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At least 19 records

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↗

Algorithmic Classification of Raman Spectra Biosignatures: Improving Life Detection Confidence

“Agnostic” biosignatures – indicators of life (or the absence of life), independent of a particular biochemistry – are increasingly considered a high standard for life detection. The Ladder of Life Detection (2018) called for investigating how combinations of independent and different potential biosignatures affect confidence. To address this gap, statistical classification of elemental abundances, isotopic fractionation, and reflectance spectroscopy (VNIR) has been implemented. Raman spectroscopy, highly desirable due to its wide availability, has the potential to improve this predictive power. This work implemented biosignature classification algorithms on Raman data alone, in preparation for combination with the other data types. Raman spectroscopy data was collected from published databases and papers as part of a manually curated dataset of “indicative” and “non-indicative of life” samples. These currently include 61 non-indicative samples (meteorites, magnetite); 3 indicative living samples (bacteria); 20 indicative non-living samples (chalk, bone); and 12 indicative mixed (with non-indicative material) samples (soil, microbial mats). Laboratory work is ongoing to characterize additional samples, particularly a greater breadth of mixed systems. Spectra were interpolated, filtered with the Savitzsky-Golay filter, and de-noised. For a preliminary examination, agnostic features were manually extracted including mean intensity, number of peaks, and mean peak width. Different peak prominences and filtering polynomials were used to refine features. Classification algorithms were implemented: k-nearest neighbors (KNN), logistic regression (LR), linear support vector machines (SVM), random forest (RF), Gaussian naïve bayes (GNB). Lastly, Monte Carlo simulations on 1,000 50%-train-test-splits were used to validate classification performance and feature significance. The preliminary feature set achieved its highest AUC of 0.52 with LR, with no strongly discriminatory features. Work to improve feature extraction, such as through deep learning with back propagation, is planned. In future work, the Raman data will be combined with the other data types, and potentially new data types such as enantiomeric excess. This project was partially supported through the NASA Ames Project EXcellence (APEX) incubator program.

Astrobiology↗

Reduction of Raman Spectroscopy Data for H2-CO2-Air Tubular Flame Measurements

An approach of reducing spontaneous Raman spectroscopy data, based on the matrix inversion method which logically removes undesired sources of the Raman scattering signals including cross-talk due to the signals from other species, is discussed. The approach contains extensive calibration of temperature-dependent system response. The Raman spectra of several cold and hot calibration flames and their resulting calibration matrix are elaborated. The structure of H2-CO2-air tubular flames, in terms of major species (CO2, O2, N2, H2O, and H2) concentrations and temperature, was successfully measured with the optical technique. The Raman spectra data used in this study are taken from a uniquely designed experimental apparatus – a tubular burner and Raman spectroscopy system at Vanderbilt University. The characteristic uncertainties for chemical species are approximately ±2% by mole fraction for hot products and ±0.5% for room temperature reactants. The approach described here for hydrogen/air tubular flames may be adapted to hydrocarbon/air tubular flames when other necessary major species, for example, CH4 and CO for methane/air tubular flame, are considered in the whole process.

Raman Spectroscopy↗

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↗

Remote sensing of subsurface water temperature by laser Raman spectroscopy

This paper describes experimental remote sensing of subsurface water temperature using the Raman spectroscopic technique. By the use of a pulsed laser and range gating detection techniques, Raman scattering is analyzed as a function of depth in a radar-like echo mode, and thus subsurface profiles of temperature and transmission are obtained. Experiments are described in which Raman data using polarization spectroscopy has been obtained from a ship as a function of depth in ocean water near Grand Bahama Island. A spectral temperature accuracy of + or - 1 C has been obtained from this data in the first two optical attenuation lengths. Raman data obtained from ocean water using the NASA airborne oceanographic lidar is also presented.

Leonard, D. A.↗

Plume Characterization of a Laboratory Model 22 N GPIM Thruster via High-Frequency Raman Spectroscopy

The Green Propellant Infusion Mission (GPIM) will demonstrate the capability of a green propulsion system, specifically, one using the monopropellant, AF-M315E. One of the risks identified for GPIM is potential contamination of sensitive areas of the spacecraft from the effluents in the plumes of AF-M315E thrusters. Plume characterization of a laboratory-model 22 N thruster via optical diagnostics was conducted at NASA GRC in a space-simulated environment. A high-frequency pulsed laser was coupled with an electron-multiplied ICCD camera to perform Raman spectroscopy in the near-field, low-pressure plume. The Raman data yielded plume constituents and temperatures over a range of thruster chamber pressures and as a function of thruster (catalyst) operating time. Schlieren images of the near-field plume enabled calculation of plume velocities and revealed general plume structure of the otherwise invisible plume. The measured velocities are compared to those predicted by a two-dimensional, kinetic model. Trends in data and numerical results are presented from catalyst mid-life to end-of-life. The results of this investigation were coupled with the Raman and Schlieren data to provide an anchor for plume impingement analysis presented in a companion paper. The results of both analyses will be used to improve understanding of the nature of AF-M315E plumes and their impacts to GPIM and other future missions.

Raman Spectroscopy↗

Raman determination of layer stresses and strains for heterostructures and its application to the cubic SiC/Si system

A set of formulas for a generalized axial stress in diamond and zinc-blende semiconductors under axial stress is derived to calculate stress-related Raman shifts. By analyzing known Raman data on cubic SiC under hydrostatic pressures, one of the Raman-stress coefficients was obtained, and the existing elastic stiffness constants of cubic SiC were optimized. A method for calculating the stress and strain in SiC films on (100) Si is proposed. It is suggested that the stress and strain expressions and the method of the stress and strain determinations in heterostructures are quite general and may be used for other systems.

Feng, Z. C.↗

The application of laser-Raman light scattering to the determination of sulfate in sea and estuarine waters

Laser-Raman light scattering is a technique for determining sulfate concentrations in sea and estuarine waters with apparently none of the interferences inherent in the gravimetric and titrametric methods. The Raman measurement involved the ratioing of the peak heights of an unknown sulfate concentration and a nitrate internal standard. This ratio was used to calculate the unknown sulfate concentration from a standard curve. The standard curve was derived from the Raman data on prepared nitrate-sulfate solutions. At the 99.7% confidence level, the accuracy of the Raman technique was 7 to 8.6 percent over the concentration range of the standard curve. The sulfate analyses of water samples collected at the mouth of the James River, Hampton, Virginia, demonstrated that in most cases sulfate had a constant concentration relative to salinity in this area.

Bandy, A. R.↗

Atmospheric Temperature from Raman Scattering

Raman scattering signatures are functions of the scattering-gas temperature, and are therefore of potential use for practical atmospheric temperature probes. The method described uses either ratios of pure rotational Raman scattering intensities for air utilizing various spectral bandpasses, or, alternatively, ratios of air-rotational to nitrogen-vibrational scattering intensities. Three aspects of work relating to the development of such probes are discussed in this presentation: (1) fundamental absolute Raman data, (2) construction of air spectra from these data, and (3) temperature-sensitivity of the signature. The fundamental data described are the absolute rotational and vibrational scattering cross sections. Recent measurements in this laboratory of rotational cross sections for N2, O2, and CO2 are emphasized, as are their use in predicting absolute magnitudes of Raman scattering signals. Next is described the computation of air rotational Raman spectra as a function of temperature calculated through use of the experimentally-measured cross sections. The spectra are based additively upon nitrogen and oxygen contributions, since pure rotational Raman scattering from water vapor is very weak. Finally, the sensitivity of the scattering intensity ratios to temperature is explored as a function of choice of spectral bandpass for the monitored rotational Raman scattering. Various compromises will be discussed which must be made in choosing bandpasses appropriate for specific purposes and experimental conditions.

Lapp, M.↗

Characterization of NU-LHT-4M Lunar Regolith Simulant Using Different Raman Configurations

As much as possible, structures to help sustain a long-term human presence on the moon will be constructed via in-situ resource utilization (ISRU) from lunar regolith. Various processes have been proposed to make lunar regolith-based construction materials, but one complication is that the lunar regolith is relatively complex in terms of composition and can vary quite significantly from one site to another. Some of these methods to make lunar regolith-based construction materials are quite sensitive to the composition and so in-situ methods for evaluating the composition of the lunar regolith could be critical. Various analytical instrumentation has been proposed for in-situ characterization of the composition of regolith on planetary bodies. Raman spectroscopy has been suggested and has some advantages over other in-situ techniques, such as potential for relatively high spatial resolution, direct determination of the mineralogy (while other methods may only infer the mineralogy), nondestructive analysis, relatively simple instrument configurations, and minimal sample preparation/handling. For example, Raman instrumentation has already been deployed in rover-based missions to Mars. Previously, we developed the Standoff Ultracompact Micro-Raman Sensor (SUCR), which is a portable Raman spectroscopy instrument capable to be integrated into a rover or onto a lander. Here, we present work on Raman spectroscopy measurements of NU-LHT-4M lunar simulant using three different Raman instruments with different configurations for collecting Raman data with the goal to explore the effect of these different configurations on the results, especially for use in a lunar environment.

Raman Spectroscopy↗

Simultaneous Conoscopic Holography and Raman Spectroscopy

A new instrument was developed for chemical characterization of surfaces that combines the analytical power of Raman spectroscopy with the three-dimensional topographic information provided by conoscopic holography. The figure schematically depicts the proposed hybrid instrument. The output of the conoscopic holographic portion of the instrument is a topographical map of the surface; the output of the Raman portion of the instrument is hyperspectral Raman data, from which the chemical and/or biological composition of the surface would be deduced. By virtue of the basic principles of design and operation of the instrument, the hyperspectral image data would be inherently spatially registered with the topographical data. In conoscopic holography, the object and reference beams of classical holography are replaced by the ordinary and extraordinary components generated by a single beam traveling through a birefringent, uniaxial crystal. In the basic conoscopic configuration, a laser light is projected onto a specimen and the resulting illuminated spot becomes a point source of diffuse light that propagates in every direction. The laser beam is rasterscanned in two dimensions (x and y) perpendicular to the beam axis (z), and at each x,y location, the pattern of interference between the ordinary and extraordinary rays is recorded. The recorded interferogram constitutes the conoscopic hologram. Of particular significance for the proposed instrument is that the conoscopic hologram contains information on the z coordinate (height) of the illuminated surface spot. Hence, a topographical map of the specimen is constructed point-by-point by rastering the laser beam in the x and y directions and correlating the x and y coordinates with the z information obtained from the interferograms. Conoscopic imaging is an established method, and conoscopic laboratory instruments for surface metrology are commercially available. In Raman spectroscopy of a surface, one measures the spectrum of laser light scattered inelastically from a laser-illuminated spot on the surface. The wavelengths of the inelastically scattered light differ from that of the incident laser beam by amounts that correspond to the energies of molecular vibrations. The resulting vibrational spectrum can be used to identify the molecules. Raman spectroscopy is a standard laboratory technique for identifying mineralogical, biological, and other specific chemical compositions.

Schramm, Harry F.↗

Raman scattering from rapid thermally annealed tungsten silicide

Raman scattering as a technique for studying the formation of tungsten silicide is presented. The tungsten silicide films have been formed by rapid thermal annealing of thin tungsten films sputter deposited on silicon substrates. The Raman data are interpreted by using data from resistivity measurements, Auger and Rutherford backscattering measurements, and scanning electron microscopy.

Kumar, Sandeep↗

Raman structural studies of the nickel electrode

The objectives of this investigation have been to define the structures of charged active mass, discharged active mass, and related precursor materials (alpha-phases), with the purpose of better understanding the chemical and electrochemical reactions, including failure mechanisms and cobalt incorporation, so that the nickel electrode may be improved. Although our primary tool has been Raman spectroscopy, the structural conclusions drawn from the Raman data have been supported and augmented by three other analysis methods: infrared spectroscopy, powder X-ray Diffraction (XRD), and x-ray absorption spectroscopy (in particular EXAFS, Extended X-ray Absorption Fine Structure spectroscopy).

Cornilsen, Bahne C.↗

Electrochemical Characterization of Carbon Nanotubes for Fuel Cell MEA's

Single-walled and multi-walled carbon nanotubes from different sources have been evaluated before and after sonication to identify structural differences and evaluate electrochemical performance. Raman spectral analysis and cyclic voltammetry in situ with QCM were the principle means of evaluating the tubes. The raman data indicates that sonication in toluene modifies the structural properties of the nanotubes. Sonication also affects the electrochemical performance of single-walled nanotubes and the multi-walled tubes differently. The characterization of different types of carbon nanotubes leads up to identifying a potential candidate for incorporating carbon nanotubes for fuel cell MEA structures.

Panagaris, Jael↗

Evaluation and Applications of Multi-Instrument Boundary-Layer Thermodynamic Retrievals

Recent reports have highlighted the need for improved observations of the boundary layer. In this study, we explore the combination of ground-based active and passive remote sensors deployed for thermodynamic profiling to analyze various boundary-layer observation strategies. Optimal-estimation retrievals of thermodynamic profiles from Atmospheric Emitted Radiance Interferometer (AERI) observed spectral radiance are compared with and without the addition of active sensor observations from a May–June 2017 observation period at the Atmospheric Radiation Measurement–Southern Great Plains Site. In all, three separate thermodynamic retrievals are considered here: retrievals including AERI data only, retrievals including AERI data and Vaisala water vapour differential absorption lidar data, and retrievals including AERI data and Raman lidar data. First, the three retrievals are compared to each other and to reference radiosonde data over the full observation period to get a bulk understanding of their differences and characterize the impact of clouds on these retrieved profiles. These analyses show that the most significant differences are in the water vapour field, where the active sensors are better able to represent the moisture gradient in the entrainment zone near boundary layer top. We also explore how differences in retrievals may impact results of applied analyses including land–atmosphere coupling, convection indices, and severe storm environmental characterization. Overall, adding active sensors to the optimal-estimation retrieval showed some added information, particularly in the moisture field. Given the costs of such platforms, the value of that added information must be weighed for the application at hand.

boundary-layer observation↗

Collisional excitation of CO by H2O - An astrophysicist's guide to obtaining rate constants from coherent anti-Stokes Raman line shape data

Rate constants for excitation of CO by collisions with H2O are needed to understand recent observations of comet spectra. These collision rates are closely related to spectral line shape parameters, especially those for Raman Q-branch spectra. Because such spectra have become quite important for thermometry applications, much effort has been invested in understanding this process. Although it is not generally possible to extract state-to-state rate constants directly from the data as there are too many unknowns, if the matrix of state-to-state rates can be expressed in terms of a rate-law model which depends only on rotational quantum numbers plus a few parameters, the parameters can be determined from the data; this has been done with some success for many systems, especially those relevant to combustion processes. Although such an analysis has not yet been done for CO-H2O, this system is expected to behave similarly to N2-H2O which has been well studies; modifications of parameters for the latter system are suggested which should provide a reasonable description of rate constants for the former.

Green, Sheldon↗

Processing Raman Spectra of High-Pressure Hydrogen Flames

The Raman Code automates the analysis of laser-Raman-spectroscopy data for diagnosis of combustion at high pressure. On the basis of the theory of molecular spectroscopy, the software calculates the rovibrational and pure rotational Raman spectra of H2, O2, N2, and H2O in hydrogen/air flames at given temperatures and pressures. Given a set of Raman spectral data from measurements on a given flame and results from the aforementioned calculations, the software calculates the thermodynamic temperature and number densities of the aforementioned species. The software accounts for collisional spectral-line-broadening effects at pressures up to 60 bar (6 MPa). The line-broadening effects increase with pressure and thereby complicate the analysis. The software also corrects for spectral interference ("cross-talk") among the various chemical species. In the absence of such correction, the cross-talk is a significant source of error in temperatures and number densities. This is the first known comprehensive computer code that, when used in conjunction with a spectral calibration database, can process Raman-scattering spectral data from high-pressure hydrogen/air flames to obtain temperatures accurate to within 10 K and chemical-species number densities accurate to within 2 percent.

Nguyen, Quang-Viet↗