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At least 631 records · Page 35
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NASA NTRSDate not supplied

Potential Discovery of Amphibole in Miller Range (MIL) 090292 via Raman Spectroscopy

Ungrouped carbonaceous chondrites have the potential to provide insights into processes on their parent bodies that may not be accessible through studying established groups. Miller Range (MIL) 090292 is an extensively aqueously altered ungrouped carbonaceous chondrite, which provides the potential to reveal new information about alteration processes on carbonaceous chondrite-like asteroids. The meteorite MIL090292 was initially classified as a CR1 chondrite. It experienced heavy aqueous alteration and, texturally, the meteorite is highly brecciated. MIL 090292 was reclassified as a C1 ungrouped chondrite after it was found that the Δ17O values of its magnetite grains do not plot along the CR mixing line. Furthermore, there is a lack of calcium carbonate grains in the sample, which are common in aqueously altered CRs –calcium is found in andradite and hedenbergite (which are not found in CRs) and phosphates. However, beyond this basic mineralogical information, there is a lack of knowledge about the petrogenetic history of the meteorite or its parent body.

Meteorite↗
NASA NTRSDate not supplied

Statistical Classification of Biosignature Information: Combining Elemental, Molecular, Reflectance, and Raman Data to Increase Life Detection Confidence

Planetary exploration missions seeking past or present signs of life carry not just a single instrument, but a suite. There is a need to study how these multiple data types can be combined to create “composite” biosignatures [1]. Algorithmic methods using existing data on living and non-living systems, though limited by the n = 1 of Earth, can nonetheless be informative. We assembled a database of 1277 measurements spanning 16 representative systems either indicative or non-indicative of life. Five classification (machine learning) methods were used on each individual data type, then on the entire set. This abstract summarizes the results; the data is described in more detail in [2], and methods in [3].

Biosignatures↗
NASA NTRSDate not supplied

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↗
NASA NTRS1993

Non-intrusive measurements in a rocket engine combustor

In recent years analytical tools to characterize combustor flow have been developed in order to support design. To facilitate anchoring of combustion related physical models and the CFD codes in which they are incorporated, considerable development and application of non-intrusive combustion diagnostic capabilities has occurred. Raman spectroscopy can be used to simultaneously detect all polyatomic molecules present in significant concentrations and to determine gas temperature. This is because all molecules possess a distinct temperature dependent Raman spectrum. A multi-point diagnostic system for non-intrusive temperature and species profiling in rocket engines has been developed at Rocketdyne. In the present effort, the system has been undergoing validation for application to rocket engine component testing. A 4 inch diameter windowed combustor with a coaxial gas-gas injector was chosen for this series of validation experiments. Initially an excimer-pumped tunable dye laser and later a solid state Nd-Yag laser served as excitation sources. The Raman signal was dispersed by a monochromator and detected by a gated, intensified Charged Coupled Device (CCD) array. Experiments were carried out prior to each series of hot fire tests to ensure that the Raman signal detected was due to a spontaneous rather than a stimulated Raman emission process. Over sixty hot fire tests were conducted during the first series of tests with the excimer/dye laser. All hot fire testing was at a mixture ratio of 0.5 and chamber pressures of approximately 100 and approximately 300 psia. The Raman spectra of hydrogen, water vapor and oxygen recorded during single element hot fire tests were reduced and analyzed. A significant achievement was the attainment of single shot Raman spectra in cold flow tests. Unfortunately, the single shot signal-to-noise ratio deteriorated to an unacceptable level during the hot fire testing. Attempts to obtain temperature data from the hydrogen Q1-branch profiles obtained in hot fire tests suggest that potentially complicating factors may render the approach of averaging data on the photodiode array invalid. A second series of hot fire tests was conducted with a 4 element coaxial injector using the Nd-Yag laser. A very compact and portable diagnostics set up was assembled for ease of alignment, relocation and flexibility. Measurements were made at several regions in the chamber in order to map concentration profiles. High spatial resolution and improved signal to noise characteristics were demonstrated.

Farhangi, S.↗
NASA NTRS1996

Trace Element Zoning and Incipient Metamictization in a Lunar Zircon: Application of Three Microprobe Techniques

We have determined major (Si, Zr, Hf), minor (Al, Y, Fe, P), and trace element (Ca, Sc, Ti, Ba, REE, Th, U) concentrations and Raman spectra of a zoned, 200 microns zircon grain in lunar sample 14161,7069, a quartz monzodiorite breccia collected at the Apollo 14 site. Analyses were obtained on a thin section in situ with an ion microprobe, an electron microprobe, and a laser Raman microprobe. The zircon grain is optically zoned in birefringence, a reflection of variable (incomplete) metamictization resulting from zo- nation in U and Th concentrations. Variations in the concentrations of U and Th correlate strongly with those of other high-field-strength trace elements and with changes in Raman spectral parameters. Concentrations of U and Th range from 21 to 55 ppm and 6 to 31 ppm, respectively, and correlate with lower Raman peak intensities, wider Raman peaks, and shifted Si-O peak positions. Concentrations of heavy rare earth elements range over a factor of three to four and correlate with intensities of fluorescence peaks. Correlated variations in trace element concentrations reflect the original magmatic differentiation of the parental melt approx. 4 b.y. ago. Degradation of the zircon structure, as reflected by the observed Raman spectral parameters, has occurred in this sample over a range of alpha-decay event dose from approx. 5.2 x 10(exp 14) to 1.4 x 10(exp 15) decay events per milligram of zircon, as calculated from the U and Th concentrations. This dose is well below the approx. 10(exp 16) events per milligram cumulative dose that causes complete metamictization and indicates that laser Raman microprobe spectroscopy is an analytical technique that is very sensitive to the radiation-induced damage in zircon.

Wopenka, Brigitte↗
NASA NTRS1999

Coherent Pump-Probe Interactions and Terahertz Intersubband Gain in Semiconductor Quantum Wells

In recent years there has been considerable interest in intersubband-transition-based infrared semiconductor quantum well (QW) lasers because of their potential applications. In the mid-infrared range, both electrically-injected quantum cascade lasers [1] and optically-pumped multiple QW lasers [2] have been experimentally realized. In these studies, optical gain is due to population inversion between the lasing subbands. It was also proposed that stimulated Raman scattering in QW systems can produce net infrared optical gain [3j. In such a nonlinear optical scheme, the appearance of optical gain that may lead to intersubband Raman lasers does not rely on the population inversion. Since, in tile resonant Raman process (Raman gain is the largest in this case), the pump field induces population redistribution among subbands in the QW s ystem, it seems that a realistic estimate of the optical gain has to include this effect. Perturbative calculations used in the previous work [3] may overestimate the Raman gain. In this paper we present a nonperturbative calculation of terahertz gain of optically-pumped semiconductor step quantum wells. Limiting optical transitions within the conduction band of QW, we solve the pump-field-induced nonequilibrium distribution function for each subband of the QW system from a set of coupled rate equations. Both intrasubband and intersubband relaxation processes in the quantum well system are included. Taking into account the coherent interactions between pump and THz (signal) waves, we we derive the susceptibility of the QW system for the THz field. For a GaAs/AlGaAs step QW, we calculate the Thz gain spectrum for different pump frequencies and intensities. Under moderately strong pumping (approximately 0.3 MW/sq cm), a significant THz gain (approximately 300/m) is predicted. It is also shown that the coherent wave interactions (resonant stimulated Raman processes) contribute significantly to the THz gain.

Liu, Ansheng↗