscopy

Hydrogen and oxygen stable isotope ratios (δ 2 H, δ 17 O, and δ 18 O values) are commonly used tracers of water. These ratios can be measured by isotope ratio infrared spectroscopy (IRIS). However, IRIS approaches are prone to errors induced by organic compounds present in plant, soil, and natural water samples. A novel approach using 17 O-excess values has shown promise for flagging spectrally contaminated plant samples during IRIS analysis. A systematic assessment of this flagging system is needed to prove it useful. Errors induced by methanol and ethanol water mixtures on measured IRIS and isotope ratio mass spectrometry (IRMS) results were evaluated. For IRIS analyses both liquid- and vapour-mode (via direct vapour equilibration) methods are used. The δ 2 H, δ 17 O, and δ 18 O values were measured and compared with known reference values to determine the errors induced by methanol and ethanol contamination. In addition, the 17 O-excess contamination detection approach was tested. This is a post-processing detection tool for both liquid and vapour IRIS triple-isotope analyses, utilizing calculated 17 O-excess values to flag contaminated samples. Organic contamination induced significant errors in IRIS results, not seen in IRMS results. Methanol caused larger errors than ethanol. Results from vapour-IRIS analyses had larger errors than those from liquid-IRIS analyses. The 17 O-excess approach identified methanol driven error in liquid- and vapour-mode IRIS samples at levels where isotope results became unacceptably erroneous. For ethanol contaminated samples, a mix of erroneous and correct flagging occurred with the 17 O-excess method. Here our results indicate that methanol is the more problematic contaminant for data corruption. The 17 O-excess method was therefore useful for data quality control. Organic contamination caused significant errors in IRIS stable isotope results. These errors were larger during vapour analyses than during liquid IRIS analyses, and larger for methanol than ethanol contamination. The 17 O-excess method is highly sensitive for detecting narrowband (methanol) contamination error in vapour and liquid analysis modes in IRIS.

60 APPLIED LIFE SCIENCES↗
NASA NTRS2001

Further Investigations of the Passive Optical Sample Assembly (POSA) - I Flight Experiment

The Passive Optical Sample Assembly-I (POSA-I), part of the Mir Environmental Effects Payload (MEEP), was designed to study the combined effects of contamination, atomic oxygen, ultraviolet radiation, vacuum, then-nal cycling, and other constituents of the space environment on spacecraft materials. The MEEP program is a Phase I International Space Station Risk Mitigation Experiment. Candidate materials for the International Space Station (ISS) were exposed in a specially designed "suitcase" carrier, with identical specimens facing either Mir or space. The payload was attached by EVA to the exterior of the Mir docking module during the STS-76 mission (f'ig. 1). It was removed during the STS-86 mission after an 18-month exposure. During the mission, it received approximately 7 x 1019 atoMS/CM2 atomic oxygen, as calculated by polymer mass loss, and 413 ESH of solar ultraviolet radiation on the Mir-facing side. The side facing away from Mir received significant contaminant deposition, so atomic oxygen fluence has not been reliably determined. The side facing away from Mir received 571 ESH of solar UV. Contamination was observed on both the Mir-facing and space-facing sides of the POSA-I experiment , with a greater amount of deposition on the space facing side than the Mir side. The contamination has been determined to be outgassed silicone photofixed by ultraviolet radiation and converted to silicate by atomic oxygen interaction. Electron spectroscopy for chemical analysis (ESCA) with depth profiling indicated the presence of 26 - 31 nm silicate on the Mir-facing side and 500 - 1000 nm silicate on the space-facing side. The depth profiling also showed that the contaminant layer was uniform, with a small amount of carbon present on the surface and trace amounts of nitrogen, phosphorus, sulfur, and tin. The surface carbon layer is likely due to post-flight exposure in the laboratory and is similar to carbonaceous deposits on control samples. EDAX and FTIR analysis concurred with ESCA for the presence of silicon, oxygen, and carbon. Nearly 400 samples were exposed on POSA-I, which included materials such as thermal control coatings polymeric films, optical materials, and multi-layer insulation blankets. A previous paper discussed the effects of the space environment exposure and contaminant deposition on candidate materials for ISS, including Z93P inorganic thermal control coating, various anodizes, and multi-layer insulation blankets. This paper details the investigation of environmental effects on the remainder of POSA-I samples, particularly the innovative conductive thermal control coatings developed by AZ Technology of Huntsville, AL and HT Research Institute of Chicago, IL. The silicone/silicate contamination had a significant impact on the solar absorptance of white inorganic thermal control coatings on the space-facing side of POSA-I. The effect of contamination on electrical conductivity is discussed. Samples of conductive anodized aluminum developed by Boundary Technologies of Buffalo Grove, IL were also exposed on POSA-I. The effects of the space environment and contaminant deposition on the optical and electrical properties of the conductive anodized aluminum are discussed.

Finckenor, Miria M.↗
NASA NTRS2004

Evaluation of a Multi-Parameter Sensor for Automated, Continuous Cell Culture Monitoring in Bioreactors

Compact and automated sensors are desired for assessing the health of cell cultures in biotechnology experiments in microgravity. Measurement of cell culture medium allows for the optirn.jzation of culture conditions on orbit to maximize cell growth and minimize unnecessary exchange of medium. While several discrete sensors exist to measure culture health, a multi-parameter sensor would simplify the experimental apparatus. One such sensor, the Paratrend 7, consists of three optical fibers for measuring pH, dissolved oxygen (p02), dissolved carbon dioxide (pC02) , and a thermocouple to measure temperature. The sensor bundle was designed for intra-arterial placement in clinical patients, and potentially can be used in NASA's Space Shuttle and International Space Station biotechnology program bioreactors. Methods: A Paratrend 7 sensor was placed at the outlet of a rotating-wall perfused vessel bioreactor system inoculated with BHK-21 (baby hamster kidney) cells. Cell culture medium (GTSF-2, composed of 40% minimum essential medium, 60% L-15 Leibovitz medium) was manually measured using a bench top blood gas analyzer (BGA, Ciba-Corning). Results: A Paratrend 7 sensor was used over a long-term (>120 day) cell culture experiment. The sensor was able to track changes in cell medium pH, p02, and pC02 due to the consumption of nutrients by the BHK-21. When compared to manually obtained BGA measurements, the sensor had good agreement for pH, p02, and pC02 with bias [and precision] of 0.02 [0.15], 1 mm Hg [18 mm Hg], and -4.0 mm Hg [8.0 mm Hg] respectively. The Paratrend oxygen sensor was recalibrated (offset) periodically due to drift. The bias for the raw (no offset or recalibration) oxygen measurements was 42 mm Hg [38 mm Hg]. The measured response (rise) time of the sensor was 20 +/- 4s for pH, 81 +/- 53s for pC02, 51 +/- 20s for p02. For long-term cell culture measurements, these response times are more than adequate. Based on these findings , the Paratrend sensor could offer automated, continuous monitoring of cell cultures with a temporal resolution of 1 minute, which is not attainable by sampling via handheld blood analyzer (i-STAT). Conclusion: The resulting bias and precision found in these cell culture-based studies is comparable to Paratrend sensor clinical results. Although the large error in p02 measurements (+/-18 mm Hg) may be acceptable for clinical applications, where Paratrend values are periodically adjusted to a BGA measurement, the O2 sensor in this bundle may not be reliable enough for the single-calibration requirement of sensors used in NASA's bioreactors. The pH and pC02 sensors in the bundle are reliable and stable over the measurement period, and can be used without recalibration to measure cell cultures in rn.jcrogravity biotechnology experiments. Future work will test additional Paratrend sensors to provide statistical assessment of sensor performance.

Pappas, D.↗
NASA NTRS1990

ALS turbomachinery technology

Advanced Development Programs are being pursued by Rocketdyne, Aerojet, and Pratt and Whitney to define and validate design approaches toward producing low-cost, reliable liquid-hydrogen and liquid-oxygen turbopumps for a 2580 kN (580 klb) thrust Advanced Launch System. The generic approach, which is evolving after 18 months of trade studies and conceptual and preliminary design efforts, is explained. In addition, the preliminary liquid-hydrogen turbopump designs produced in parallel tasks by Rocketdyne and Aerojet and the liquid-oxygen turbopump design produced by Pratt and Whitney are described, and technology features and issues are discussed.

Csomor, A.↗