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DOE OSTI2025

Machine Learning in the Context of Laser-Induced Breakdown Spectroscopy

The integration of machine learning (ML) with Laser-Induced Breakdown Spectroscopy (LIBS) has revolutionized the analytical capabilities of LIBS. The combi-nation of both methods enables more accurate and efficient data analysis. While LIBS itself is a powerful technique for elemental analysis, the vast amount of spectral data it generates can be hard to interpret. Machine learning addresses these challenges by leveraging algorithms that can learn from data, identify patterns, and make predictions without explicit programming for the interpretation of each specific task. In LIBS application, ML techniques are used to enhance various analytical processes. For example, ML algorithms can classify materials based on their spectral fingerprints, predict the concentration of elements in a sample, and identify underlying patterns within complex datasets. Here, this application improves the precision of LIBS analyses while significantly reducing the time required for data processing and interpretation. In this chapter, the fundamental concepts of ML will be discussed first. Following this, the process of data splitting and the importance of feature selection will be examined. Several machine learning methods will then be closely examined, exploring how each can benefit LIBS analysis and highlighting their respective advantages and shortcomings. This structured approach will provide a comprehensive understanding of the integration of ML in the context of LIBS analysis.

47 OTHER INSTRUMENTATION↗

DOE OSTI2024

Rupture Jumping and Seismic Complexity in Models of Earthquake Cycles for Fault Stepovers with Off-Fault Plasticity

ABSTRACT Fault stepovers are prime examples of geometric complexity in natural fault zones that may affect seismic hazard by determining whether an earthquake rupture continues propagating or abruptly stops. However, the long-term pattern of seismicity near-fault stepovers and underlying mechanisms of rupture jumping in the context of earthquake cycles are rarely studied. Leveraging a hybrid numerical scheme combining the finite element and the spectral boundary integral methods, FEBE, we carry out fully dynamic simulations of sequences of earthquakes and aseismic slip for both compressive and tensile stepovers with off-fault plasticity. We consider a rate-and-state friction law for the fault friction and pressure-sensitive Drucker–Prager plasticity for the off-fault bulk response. We observe that the accumulation of plastic deformation, an indication of off-fault damage, is significantly different in the two cases, with more plastic deformation projected in the overlapping region for the tensile stepover. The seismic pattern for a tensile stepover is more complex than for a compressive stepover, and incorporating plasticity also increases complexity, relative to the elastic case. A tensile stepover with off-fault plasticity shows rupture segmentation, temporal clustering, and frequent rupture jumping from one fault to another. These results shed light on possible mechanisms of rupture jumping in fault stepovers as well as the long-term evolution of the fault zone.

Geochemistry & Geophysics↗

DOE OSTI2021

A Method to Extract Spatially Resolved Polycyclic Aromatic Hydrocarbon Emission from Spitzer Spectra: Application to M51

The mid-infrared spectrum contains rich diagnostics to probe the physical properties of galaxies, among which the pervasive emission features from polycyclic aromatic hydrocarbons (PAHs) offer promising means of estimating the star formation rate (SFR) relatively immune from dust extinction. This paper investigates the effectiveness of PAH emission as a SFR indicator on subkiloparsec scales by studying the Spitzer/IRS mapping-mode observations of the nearby grand-design spiral galaxy M51. We present a new approach of analyzing the spatial elements of the spectral data cube that simultaneously maximizes spatial resolution and spatial coverage, while yielding reliable measurements of the total, integrated 5–20 μm PAH emission. We devise a strategy of extracting robust PAH emission using spectra with only partial spectral coverage, complementing missing spectral regions with properly combined mid-infrared photometry. We find that in M51 the PAH emission correlates tightly with the extinction-corrected far-ultraviolet, near-ultraviolet, and Hα emission, from scales of ∼0.4 kpc close to the nucleus to 6 kpc out in the disk of the galaxy, indicating that PAH serves as an excellent tracer of SFR over a wide range of galactic environments. But regional differences exist. Close to the active nucleus of M51 the 6.2 μm feature is weaker, and the overall level of PAH emission is suppressed. The spiral arms and the central star-forming region of the galaxy emit stronger 7.7 and 8.6 μm PAH features than the inter-arm regions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Chemical Compositions of Red Giant Stars from Habitable Zone Planet Finder Spectroscopy

We have used the Habitable Zone Planet Finder (HPF) to gather high-resolution, high signal-to-noise near-infrared spectra of 13 field red horizontal branch (RHB) stars, one open cluster giant, and one very metal-poor halo red giant. The HPF spectra cover the 0.81–1.28 μm wavelength range of the zyJ bands, partially filling the gap between the optical (0.4–1.0 μm) and infrared (1.5–2.4 μm) spectra already available for the program stars. We derive abundances of 17 species from LTE-based computations involving equivalent widths and spectrum syntheses, and estimate abundance corrections for the species that are most affected by departures from LTE in RHB stars. Generally good agreement is found between HPF-based metallicities and abundance ratios and those from the optical and infrared spectral regions. Light element transitions dominate the HPF spectra of these red giants, and HPF data can be used to derive abundances from species with poor or no representation in optical spectra (e.g., C i, P i, S i, K i). Attention is drawn to the HPF abundances in two field solar-metallicity RHB stars of special interest: one with an extreme carbon isotope ratio, and one with a rare, very large lithium content. The latter star is unique in our sample in exhibiting very strong He i 10830 Å absorption. The abundances of the open cluster giant concur with those derived from other wavelength regions. Detections of C i and S i in HD 122563 are reported, yielding the lowest metallicity determination of [S/Fe] from more than one multiplet.

47 OTHER INSTRUMENTATION↗

NASA NTRS1973

An interpretation of a geologic map of Fannin County, Texas, prepared by ADP techniques from ERTS MSS data

Multispectral scanner data, collected by ERTS-1 from an area in northeast Texas underlain by structurally simple cretaceous sedimentary rocks, were analyzed using several automatic data processing techniques. Training areas for the computer analysis were selected in three ways using: (1) an unsupervised classifier, (2) the unsupervised classifier to further refine training areas, and (3) available ground information. The first two methods utilize the capability of the unsupervised classifier to the unsupervised classifier to group resolution elements with similar spectral properties. With the imagery produced by these procedures, several geologic features can be identified. The most easily recognizable features are streams and other water bodies. The approximate location of contacts between several rock units can be mapped.

Henderson, J. A., Jr.↗

NASA NTRS1980

Mechanisms of nitrogen heterocycle influence on turbine fuel stability

Lewis bases were extracted from a Utah COED syncrude via ligand exchange. Addition of this extract to Jet A at levels as low as 5 ppm N produced deterioration of stability in both JFTOT and accelerated storage tests (7 days at 394 K with 13:1air to fuel ratio). Comparable effects on Jet A stability were obtained by addition of pyridine and quinoline, while pyrrole and indole were less detrimental at the same concentration level. The weight of deposit produced accelerated storage tests was found to be proportional to the concentration of added nitrogen compound. Over the narrow temperature range accessible with the experimental method, Arrhenius plots obtained by assuming specific rate to be proportional to the weight of material deposited in seven days exhibit greater slopes in the presence of those nitrogen compounds producing the greater deposition rates. It is shown that despite variation in appearance the elemental composition and spectral characteristics of the deposits are unaffected by addition of the nitrogen compounds. The linearity of the Arrhenius plots and of a plot of Arrhenius slope versus intercept for all the compounds suggests a constancy of mechanism over the range of temperature and heterocycles studied.

Daniel, S. R.↗

NASA NTRS1988

The analysis of spectra of novae taken near maximum

A project to analyze ultraviolet spectra of novae obtained at or near maximum optical light is presented. These spectra are characterized by a relatively cool continuum with superimposed permitted emission lines from ions such as Fe II, Mg II, and Si II. Spectra obtained late in the outburst show only emission lines from highly ionized species and in many cases these are forbidden lines. The ultraviolet data will be used with calculations of spherical, expanding, stellar atmospheres for novae to determine elemental abundances by spectral line synthesis. This method is extremely sensitive to the abundances and completely independent of the nebular analyses usually used to obtain novae abundances.

Stryker, L. L.↗

NASA NTRS1988

PIA update: Correlation analyses of mass spectra

The PIA instrument aboard the Giotto spacecraft (a time of flight spectrometer) has been presented elsewhere. The mass spectra used in this analysis were decoded and mass numbers assigned according to the presence of carbon and silver, using the global values for these elements in their spectral absence. The results presented here were obtained using a frequency of occurrence based on analysis which correlated how often mass numbers appear in the mass spectra and which mass numbers tend to occur together in the same spectra; no amplitude information is utilized. The data are presented as plots of mass vs coincident mass for different subsets of the PIA data set, with both axes having units of atomic mass. Frequency contours are plotted at approximately five percent contour intervals, relative to the maximum AMU occurrence in that plot. The plots presented are symmetrical about the matrix diagonal, i.e., every mass is coincident with itself in a given spectra.

Mason, L. W.↗

NASA NTRS1989

Numerical algorithms for computations of feedback laws arising in control of flexible systems

Several continuous models will be examined, which describe flexible structures with boundary or point control/observation. Issues related to the computation of feedback laws are examined (particularly stabilizing feedbacks) with sensors and actuators located either on the boundary or at specific point locations of the structure. One of the main difficulties is due to the great sensitivity of the system (hyperbolic systems with unbounded control actions), with respect to perturbations caused either by uncertainty of the model or by the errors introduced in implementing numerical algorithms. Thus, special care must be taken in the choice of the appropriate numerical schemes which eventually lead to implementable finite dimensional solutions. Finite dimensional algorithms are constructed on a basis of a priority analysis of the properties of the original, continuous (infinite diversional) systems with the following criteria in mind: (1) convergence and stability of the algorithms and (2) robustness (reasonable insensitivity with respect to the unknown parameters of the systems). Examples with mixed finite element methods and spectral methods are provided.

Lasiecka, Irena↗

NASA NTRS1991

A drag measurement technique for free piston shock tunnels

A new technique is described for measuring drag with 100-microsecond rise time on a nonlifting model in a free piston shock tunnel. The technique involves interpretation of the stress waves propagating within the model and its support. A finite element representation and spectral methods are used to obtain a mean square optimal estimate of the time history of the aerodynamic loading. Thus, drag is measured instantaneously and the previous restriction caused by the mechanical time constant of balances is overcome. The effectiveness of the balance is demonstrated by measuring the drag on cones with 5 and 15 deg semi-vertex angles in nominally Mach 5.6 flow with stagnation enthalpies from 2.6 to 33 MJ/kg.

Sanderson, S. R.↗

NASA NTRS2003

Development of a High-Pressure Gaseous Burner for Calibrating Optical Diagnostic Techniques

In this work-in-progress report, we show the development of a unique high-pressure burner facility (up to 60 atm) that provides steady, reproducible premixed flames with high precision, while having the capability to use multiple fuel/oxidizer combinations. The highpressure facility has four optical access ports for applying different laser diagnostic techniques and will provide a standard reference flame for the development of a spectroscopic database in high-pressure/temperature conditions. Spontaneous Raman scattering (SRS) was the first diagnostic applied, and was used to successfully probe premixed hydrogen-air flames generated in the facility using a novel multi-jet micro-premixed array burner element. The SRS spectral data include contributions from H2, N2, O2, and H2O and were collected over a wide range of equivalence ratios ranging from 0.16 to 4.9 at an initial pressure of 10-atm via a spatially resolved point SRS measurement with a high-performance optical system. Temperatures in fuel-lean to stoichiometric conditions were determined from the ratio of the Stokes to anti-Stokes scattering of the Q-branch of N2, and those in fuel-rich conditions via the rotational temperature of H2. The SRS derived temperatures using both techniques were consistent and indicated that the flame temperature was approximately 500 K below that predicted by adiabatic equilibrium, indicating a large amount of heat-loss at the measurement zone. The integrated vibrational SRS signals show that SRS provides quantitative number density data in high-pressure H2-air flames.

Kojima, Jun↗

NASA NTRS2011

PING Gamma Ray and Neutron Measurements of a Meter-Sized Carbonaceous Asteroid Analog

Determining the elemental composition of carbonaceous (spectral type C) asteroids is still one of the basic problems when studying these objects. The only main source of elemental composition information for asteroids is from their optical, NIR and IR properties, which include their spectral reflectance characteristics, albedo, polarization, and the comparison of optical spectroscopy with meteorite groups corresponding to asteroids of every spectral type. Unfortunately, these sources reflect observations from widely contrasting spatial scales that presently yield a void in the continuum of microscopic and macroscopic evidence, a lack of in situ measurement confirmation, and require deeper sensing techniques to discern the nature of these asteroids. The Probing In situ with Neutrons and Gamma rays (PING) instrument is ideally suited to address this problem because it can be used to determine the bulk elemental composition, H and C content, the average atomic weight and density of the surface and subsurface layers of C-type asteroids, and can provide measurements used to determine the difference between and distinguish between different types of asteroids. We are currently developing the PING instrument that combines gamma ray and neutron detectors with a 14 Me V pulsed neutron generator to determine the in-situ bulk elemental abundances and geochemistry of C-type asteroids with a spatial resolution of 1 m down to depths of tens of cm to 1 m. One aspect of the current work includes experimentally testing and optimizing PING on a known meter-sized Columbia River basalt C-type asteroid analog sample that has a similar composition and the same neutron response as that of a C-type asteroid. An important part of this effort focuses on utilizing timing measurements to isolate gamma rays produced by neutron inelastic scattering, neutron capture and delayed activation processes. Separating the gamma ray spectra by nuclear processes results in higher precision and sensitivity elemental composition measurements. Using gated data acquisition techniques allows for the unambiguous identification of gamma ray lines from different isotopes and nuclear processes, especially in situations when limited detector resolution results in overlapping gamma ray lines that cannot be individually resolved. In this paper, we will present the PING basalt layering experimental data, taken at the test facility at NASA Goddard Space Flight Center using the time tagged event-by-event data analysis technique, compared to our MCNPX computer simulation results for the C-type asteroid and basalt layering simulant models. Comparison of these data will show the advantages, validity, and measurement sensitivity of PING's nuclear interrogation methods to obtain more precise and sensitive in situ bulk elemental composition and density measurements of the subsurface of asteroids.

Bodnarik, J.↗

DOE OSTI2022

Constraints on ion velocity distributions from fusion product spectroscopy

Abstract Recent inertial confinement fusion experiments have shown primary fusion spectral moments which are incompatible with a Maxwellian velocity distribution description. These results show that an ion kinetic description of the reacting ions is necessary. We develop a theoretical classification of non-Maxwellian ion velocity distributions using the spectral moments. At the mesoscopic level, a monoenergetic decomposition of the velocity distribution reveals there are constraints on the space of spectral moments accessible by isotropic distributions. General expressions for the directionally dependent spectral moments of anisotropic distributions are derived. At the macroscopic level, a distribution of fluid element velocities modifies the spectral moments in a constrained manner. Experimental observations can be compared to these constraints to identify the character and isotropy of the underlying reactant ion velocity distribution and determine if the plasma is hydrodynamic or kinetic.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2009

Spectrum Analyzers Incorporating Tunable WGM Resonators

A photonic instrument is proposed to boost the resolution for ultraviolet/ optical/infrared spectral analysis and spectral imaging allowing the detection of narrow (0.00007-to-0.07-picometer wavelength resolution range) optical spectral signatures of chemical elements in space and planetary atmospheres. The idea underlying the proposal is to exploit the advantageous spectral characteristics of whispering-gallery-mode (WGM) resonators to obtain spectral resolutions at least three orders of magnitude greater than those of optical spectrum analyzers now in use. Such high resolutions would enable measurement of spectral features that could not be resolved by prior instruments.

Savchenkov, Anatoliy↗

NASA NTRS2022

Full Spectrum Fitting Analysis of Bulk Elemental Composition Analyzer (BECA) Gamma Ray Data

The Bulk Elemental Composition Analyzer (BECA) is an instrument developed through NASA’s Development and Advancement of Lunar Instrumentation (DALI) program to measure the in situ bulk elemental composition of the lunar regolith from either a lander or rover platform. BECA uses active neutron and gamma ray spectroscopy to make these measurements and thus consists of a Pulsed Neutron Generator (PNG), a CeBr3 scintillator Gamma Ray Spectrometer (GRS), and two He-3 neutron detectors. As shown in Figure 1, the PNG emits 14.1 MeV neutrons that induce lunar materials to emit gamma rays with energies characteristic of the elements that produced them. The GRS measures the energy spectra of these gamma rays to identify the elements present and establish their absolute concentrations in the regolith. The analysis of BECA’s gamma ray spectral data yields quantitative elemental concentrations by mass (wt.%) in the material directly beneath the lunar lander or rover. A Compact Neutron Monitor (CNM) attached to the PNG precisely measures the output of 14.1 MeV neutrons to enable quantification of absolute elemental abundances.

Mauricio Ayllon Unzueta↗

NASA NTRS1988

Tuning and scanning control system for high resolution alexandrite lasers

An alexandrite laser is spectrally narrowed and tuned by the use of three optical elements. Each element provides a successively higher degree of spectral resolution. The digitally controlled tuning and scanning control servo system simultaneously positions all three optical elements to provide continuous high resolution laser spectral tuning. The user may select manual, single, or continuous modes of automated scanning of ranges up to 3.00/cm and at scan rates up to 3.85/cm/min. Scanning over an extended range of up to 9.999/cm may be achieved if the highest resolution optic is removed from the system. The control system is also capable of being remotely operated by another computer or controller via standard RS-232 serial data link.

Smith, James C.↗

NASA NTRS1988

Energy spectra of cosmic-ray nuclei from 50 to 2000 GeV per amu

A direct measurement of the elemental composition of cosmic rays up to energies of several TeV/amu was performed during the Spacelab 2 flight of the Space Shuttle. Results on the spectral shape for the elements C, O, Ne, Mg, Si, and Fe, obtained from this experiment, are presented. It was found that the C and O energy spectra retain a power-law spectrum in energy with an exponent Gamma of about 2.65. The Fe spectrum is flatter (Gamma of about 2.55) up to a particle energy of about 10 to the 14th eV, indicating a steady increase in the relative abundance of iron in cosmic rays up to this energy. The energy spectra of Ne, Mg, and Si are steeper than anticipated. This behavior is unexpected within current models of cosmic-ray acceleration.

Grunsfeld, John M.↗

DOE OSTI2020

Evaluation of analytical performance of double pulse laser-induced breakdown spectroscopy for the detection of rare earth elements

Double pulse laser-induced breakdown spectroscopy (DP-LIBS) in collinear configuration was demonstrated to enhance the signal intensity of three rare earth elements (REEs), Eu, Gd, Pr, and Y (Yttrium is included because of its similar chemical properties and occurrence in similar deposits as REE). Significant enhancement in spectral signals of all elements was observed with an aid of second laser. Two laser pulses of 1064 nm wavelength were employed in collinear geometry on the Pr 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , and Y 2 O 3 pellets to obtain emission spectra. For selected strong emission lines of Eu and Gd signal enhancement was found to be 3 to 7-fold and that for Y and Pr lines was observed to be 3 to 13-fold compared to single-pulse laser-induced breakdown spectroscopy (SP-LIBS). Role of inter-pulse delay between two pulses in DP-LIBS was found to be very crucial. Furthermore, while comparing selected ionic and neutral lines, ionic lines were found to have larger signal enhancement in DP-LIBS at the experimental conditions used in this study.

47 OTHER INSTRUMENTATION↗