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324 records · Page 18

Performance and lifetime assessment of MPD arc thruster technology

A summary of performance and lifetime characteristics of pulsed and steady-state magnetoplasmadynamic (MPD) thrusters is presented. The technical focus is on cargo vehicle propulsion for exploration-class missions to the Moon and Mars. Relatively high MPD thruster efficiencies of 0.43 and 0.69 have been reported at about 5000 s specific impulse using hydrogen and lithium, respectively. Efficiencies of 0.10 to 0.35 in the 1000 to 4500 s specific impulse range have been obtained with other propellants (e.g., Ar, NH3, N2). Thermal efficiency data in excess of 0.80 at MW power levels using pulsed thrusters indicate the potential of high MPD thruster performance. Extended tests of pulsed and steady-state MPD thrusters yield total impulses at least two to three orders of magnitude below that necessary for cargo vehicle propulsion. Performance tests and diagnostics for life-limiting mechanisms of megawatt-class thrusters will require high fidelity test stands which handle in excess of 10 kA and a vacuum facility whose operational pressure is less than 3 x 10 to the -4 torr.

Sovey, James S.↗

Performance and lifetime assessment of MPD arc thruster technology

A summary of performance and lifetime characteristics of pulsed and steady-state magnetoplasmadynamic (MPD) thrusters is presented. The technical focus is on cargo vehicle propulsion for exploration-class missions to the Moon and Mars. Relatively high MPD thruster efficiencies of 0.43 and 0.69 have been reported at about 5000 s specific impulse using hydrogen and lithium, respectively. Efficiencies of 0.10 to 0.35 in the 1000 to 4500 s specific impulse range have been obtained with other propellants (e.g., Ar, NH3, N2). Thermal efficiency data in excess of 0.80 at MW power levels using pulsed thrusters indicate the potential of high MPD thruster performance. Extended tests of pulsed and steady-state MPD thrusters yield total impulses at least two to three orders of magnitude below that necessary for cargo vehicle propulsion. Performance tests and diagnostics for life-limiting mechanisms of megawatt-class thrusters will require high fidelity test stands which handle in excess of 10 kA and a vacuum facility whose operational pressure is less than 3 x 10 to the -4 torr.

Sovey, James S.↗

Design and Study of Inductively Coupled Plasma Chamber Components Using the SupRISE Test Device at DIII-D

The DIII-D National Fusion Facility aims to increase the auxiliary heating power for the tokamak by upgrading the Neutral Beam Injection (NBI) system. In collaboration with North Carolina State University, the conventional ‘arc and filament’ NBI ion sources will be converted to inductively coupled plasma (ICP) sources which utilize radio frequency (RF) coupling to maximize reliability for high power operation. In support of this initiative, a full scale test device (SupRISE, Superior Radiofrequency Ion Source Experiment) is currently under construction at the DIII-D Facility. In preparation for the construction of a full scale prototype that can be installed on the DIII-D NBI system, experiments on SupRISE will be conducted to determine the optimal RF frequency for high power coupling, Faraday shield slit configuration, and ICP chamber length. SupRISE is comprised of an approximately 30 x 70 cm quartz dielectric vessel with an internal Faraday shield enclosed in a secondary vacuum chamber to ensure structural stability of the dielectric. Actively cooled front and back plates are designed to reduce the thermal stresses on the plasma facing components and mate with the existing accelerator used by the NBI system at DIII-D. 50 kW of RF power will be coupled to the plasma through the quartz over a variable frequency range of 4-8 MHz to sustain a plasma density of ∼ 10 18 m −3 for a 10 s ON, 210 s OFF duty cycle. Various modelling efforts have been employed to simulate the thermal and stress profiles over the primary components of the SupRISE device as well as the inductance behavior of the RF antenna. These simulation results and the final design for SupRISE will be presented. An additional reduced-scale predecessor ICP source (called RISE) has been used to develop a predictive match model that will be applied to frequency optimization studies on SupRISE. Furthermore, the outcomes of this research and complementary efforts at North Carolina State University are essential for the incorporation of ICP NBI positive ion sources at the DIII-D facility.

DIII-D↗

Structural Tolerance of Zirconium Diboride under Electron Irradiation through in-situ Convergent Beam Electron Diffraction and Energy-dispersive X-ray Spectroscopy

Zirconium diboride (ZrB 2 ) is a ultra-high temperature ceramic with high melting temperature (>3000 K), super strength and hardness, good thermal conductivity, and excellent resistance to plasma erosion and chemical erosion, being widely applied in hypersonic flight, arc-electrodes, refractory materials, and plasma-facing materials in fusion reactors. Therefore, the structural stability of the material is essential for the applications. Up to now, the material was investigated under neutron irradiation and high-energy ion irradiations. It was reported that the neutron irradiation caused swelling and catastrophic cracking. High-energy ions (30 keV He + ) changed the surface morphology and caused the bright blue and brown colors on ZrB 2 surfaces between 920 K and 1120 K. The electron irradiation tolerance of the material has not been reported yet. Here we used convergent beam electron diffraction (CBED) and energy-dispersive X-ray spectroscopy (EDS) to investigate structural tolerances of ZrB 2 crystals under high-energy electrons at room temperature under vacuum. Finally, the investigation would benefit the understanding of its structural tolerance at microscales.

42 ENGINEERING↗

Electronic absorption spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. II. The phenanthrene cation (C14H10+) and its 1-methyl derivative

The ultraviolet, visible, and near infrared absorption spectra of phenanthrene (C14H10), 1-methylphenanthrene [(CH3)C14H9], and their radical ions [C14H10+; (CH3)C14H9+], formed by vacuum-ultraviolet irradiation, were measured in neon matrices at 4.2 K. The associated vibronic band systems and their spectroscopic assignments are discussed. The oscillator strengths were calculated for the phenanthrene ion and found lower than the theoretical predictions. This study presents the first spectroscopic data for phenanthrene and its methyl derivative trapped in a neon matrix where the perturbation of the isolated species by its environment is minimum; a condition crucial to astrophysical applications.

NASA Discipline Exobiology↗

Arcjet exploratory tests of ARC optical window design for the AFE vehicle

Tests were made in the 20 MW arc jet facility at the NASA ARC to determine the suitability of sapphire and fused silica as window materials for the Aeroassist Flight Experiment (AFE) entry vehicle. Twenty nine tests were made; 25 at a heating rate about 80 percent of that expected during the AFE entry and 4 at approximately the full, 100 percent AFE heating rate profile, that produces a temperature of about 2900 F on the surface of the tiles that protect the vehicle. These tests show that a conductively cooled window design using mechanical thermal contacts and sapphire is probably not practical. Cooling the window using mechanical thermal contacts produces thermal stresses in the sapphire that cause the window to crack. An insulated design using sapphire, that cools the window as little as possible, appears promising although some spectral data in the vacuum-ultra-violet (VUV) will be lost due to the high temperature reached by the sapphire. The surface of the insulated sapphire windows, tested at the 100 percent AFE heating rate, showed some slight ablation, and cracks appeared in two of three test windows. One small group of cracks were obviously caused by mechanical binding of the window in the assembly, which can be eliminated with improved design. Other cracks were long, straight, thin crystallographic cracks that have very little effect on the optical transmission of the window. Also, the windows did not fall apart along these crystallographic cracks when the windows were removed from their assemblies. Theoretical results from the thermal analysis computer program SINDA indicate that increasing the window thickness from 4 to 8 mm may enable surface ablation to be avoided. An insulated design using a fused silica window tested at the nominal AFE heating rate experienced severe ablation, thus fused silica is not considered to be an acceptable window material.

Whiting, Ellis E.↗

Characterization of CO 4th Positive Radiation in CO2-Ar Mixtures

This paper presents measurements and simulations of CO 4th Positive spectra obtained in NASA Ames Research Center's Electric Arc Shock Tube (EAST) and CentraleSupelec's Plasma Torch. The experiments were aimed at measuring optically thin emission for the main band features of CO 4th Positive by using test gas mixtures of CO2 and Ar. By using mixtures of CO2 and Ar, the temperature of the flow (and consequently black-body curve) is increased compared to using pure CO2 (or CO2 / N2 mixtures). This temperature increase allows for emission spectroscopy of features that would nominally be black-body limited for conditions relevant to Mars entry. The CO 4th Positive system is the focus of this study as it accounts for a large percentage of the emitted radiation for Martian entry, and also due to the difficulties of obtaining experimental validation data due to the emission appearing in the Vacuum Ultraviolet (VUV) spectral range. The focus of this paper is to provide a comprehensive comparison between the EAST and plasma torch data along with various CO 4th Positive databases available in the literature. Previously reported VUV CO2 / N2 EAST data required a larger temperature than would be predicted based upon equilibrium shock relations. The need for the temperature increase implies that the EAST experiment did not fully equilibrate. Thus, it is presumed that the EAST data did not obtain an equilibrium condition. The plasma torch data, on the other hand, is very consistent with equilibrium assumptions. Thus, the equilibrium data obtained in the plasma torch is utilized to construct the CO 4th Positive emission model, which is then applied to the EAST data with a non-equilibrium interpretation.

A. M. Brandis↗

Purification Procedures for Single-Wall Carbon Nanotubes

This report summarizes the comparison of a variety of procedures used to purify carbon nanotubes. Carbon nanotube material is produced by the arc process and laser oven process. Most of the procedures are tested using laser-grown, single-wall nanotube (SWNT) material. The material is characterized at each step of the purification procedures by using different techniques including scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), Raman, X-ray diffractometry (XRD), thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR), and high-performance liquid chromatography (HPLC). The identified impurities are amorphous and graphitic carbon, catalyst particle aggregates, fullerenes, and hydrocarbons. Solvent extraction and low-temperature annealing are used to reduce the amount of volatile hydrocarbons and dissolve fullerenes. Metal catalysts and amorphous as well as graphitic carbon are oxidized by reflux in acids including HCl, HNO3 and HF and other oxidizers such as H2O2. High-temperature annealing in vacuum and in inert atmosphere helps to improve the quality of SWNTs by increasing crystallinity and reducing intercalation.

Gorelik, Olga P.↗

SIM Narrow and wide angle astrometric demonstration on the MAM testbed.

The Space Interferometry Mission (SIM) requires fringe measurements to the level of picometers in order to produce astrometric data at the micro-arc-second level. To be more specific, it is necessary to measure both the position of the starlight central fringe and the change in the internal optical path of the interferometer to tens of picometers. The internal path is measured with a small heterodyne metrology beam, whereas the starlight fringe position is estimated with a CCD sampling a large concentric annular beam. One major challenge for SIM is to align the metrology beam with the starlight beam to keep the consistency between these two sensors at the system level while articulating the instrument optics over the field of regard. The Micro-Arcsecond Metrology testbed (MAM), developed at the Jet Propulsion Laboratory, features an optical interferometer with a white light source, all major optical components of a stellar interferometer and heterodyne metrology sensors. The setup is installed inside a large vacuum chamber in order to mitigate the atmospheric and thermal disturbances. Astrometric observations are simulated by articulating the optics over the 15 degrees field of regard to generate multiple artificial stars. Recent data show agreement between the metrology and starlight paths to 20pm in the narrow angle field and to 350pm in the full wide angle field of regard of SIM. This paper describes the MAM optical setup, the observation process, the current data and how the performance relates to SIM.

Catanzarite, Joseph H.↗

Scattering of water from the glycerol liquid-vacuum interface

Molecular dynamics calculations of the scattering of D2O from the glycerol surface at different collision energies are reported. The results for the trapping probabilities and energy transfer are in good agreement with experiments. The calculations demonstrate that the strong attractive forces between these two strongly hydrogen bonding molecules have only a minor effect on the initial collision dynamics. The trapping probability is influenced to a significant extent by the repulsive hard sphere-like initial encounter with the corrugated surface and, only at a later stage, by the efficiency of energy flow in the multiple interactions between the water and the surface molecules.

NASA Center ARC↗

Limits on the UV Photodecomposition of Carbonates on Mars

The effect of UV (ultraviolet) light on the stability of calcium carbonate in a simulated martian atmosphere was experimentally investigated. Sample cells containing C-13 labeled calcite were irradiated with a Xe arc lamp in 10 mbar of simulated martian atmosphere and a quadrupole mass spectrometer was used to monitor the headspace gases for the production of (13)CO2. We found no experimental evidence of the UV photodecomposition of calcium carbonate in a simulated martian atmosphere. Extrapolating the lower limit of detection of our experimental system to an upper limit of carbonate decomposition on Mars yields a quantum efficiency of 3.5 x 10(exp -8) molecules/photon over the wavelength interval of 190-390 nm and a maximum UV photodecomposition rate of 1.2 x 10(exp -13) kg m(exp -2) s(exp -1) from a calcite surface. The maximum loss of bulk calcite due to this process would be 2.5 nm yr(exp -1). However, calcite is expected to be thermodynamically stable on the surface of Mars and potential UV photodecomposition reaction mechanisms indicate that while calcium carbonate may decompose under vacuum, it would be stable in a CO2 atmosphere. Given the expected stability of carbonate on Mars and our inability to detect carbonate decomposition, we conclude that it is unlikely that the apparent absence of carbonate on the martian surface is due to UV photo decomposition of calcite in the current environment.

Quinn, Richard↗

Evaluation of an Interferometric Sensor for In-Space Detection of Gas Leaks

Space mission planning often involves long-term storage of volatile liquids or high-pressure gases. These may include cryogenic fuels and oxidizers, high-pressure gases, and life-support-critical consumables. The risk associated with the storage of fluids and gases in space systems has long been an issue and the ability to retain these fluids is often tied to mission success. A leak in the storage or distribution system can cause many different problems, including a simple, but mission endangering, loss of inventory or, in severe cases, unbalanced thrust loads on a flight vehicle. Cryogenic propellants are especially difficult to store, especially over a long duration. The propellant can boil off and be lost through the insulating walls of the tank or simple thermal cycling of the fittings, valves, and propellant feed lines may unseat seals allowing the fluid to escape. Current NASA missions call for long-duration in-space storage of propellants, oxidizers, and life support supplies. Leaks of a scale detectable through a pressure drop in the storage tank are often catastrophic and have long been the focus of ground-based mitigation efforts where redundant systems are often employed. However, there is presently no technology available for detecting and monitoring low-level, but still mission-endangering, gas leaks in space. Standard in-space gas detection methods either have a very limited pressure range over which they operate effectively or are limited to certain gases. Mass spectrometer systems are able to perform the detection tasks, but their size, mass and use of high voltage, which could potentially lead to an arc that ignites a combustible propellent, severely limit their usefulness in a space system. In this paper, we present results from testing of the light-based interferometric gas monitoring and leak detection sensor shown in Fig. 1. The output of the sensor is an interference fringe pattern that is a function of the gas density, and commensurate index of refraction, in the sample region. Changes in the density of gas cause the interference fringes to move across a photodiode detector, providing a temporal history of the leak. The sensor is fiber coupled and constructed from solid optics, allowing for placement almost anywhere on the spacecraft. It is also advantageous in that it consumes very little power and does not introduce an ignition source. Data are presented demonstrating the capability of the sensor to measure density variations in different gas species. In addition, the transient response of the sensor in vacuum is demonstrated. These data extend and improve upon the results previously presented by the authors in Ref. [1].

Polzin, Kurt A.↗

Full Facility Shock Frame Simulations of the Electric Arc Shock Tube

Radiative heating computations are performed for high speed lunar return experiments conducted in the Electric Arc Shock Tube (EAST) facility at NASA Ames Research Center. The nonequilibrium radiative transport equations are solved via NASA's in-house radiation code NEQAIR using flow field input from US3D flow solver. The post-shock flow properties for the 10 km/s Earth entry conditions are computed using the stagnation line of a blunt-body and a full facility CFD (Computational Fluid Dynamics) simulation of the EAST shock tube. The shocked gas in the blunt-body flow achieves a thermochemical equilibrium away from the shock front whereas EAST flow exhibits a nonequilibrium behavior due to strong viscous dissipation of the shock by boundary layer. The full-tube flow calculations capture the influence of the boundary layer on the shocked gas state and provide a realistic fluid dynamic input for the radiative predictions. The integrated radiance behind the shock is calculated in NEQAIR for wavelength regimes from Vacuum-UltraViolet (VUV) to InfraRed (IR), which are pertinent to the emission characteristics of high enthalpy shock waves in air. These radiance profiles are validated against corresponding EAST shots. The full-tube simulations successfully predict a sharp radiance peak at the shock front which gets smeared in the test data due to the spatial resolution in the measurements. The full facility based radiance behind the shock shows a slightly better match with the test data in the VUV and Red spectral regions, as compared to that from a blunt-body based predictions. The UV radiance is very similar for both geometries and under-predicts the test behavior. The IR test data matches better with the blunt-body based predictions where the full-tube simulations show a significant over-prediction.

Radiation↗

Vacuum ultraviolet instrumentation for solar irradiance and thermospheric airglow

A NASA sounding rocket experiment was developed to study the solar extreme ultraviolet (EUV) spectral irradiance and its effect on the upper atmosphere. Both the solar flux and the terrestrial molecular nitrogen via the Lyman-Birge-Hopfield bands in the far ultraviolet (FUV) were measured remotely from a sounding rocket on October 27, 1992. The rocket experiment also includes EUV instruments from Boston University (Supriya Chakrabarti), but only the National Center for Atmospheric Research (NCAR)/University of Colorado (CU) four solar instruments and one airglow instrument are discussed here. The primary solar EUV instrument is a 1/4 meter Rowland circle EUV spectrograph which has flown on three rockets since 1988 measuring the solar spectral irradiance from 30 to 110 nm with 0.2 nm resolution. Another solar irradiance instrument is an array of six silicon XUV photodiodes, each having different metallic filters coated directly on the photodiodes. This photodiode system provides a spectral coverage from 0.1 to 80 nm with about 15 nm resolution. The other solar irradiance instrument is a silicon avalanche photodiode coupled with pulse height analyzer electronics. This avalanche photodiode package measures the XUV photon energy providing a solar spectrum from 50 to 12,400 eV (25 to 0.1 nm) with an energy resolution of about 50 eV. The fourth solar instrument is an XUV imager that images the sun at 17.5 nm with a spatial resolution of 20 arc-seconds. The airglow spectrograph measures the terrestrial FUV airglow emissions along the horizon from 125 to 160 nm with 0.2 nm spectral resolution. The photon-counting CODACON detectors are used for three of these instruments and consist of coded arrays of anodes behind microchannel plates. The one-dimensional and two-dimensional CODACON detectors were developed at CU by Dr. George Lawrence. The pre-flight and post-flight photometric calibrations were performed at our calibration laboratory and at the Synchrotron Ultraviolet Radiation Facility (SURF) at the National Institute of Standards and Technology (NIST) in Gaithersburg, Maryland.

Woods, Thomas N.↗

Investigation of Non-Equilibrium Radiation for Earth Entry

For Earth re-entry at velocities between 8 and 11.5 km/s, the accuracy of NASA's computational uid dynamic and radiative simulations of non-equilibrium shock layer radiation is assessed through comparisons with measurements. These measurements were obtained in the NASA Ames Research Center's Electric Arc Shock Tube (EAST) facility. The experiments were aimed at measuring the spatially and spectrally resolved radiance at relevant entry conditions for both an approximate Earth atmosphere (79% N2 : 21% O2 by mole) as well as a more accurate composition featuring the trace species Ar and CO2 (78.08% N2 : 20.95% O2 : 0.04% CO2 : 0.93% Ar by mole). The experiments were configured to target a wide range of conditions, of which shots from 8 to 11.5 km/s at 0.2 Torr (26.7 Pa) are examined in this paper. The non-equilibrium component was chosen to be the focus of this study as it can account for a significant percentage of the emitted radiation for Earth re-entry, and more importantly, non-equilibrium has traditionally been assigned a large uncertainty for vehicle design. The main goals of this study are to present the shock tube data in the form of a non-equilibrium metric, evaluate the level of agreement between the experiment and simulations, identify key discrepancies and to examine critical aspects of modeling non-equilibrium radiating flows. Radiance pro les integrated over discreet wavelength regions, ranging from the Vacuum Ultra Violet (VUV) through to the Near Infra-Red (NIR), were compared in order to maximize both the spectral coverage and the number of experiments that could be used in the analysis. A previously defined non-equilibrium metric has been used to allow comparisons with several shots and reveal trends in the data. Overall, LAURA/HARA is shown to under-predict EAST by as much as 40% and over-predict by as much as 12% depending on the shock speed. DPLR/NEQAIR is shown to under-predict EAST by as much as 50% and over-predict by as much as 20% depending on the shock speed. The one standard deviation scatter in the EAST results was calculated to be 31%. An estimate for the upper bound of the absolute error in wall-directed heat flux was calculated. Below 9 km/s, where the relative difference is large, the absolute error in radiative heat flux due to non-equilibrium models is estimated to be less then 1 W/sq cm. At the highest shock speed of 11 km/s, the error in non-equilibrium is estimated to be less than 20 W/sq cm.

Shock Tube↗

Modular In-Chamber Electron Beam Welding – Process Planning: Welding, Cladding, Inspection, and Manufacturing

Electron beam welding (EBW) is commonly employed by industry today to join relatively thin section components. Industrial sectors which utilize the technology include; automotive, aircraft, aerospace, defense, medical, oil & gas, etc. The ability to produce single pass, thick section (up to 6 inches, 150mm) welds has also been available for more than 40 years; however, the technology has not been deployed for civil nuclear manufacturing and fabrication such as reactor pressure vessels, steam generators, or pressurizers. Instead, thick section joining is performed much in the same manner it has been for decades using submerged arc or gas tungsten arc welding processes. Recent research performed under U.S. Department of Energy (DOE) project DE-NE0008629 has demonstrated that the overall welding time to produce one major reactor pressure vessel (RPV) girth weld can be reduced from weeks to less than 90 minutes, while maintaining exceptional quality and inspection characteristics. The subject project (DE-NE0008846) investigates a modular in-chamber (MIC) EBW approach which allows various RPV sections to be joined within a “modular” chamber. The MIC-EBW approach utilizes individual modules that can be stacked and de-stacked to various heights to enable production girth welds to be performed at a given elevation. This report describes the various processing methodology necessary to complete major girth weldments for the NuScale Power small modular reactor including welding development, manufacturing, production sequence, inspection, and cladding.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Analysis of Water Recovery Rate from the Heat Melt Compactor

Human space missions generate trash with a substantial amount of plastic (20% or greater by mass). The trash also contains water trapped in food residue and paper products and other trash items. The Heat Melt Compactor (HMC) under development by NASA Ames Research Center (ARC) compresses the waste, dries it to recover water and melts the plastic to encapsulate the compressed trash. The resulting waste disk or puck represents an approximately ten-fold reduction in the volume of the initial trash loaded into the HMC. In the current design concept being pursued, the trash is compressed by a piston after it is loaded into the trash chamber. The piston face, the side walls of the waste processing chamber and the end surface in contact with the waste can be heated to evaporate the water and to melt the plastic. Water is recovered by the HMC in two phases. The first is a pre-process compaction without heat or with the heaters initially turned on but before the waste heats up. Tests have shown that during this step some liquid water may be expelled from the chamber. This water is believed to be free water (i.e., not bound with or absorbed in other waste constituents) that is present in the trash. This phase is herein termed Phase A of the water recovery process. During HMC operations, it is desired that liquid water recovery in Phase A be eliminated or minimized so that water-vapor processing equipment (e.g., condensers) downstream of the HMC are not fouled by liquid water and its constituents (i.e., suspended or dissolved matter) exiting the HMC. The primary water recovery process takes place next where the trash is further compacted while the heated surfaces reach their set temperatures for this step. This step will be referred to herein as Phase B of the water recovery process. During this step the waste chamber may be exposed to different selected pressures such as ambient, low pressure (e.g., 0.2 atm), or vacuum. The objective for this step is to remove both bound and any remaining free water in the trash by evaporation. The temperature settings of the heated surfaces are usually kept above the saturation temperature of water but below the melting temperature of the plastic in the waste during this step to avoid any encapsulation of wet trash which would reduce the amount of recovered water by blocking the vapor escape. In this paper, we analyze the water recovery rate during Phase B where the trash is heated and water leaves the waste chamber as vapor, for operation of the HMC in reduced gravity. We pursue a quasi-one-dimensional model with and without sidewall heating to determine the water recovery rate and the trash drying time. The influences of the trash thermal properties, the amount of water loading, and the distribution of the water in the trash on the water recovery rates are determined.

Heat Melt Compactor↗

Microbial Pigments and Their Degradation Products as Biosignatures

Carotenoids are a class of vibrant biological pigments that have a characteristic chemical structure centered around a polyene core (Lu et al. 2018). Carotenoids and their derivatives are candidate biosignatures because they can persist in the terrestrial geologic record for up to 1.73 billion years (Vinnichenko et al. 2020), have specific structures that are likely the result of complex pathways, mediate the survival of many microorganisms in Mars and Ocean Worlds analog environments, and are detectable with multiple techniques, including Raman spectroscopy. In this project, we aim to investigate the detectability of carotenoid pigments with different spectroscopic methods to inform future instrument selection. We compare the spectra of five unaltered carotenoids, two model compounds, and carotenoid-forming archaeon with visible and deep UV Raman spectroscopy and UVVis absorption spectrophotometry. We then use one model pigment, beta-carotene, to evaluate the likelihood that unique spectral properties of carotenoids, or their refractory byproducts, would be preserved and detectable on a remote planetary surface by exposing it to simulated conditions for Mars. Sample Acquisition. Pigments betacarotene, lutein, zeaxanthin, astaxanthin, and lycopene were purchased from Sigma Aldrich. Halobacterium salinarum NRC-1 was acquired from Carlina Biological and grown in Halobacterium media. Mineral salts including sodium sulfate, sodium carbonate, and halite were used to form matrices in which the beta-carotene was embedded before exposure. Pigment-mineral mixes were at a 1:10 ratio in water. Analytical Techniques. Deep UV Raman data were collected on a custom laboratory mapping spectrometer called MOBIUS (Mineral and Organic Based Investigations using Ultraviolet Spectroscopy), which is an analog to the SHERLOC instrument on the Mars 2020 Perseverance rover (Bhartia et al. 2021). It features a 248.56 nm NeCu pulsed laser, liquid nitrogen-cooled detector, and tunable optical setup. Visible Raman data were collected using a Horiba Jobin Yvon LabRam HR spectrometer with a frequencydoubled Nd:YAG laser (532 nm) and a HeNe laser (633 nm). A VWR 6300 PC UV/Visible Spectrophotometer was used to collect absorption data for carotenoid solutions, model compounds, and solvents in UVpermissible capped cuvettes. Data were collected from 190-1100 nm at 1 nm increments. All spectral data were analyzed using Igor Pro 9 (Wavemetrics). Irradiation. We used a vacuum chamber equipped with a cryostat and a flood electron gun to simulate Martian surface temperatures, low pressures, and ionizing radiation (10keV, 10μA for 6h at 200K for our initial tests). The samples were prepared by drying the pigment-mineral mix onto polished metal tabs, then mounted on the cryostat for processing. Samples were then analyzed directly on the tabs after exposure. Results: In comparing the visible and deep UV Raman spectra of unaltered pigments, we found that they differed drastically. Carotenoids are often studied with visible Raman and typically have peaks at 1525 cm-1 and 1157 cm-1, due to the stretching of the C=C and C-C bonds in the polyene structure. However, in deep UV, the strongest feature is at ~1630 cm-1 and is broad, possibly indicating that multiple peaks are forming this feature. This stark difference is likely due to different preresonant enhancement effects. The UV-Vis results show that there is an absorption band in the deep UV <300 nm, which supports the hypothesis that the 248.6 nm excitation is interrogating another aspect of carotenoids than visible Raman. Our preliminary exposure tests indicated that pigments – even without minerals present - were largely unaltered in the applied conditions, with only a slight broadening in the primary polyene peaks apparent in the visible Raman data. Figure 1. A) Visible vs. deep UV Raman spectra of unaltered beta carotene. B) Schematic of exposure. Conclusions: Our results to date indicate that deep UV and visible Raman spectroscopy, both techniques with planetary mission heritage from Mars 2020 (Wiens et al. 2021, Bhartia et al. 2021), may be used in a complementary manner to observe carotenoids. In addition, we find that beta-carotene is largely resistant to our current exposure conditions, though there may be some amount of amorphization of the material which could cause the broadening of the peaks at 1525 and 1157 cm-1. As a next step, we aim to increase the dosage and duration of exposure to observe degradation of the parent pigment, possibly add UV as a factor via an Ar mini-arc UV lamp and use GC-MS to characterize possible degradation products.

pigments↗