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At least 253 records · Page 14

A Mars 2020 Perseverance SuperCam Perspective on the Igneous Nature of the Máaz Formation at Jezero Crater, Mars

The Mars2020 Perseverance rover landed in Jezero crater in February 2020,and first encountered the Máaz formation (or Crater floor-fractured rough(Cf-fr) unit previously mapped based on orbital data[1]).In this study, we use data from the SuperCam instrument(SCAM) to show that the Máaz formation has an igneous origin. SuperCam is a remote-sensing instrument onboard Perseverance, and investigates the texture, mineralogy, and chemistry of rocks and soils, as well as atmospheric features [2,3]. SuperCam comprises the Remote Micro Imager (RMI) to provide high-resolution images, laser-induced breakdown spectroscopy (LIBS)to investigate the major and minor element chemistry of materials, Raman, and passive visible-near infrared (VISIR) spectroscopy to analyze the mineralogy of targets, and time-resolved luminescence spectroscopy (TRLS)to measure organic fluorescence and inorganic luminescence. In addition, the microphone (MIC) can constrain the rock hardness through measurements of the shockwave of LIBS shots. In this study, we use LIBS-based major-oxide compositions (MOC),quantified using the calibration in [2].

Mars 2020↗

Heating and Sampling Efficiency Evaluation for the Nephele Venus Cloud Sampling Mission Concept

Nephele [1] is a descent probe concept with a unique combination of entry (3D-CC+HEEET), sampling (flow-through passive impactors), and optics (laser-induced breakdown spectroscopy, or LIBS, and surface-enhanced Raman spectroscopy, or SERS), technologies with two key innovations (Figure 1). The first is the integration of the aerosol sampling inlet into the aeroshell body, allowing the possibility of sampling during passive descent without separation. The second is the use of the aerosol capture surface as an optical analysis substrate, allowing fast-cadence aerosol analysis via a dual optical spectrometer instead of mass spectrometry. Although this concept shares some features with other efforts such as Cupid’s Arrow [1] (single-body sample capture system), DAVINCI [2] and Venera-D [3] (use of an optical spectrometer), Nephele is unique in its physical integration of the sonde body, aerosol and gas sampler, and analysis instrumentation. This innovation is designed to eliminate the need for a controlled descent to achieve a detailed atmospheric aerosol transect, which offers in situ planetary science in a small spacecraft envelope. Aeroshell designs with inlets for free-falling sondes are well-understood, though not yet assessed for aerosol capture efficiency. A HEEET aeroshell with a specialized nose inlet material comprised of Carbon-Carbon is proposed for this mission concept.

Venus↗

Heating and Sampling Efficiency Evaluation for the Nephele Venus Cloud Sampling Mission Concept

Nephele is a descent probe concept with a unique combination of entry (3D-CC+HEEET), sampling (flow-through passive impactors), and optics (laser-induced breakdown spectroscopy, or LIBS, and surface-enhanced Raman spectroscopy, or SERS), technologies with two key innovations. The first is the integration of the aerosol sampling inlet into the aeroshell body, allowing the possibility of sampling during passive descent without separation. The second is the use of the aerosol capture surface as an optical analysis substrate, allowing fast-cadence aerosol analysis via a dual optical spectrometer instead of mass spectrometry. Although this concept shares some features with other efforts such as Cupid’s Arrow (single-body sample capture system), DAVINCI and Venera-D (use of an optical spectrometer), Nephele is unique in its physical integration of the sonde body, aerosol and gas sampler, and analysis instrumentation. This innovation is designed to eliminate the need for a controlled descent to achieve a detailed atmospheric aerosol transect, which offers in situ planetary science in a small spacecraft envelope. Aeroshell designs with inlets for free-falling sondes are well-understood, though not yet assessed for aerosol capture efficiency. A HEEET aeroshell with a specialized nose inlet material comprised of Carbon-Carbon is proposed for this mission concept.

Venus↗

Petrological Traverse of the Olivine Cumulate Séítah Formation at Jezero Crater, Mars: A Perspective From SuperCam Onboard Perseverance

Séítah is the stratigraphically lowest formation visited by Perseverance in the Jezero crater floor. We present the data obtained by SuperCam: texture by imagery, chemistry by Laser-Induced Breakdown Spectroscopy, and mineralogy by Supercam Visible and Infrared reflectance and Raman spectroscopy. The Séítah formation consists of igneous, weakly altered rocks dominated by millimeter-sized grains of olivine with the presence of low-Ca and high-Ca pyroxenes, and other primary minerals (e.g., plagioclase, Cr-Fe-Ti oxides, phosphates). Along a ∼140 m long section in Séítah, SuperCam analyses showed evidence of geochemical and mineralogical variations, from the contact with the overlying Máaz formation, going deeper in the formation. Bulk rock and olivine Mg#, grain size, olivine content increase gradually further from the contact. Along the section, olivine Mg# is not in equilibrium with the bulk rock Mg#, indicating local olivine accumulation. These observations are consistent with Séítah being the deep ultramafic member of a cumulate series derived from the fractional crystallization and slow cooling of the parent magma at depth. Possible magmatic processes and exhumation mechanisms of Séítah are discussed. Séítah rocks show some affinity with some rocks at Gusev crater, and with some Martian meteorites suggesting that such rocks are not rare on the surface of Mars. Séítah is part of the Nili Fossae regional olivine-carbonate unit observed from orbit. Future exploration of Perseverance on the rim and outside of the crater will help determine if the observations from the crater floor can be extrapolated to the whole unit or if this unit is composed of distinct sub-units with various origins.

Mars 2020↗

Mineral composition of Al-rich float rocks in Jezero crater as seen by Super-Cam

During its traverse across the Jezero crater floor and western fan, the Perseverance rover encountered > 4000 float rocks – of variable size (up to ~ 50 cm) scattered on the ground without apparent connection to the surrounding stratigraphy [1]. Analysis performed using the SuperCam instrument’s [2,3,4], Laser Induced Breakdown Spectroscopy (LIBS) revealed a high concentration of Al 2 O 3 , Cr, Ti and Ni [5], and very low of Fe, Mg, Ca and Na [5, 1]. SuperCam’s infrared reflectance spectroscopy (IRS, between 1.3 and 2.6 μm) showed the presence of Al-rich aqueous alteration minerals (characteristic absorption bands of kaolinite and Al-smectites at 1.4 and 2.2 μm) as well as some (likely Cr-) spinels, identified uthrough their broad asymmetric 2 μm band, responsible for the concavity of IR spectra. These mineral species alone do not fully account for the spectral shapes; hence, the objective is to further investigate spectral modeling to determine the most probable mineral assemblages. Here, we present the results of modeling 17 light-toned float rocks, up to Sol 924, complementary to [1].

C. Royer↗

High Precision and Spatial Resolution Chemical Interrogation of Planetary Materials Using fs-LA/LIBS in Tandem With Multi-Collector ICP-MS

Combining femtosecond laser ablation (fs-LA) with laser-induced breakdown spectroscopy (LIBS), together with multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS), can provide remarkable insights into the composition, structure, and therefore geologic history of planetary materials and their terrestrial analogs. Using the Applied Spectra iX-fs-Tandem LA-LIBS Instrument and the Nu SP1700 MC-ICP-MS housed within the Center for Isotope Cosmochemistry and Geochronology at NASA Johnson Space Center, we present preliminary tandem fs-LA-(MC)-ICP-MS/LIBS measurements of planetary analog materials. The synergistic integration of fs-LA-LIBS offers high spatial resolution elemental mapping, enabling the identification of microscale variations within samples. Simultaneously, the MC-ICP-MS can deliver precise isotopic analyses, and integrating the two datasets yields a wealth of geochemical information for a given sample. LA-based chemical mapping experiment designs are contingent on the information sought (i.e., quantitative, or semi-quantitative) and the preferred or available volume of material removed for the analysis. For example, occasionally, there are significant limitations in the depth of ablation due to the sample value, the amount of material available, or simply the need to coordinate with other in-situ techniques. In these limited sample scenarios, the “depth-controlled” chemical maps allow for precise post-mapping ion-polishing of the sample, while the isotopic and elemental maps can be used for targeting future analyses (e.g., conventional LA analyses, SIMS analyses, and micro milling for solution ICP-MS/TIMS). The emerging methodology will establish a powerful tool for investigation of astromaterials and materials returned by future planetary sample science missions.

Jacob B Setera↗

Multiple stage sorting

A material sorting system sorts materials utilizing multiple stages of classification and sorting, including a vision system that implements a machine learning system in order to identify or classify each of the materials, and Laser Induced Breakdown Spectroscopy to perform a subsequent classification and sorting of the remaining materials.

97 MATHEMATICS AND COMPUTING↗

Evaluation of Material Balance Approaches for Hanford Direct-Feed Low Activity Waste Processing - 20022

The Hanford Site has accumulated millions of gallons of tank waste from reprocessing spent fuel to recover plutonium, uranium, cesium, and strontium. The supernatant from the accumulated tank waste will be treated using a Direct Feed Low-Activity Waste approach. The supernatant will be treated to remove solids and cesium in the Tank-Side Cesium Removal process in the Hanford tank farm, then vitrified in a semi-batch process in the Hanford Waste Treatment and Immobilization Plant (WTP). Currently, each batch of feed is sampled at three locations prior to being fed to the melter: the feed qualification tank in the Hanford tank farm as well as the concentrate receipt vessel (CRV) and melter feed preparation vessel (MFPV) in the WTP. The feed qualification sample is taken from a large batch of accumulated feed, only two to three samples are expected each year. Approximately 275 samples from the CRVs and 1100 samples from the MFPV are expected each year. An evaluation was performed to determine if a material balance based on the feed qualification sample could replace most of the sampling in the CRVs and MFPVs. The evaluation consisted of three elements: (1) determination of the practicality of using a material balance to estimate the stream composition of the CRV and MFPV contents, (2) evaluation of whether the material balance could be automated using the existing process control system, and (3) determination of the uncertainty in glass composition using the material balance approach. It is assumed that periodic sampling at the CRV and MFPV would be performed periodically to re-baseline the material balance, evaluations are in progress to determine the frequency of this periodic sampling. Process sample locations downstream of the melter were reviewed as well, but the partitioning of semi-volatile species in the melter was determined to preclude extending the material balance approach past the melter. It was determined that replacement of the CRV sample location was feasible and did not increase process uncertainty or significantly impact waste loading. Replacement of the MFPV sample was also determined to be feasible, but that measurement of the glass former chemical addition may be needed prior to addition of these chemicals to the MFPV. This measurement could be performed by an in situ laser-induced breakdown spectroscopy (LIBS) system. Limited tests were performed to evaluate LIBS for direct measurements of the low-activity waste melter feed. The use of a material balance would eliminate over 1200 samples each year if only 10% of the CRV and MFPV batches are sampled and could likely allow the WTP laboratory to operate on days only versus 24/7 operation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Laser-Plasma Spectroscopy of Hydroxyl with Applications

This article discusses laser-induced laboratory-air plasma measurements and analysis of hydroxyl (OH) ultraviolet spectra. The computations of the OH spectra utilize line strength data that were developed previously and that are now communicated for the first time. The line strengths have been utilized extensively in interpretation of recorded molecular emission spectra and have been well-tested in laser-induced fluorescence applications for the purpose of temperature inferences from recorded data. Moreover, new experiments with Q-switched laser pulses illustrate occurrence of molecular recombination spectra for time delays of the order of several dozen of microseconds after plasma initiation. The OH signals occur due to the natural humidity in laboratory air. Centrifugal stretching of the Franck-Condon factors and r-centroids are included in the process of determining the line strengths that are communicated as a Supplementary File. Laser spectroscopy applications of detailed OH computations include laser-induced plasma and combustion analyses, to name but two applications. This work also includes literature references that address various diagnosis applications.

47 OTHER INSTRUMENTATION↗

Evolution and persistence of SiO emission in nanosecond laser ablation plumes

Analyzing laser-produced plasmas in a controlled oxygen-containing environment provides insight into the formation and evolution of molecular species through gas-phase oxidation. This study explores the role of ambient pressure and oxygen availability in forming SiO molecular species in laser ablation plumes. The self-emission emanating during the reactive ablation of Si targets was characterized by optical emission spectroscopy and optical time-of-flight techniques. Our results showed that the SiO species formation was greatly influenced by both the ambient pressure and oxygen availability. The intensity and the persistence of SiO emission bands are lower at higher oxygen concentrations, indicating they are depopulated by the formation of more complex silicon oxides. The oxygen partial pressure effects on plume chemistry showed that SiO formation is favored even with a minimal oxygen concentration in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser-Plasma Spatiotemporal Cyanide Spectroscopy and Applications

This article reports new measurements of laser-induced plasma hypersonic expansion measurements of diatomic molecular cyanide (CN). Focused, high-peak-power 1064 nm Q-switched radiation of the order of 1 TW/cm 2 generated optical breakdown plasma in a cell containing a 1:1 molar gas mixture of N 2 and CO 2 at a fixed pressure of 1.1 × 10 5 Pascal and in a 100 mL/min flow of the mixture. Line-of-sight (LOS) analysis of recorded molecular spectra indicated the outgoing shockwave at expansion speeds well in excess of Mach 5. Spectra of atomic carbon confirmed increased electron density near the shockwave, and, equally, molecular CN spectra revealed higher excitation temperature near the shockwave. Results were consistent with corresponding high-speed shadowgraphs obtained by visualization with an effective shutter speed of 5 nanoseconds. In addition, LOS analysis and the application of integral inversion techniques allow inferences about the spatiotemporal plasma distribution.

36 MATERIALS SCIENCE↗

Laser Ablation Plasmas and Spectroscopy for Nuclear Applications

The development of measurement methodologies to detect and monitor nuclear-relevant materials remains a consistent and significant interest across the nuclear energy, nonproliferation, safeguards, and forensics communities. Optical spectroscopy of laser-produced plasmas is becoming an increasingly popular diagnostic technique to measure radiological and nuclear materials in the field without sample preparation, where current capabilities encompass the standoff, isotopically resolved and phase-identifiable (e.g., UO and UO[Formula: see text]) detection of elements across the periodic table. These methods rely on the process of laser ablation (LA), where a high-powered pulsed laser is used to excite a sample (solid, liquid, or gas) into a luminous microplasma that rapidly undergoes de-excitation through the emission of electromagnetic radiation, which serves as a spectroscopic fingerprint for that sample. This review focuses on LA plasmas and spectroscopy for nuclear applications, covering topics from the wide-area environmental sampling and atmospheric sensing of radionuclides to recent implementations of multivariate machine learning methods that work to enable the real-time analysis of spectrochemical measurements with an emphasis on fundamental research and development activities over the past two decades. Background on the physical breakdown mechanisms and interactions of matter with nanosecond and ultrafast laser pulses that lead to the generation of laser-produced microplasmas is provided, followed by a description of the transient spatiotemporal plasma conditions that control the behavior of spectroscopic signatures recorded by analytical methods in atomic and molecular spectroscopy. High-temperature chemical and thermodynamic processes governing reactive LA plasmas are also examined alongside investigations into the condensation pathways of the plasma, which are believed to serve as chemical surrogates for fallout particles formed in nuclear fireballs. Laser-supported absorption waves and laser-induced shockwaves that accompany LA plasmas are also discussed, which could provide insights into atmospheric ionization phenomena from strong shocks following nuclear detonations. Furthermore, the standoff detection of trace radioactive aerosols and fission gases is reviewed in the context of monitoring atmospheric radiation plumes and off-gas streams of molten salt reactors. Finally, concluding remarks will present future outlooks on the role of LA plasma spectroscopy in the nuclear community.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Filament-induced breakdown spectroscopy signal enhancement using optical wavefront control

Filament-induced breakdown spectroscopy (FIBS) is an analytical method that holds significant promise for remote sensing. In FIBS, it is desirable to maximize the intensity and improve the reproducibility of a selected spectroscopic feature. Here, we demonstrate the use of wavefront control in conjunction with a genetic algorithm in FIBS of metallic copper and show that this approach can increase the efficacy of filament-induced breakdown signal production. Through wavefront optimization, we enhance the intensity of a chosen characteristic spectroscopic feature of copper by a factor of approximately 3 when performing filamentation over a 1-meter distance. The relative standard deviation of signal intensity is reduced from ~17% to ~12% after optimization. We find that modification of the wavefront by introduction of astigmatism and coma maximizes the signal intensity, and these aberrations appear in two distinct trials of the genetic algorithm. We compare these findings to previous work on multiple filament control and discuss the possible mechanisms that lead to signal enhancement associated with both the beam amplitude and phase profile. A broader use of wavefront control with feedback may improve the performance of FIBS in remote sensing applications.

42 ENGINEERING↗

Evolution of LIBS technology to mobile instrumentation for expediting firearm-related investigations at the laboratory and the crime scene

Gunshot residue (GSR) is one of the few forensic disciplines that lack accurate screening techniques. This study proposes using a mobile LIBS instrument to detect inorganic GSR and compares performance to a previously validated laboratory instrument. The mobile LIBS is designed with advanced configurations specifically for on-site GSR analysis, including a CMOS detector and a sampling chamber that holds up to six typical GSR collection devices with separate gas flow ports to prevent cross-contamination. A significant novelty of the portable instrument is its image magnification, which allows quick searching and visualization of GSR particle morphology. The single-particle imaging and elemental composition capability is one of a kind and offers superior confirmatory features for GSR. The mobile LIBS performance was evaluated for residues collected from the hands of shooters (100 samples) and non-shooters (200 background samples), analyzed sequentially by the mobile instrument and then the laboratory instrument. Accuracies better than 98.8% were obtained by both instruments, demonstrating their suitability for trace IGSR detection from skin specimens. Implementation of this methodology is anticipated to drastically speed up response times (i.e., from several hours per sample by standard SEM-EDS practice to a few minutes by LIBS). The screening methods can be easily incorporated into workflows to improve decision-making processes at the crime scene and laboratory settings, reduce backlogs, and improve case management.

47 OTHER INSTRUMENTATION↗

Towards Portable Laser Desorption Postionization Mass Spectrometry Utilizing Microchip Laser Pulses

A 355 nm, 1.5 ns, up to 1 kHz microchip laser system has been tested to both yield ablation spots and postionize material within a plasma plume. A 30 µJ pulse energy microchip laser successfully ablated all samples: 6601 aluminum, 316 and 304 stainless steel, and Mo metal. While visible ablation craters were observed on all samples mentioned above, the stainless-steel samples displayed visible color changes in the resolidified iron, indicating ionization with the 355 nm pulses during ablation. Additionally, when used to intercept a plasma plume of Cs 2 CO 3 made with a separate laser system, the microchip laser pulses yielded Cs + emission signal otherwise not observed. With these experiments completed, the microchip laser has been successfully verified for readiness to be integrated into the front end of a mass spectrometer system as the ion source.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

In-situ chemical imager

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in-situ instruments scanning probe microscopy lase↗