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At least 253 records · Page 14

Variability in Mt. Sharp Group Bedrock as Seen By ChemCam Passive and Active Spectra

The Curiosity rover landed in Gale crater in August 2012 and has since been travelling up the central sedimentary mound known as Mt. Sharp. The ChemCam instrument on Curiosity was designed primarily for the use of Laser Induced Breakdown Spectroscopy (LIBS), where a laser ablates a small amount of material from the target and the spectrum of the resulting plasma yields elemental abundance data. ChemCam’s three spectrometers range from 240-905 nm and can also take passive spectra (without the use of the laser). The spectral range ChemCam passive spectra observe is sensitive to charge-transfer and crystal field absorptions related to iron-bearing minerals. In the first 2934 sols of Curiosity’s mission, 9,400 passive spectra were taken of bedrock targets in Mt. Sharp’s Murray and Carolyn Shoemaker formations. We examine these spectra using spectral slope/ratio and band depth calculations as well as Principal Component Analysis (PCA). For the first time, paired passive spectra and LIBS elemental abundances are compared on a large scale. Finally, CheMin data are compared to ChemCam passive observations to understand sources of spectral variability.

H T Manelski↗

Using the Potassium-Argon Laser Experiment (KArLE) to Date Ancient, Low-K Chondritic Meteorites

Several laboratories have been investigating the feasibility of in situ K-Ar dating for use in future landing planetary missions. One drawback of these laboratory demonstrations is the insufficient analogy of the analyzed analog samples with expected future targets. We present the results obtained using the K-Ar laser experiment (KArLE) on two old and K-poor chondritic samples, Pułtusk and Hvittis, as better lunar analogs. The KArLE instrument uses laser ablation to vaporize rock samples and quantifies K content by laser-induced breakdown spectroscopy (LIBS), Ar by quadrupole mass spectrometry (QMS), and ablated mass by laser profilometry. We performed 64 laser ablations on the chondrites to measure spots with a range of K 2 O and Ar content and used the data to construct isochrons to determine the chondrite formation age. The KArLE isochron ages on Pułtusk and Hvittis are 5059 ± 892 Ma and 4721 ± 793 Ma, respectively, which is within the uncertainty of published reference ages, and interpreted as the age of their formation. The uncertainty (2σ) on the KArLE ages obtained in this study is better than 20% (18% for Pułtusk and 17% for Hvittis). The precision, which compares our obtained ages to the reference ages, is also better than 20% (11% for Pułtusk and 4% for Hvittis). These results are encouraging for understanding the limits of this technique to measure ancient planetary samples and for guiding future improvements to the instrument.

Fanny Cattani↗

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↗

Center for Isotope Cosmochemistry and Geochronology at NASA Johnson Space Center

The Center for Isotope Cosmochemistry and Geochronology (CICG) at the NASA Johnson Space Center, led by Justin Simon, applies novel elemental and isotopic analytical techniques to understand solar system formation, from processes occurring during the earliest Solar Nebula, to the evolution of planetary bodies during planet formation and differentiation. CICG consists of an integrated suite of labs including dedicated spaces for specialized handling and preparation of meteorites and planetary return samples, metal-free clean chemistry, and mass spectrometry. In addition to a Thermo-Scientific Triton thermal ionization mass spectrometer (TIMS) for high precision isotopic analyses in processed samples, CICG houses two additional mass spectrometry instruments with added laser ablation capabilities for high spatial resolution in-situ measurements: (1) a Thermo-Scientific Element-XR inductively coupled mass spectrometer (ICP-MS) with a Teledyne Photon Machines Analyte Excite+ laser ablation system, and (2) a Nu Sapphire 1700 multi-collector ICP-MS, a large geometry instrument with a multi-pole collision cell for interference removal, with an Applied Spectra J200 tandem laser induced breakdown spectroscopy (LIBS) femto-second laser ablation system. We detail the analytical capabilities of CICG in the context of current and future research projects related to the studies of protoplanetary disk evolution via early-formed Solar System solids, volatile abundances and distribution within the inner solar system, and geochemical and temporal investigations related to planet formation and differentiation. We also highlight opportunities through the relationship with the Center of the Advancement of Space Safety and Mission Assurance Research (CASSMAR) at the University of Texas at El Paso. CICG is open to collaborations and participates in the NASA Facility for Astromaterials Research (NFAR) program, which accepts research proposals for access to the unique facility capabilities.

Jacob B. Setera↗

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↗

Application of High-Spatial Resolution LA-MC-ICP-MS in Planetary Materials

High-precision stable and radiogenic isotopic measurements of planetary materials can help elucidate processes taking place during early Solar System formation, as well as during subsequent planetary differentiation. Laser Ablation Multi Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS) adds the valuable ability of preserving the spatial context of these isotopic measurements, by sampling small sample volumes (~10 – 60 um diameter) using a pulsed laser system. In the Center for Isotope Cosmochemistry and Geochronology (CICG) at NASA Johnson Space Center, these in-situ isotopic measurements are primarily made using the Applied SpectraTM iX-fs-Tandem LA-LIBS Instrument coupled to the Nu InstrumentsTM SP1700 MC-ICP-MS. The instrumental set-up also provides simultaneous Laser Induced Breakdown Spectroscopy (LIBS) measurements and the potential use of a low energy path with a collision/reaction cell for additional interference removal, though we focus here on the typical high-energy LA-MC-ICP-MS operation. We will provide examples of stable (e.g., Mg) and radiogenic (e.g., Lu-Hf) isotopic systems measured in planetary materials and their terrestrial analogs. The measurement of mass dependent Mg isotopic variations is an important tool for reconstructing processes such as evaporation and condensation of solids in the solar nebula. For early Solar System samples, Mg isotope measurements are also important for the short-lived (t1/2 = 0.7 Ma) Al-Mg chronometer. During laser ablation analyses, the measurement of the Al-Mg isotopic system is made in medium mass resolution (RP ~9500 at ~20% transmission) to limit interferences from 48Ti2+ and 48Ca2+ on 24Mg+, in addition to 52Cr2+ and 12C14N+ on 26Mg+. Measured in the mineral zircon, the 176Lu-176Hf decay system is often used for understanding the growth of continents on Earth, and is also a vital aid in deciphering early large-scale planetary differentiation processes, such as the crystallization of the lunar magma ocean, which is thought to be responsible for much of the Moon’s crust. Lu-Hf measurements are made in low resolution mode (RP <2000), with 10 ion masses (from 171Yb to 180Hf) measured simultaneously to facilitate corrections for isobaric interferences from 176Yb and 176Lu on 176Hf.

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↗

Online Molten Salt and Gas Monitoring Using Combined Spectroscopic Methods

The nonproliferation of nuclear material and the development of safeguards technologies to sample and analyze fuel salt is a challenge for molten salt reactor (MSR) developers. We seek online monitoring using combined spectroscopic methods of two distinct material phases from MSR’s. Molten salt transformed to aerosol phase allows for Light Induced Breakdown spectroscopy (LIBS) without adverse splashing (ARPA-E). Vaporized used nuclear fuel through chlorine-based volatility (CBV) allows for uranium separation based on boiling point differences

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

High power actively Q-switched downhole LIBS analysis systems

An actively Q-switched laser induced breakdown spectroscopy (LIBS) probe, utilizing an optical fiber, a pump beam transmitted through the optical fiber, a coupler, and a lens for collimating the pump beam. The actively Q-switched laser, coupled to a sensor which provides information to a computer that controls a high voltage pulser providing a pulse to a Pockels cell located within the laser which can selectively cause the laser to pulse, resulting in high energy pulses and a second lens for focusing the output pulse such that it creates a plasma or spark. The light from the spark is captured and directed back through an optical system to remote equipment for elemental and/or molecular analysis.

McIntyre, Dustin Langdon↗

LIBS Applications to Liquids and Solids in Liquids

In this chapter, LIBS instrumentation and data collection system used for the analysis of liquids and solids in liquids are discussed. LIBS measurements of bulk liquid samples and solids submerged in aqueous media, measurements made by focusing laser pulses on liquid surfaces, and measurements of liquids after various sample treatments are presented. In addition, the working mechanism of NETL‐developed field‐deployable LIBS sensor and its preliminary performance in field measurements are also reported.

atomic emission spectroscopy↗

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↗