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Chemical composition of Martian fines

Of the 21 samples acquired for the Viking X-ray fluorescence spectrometer, 17 were analyzed to high precision. Compared to typical terrestrial continental soils and lunar mare fines, the Martian fines are lower in Al, higher in Fe, and much higher in S and Cl concentrations. Protected fines at the two lander sites are almost indistinguishable, but concentration of the element S is somewhat higher at Utopia. Duricrust fragments, successfully acquired only at the Chryse site, invariably contained about 50% higher S than fines. No elements correlate positively with S, except Cl and possibly Mg. A sympathetic variation is found among the triad Si, Al, Ca; positive correlation occurs between Ti and Fe. Sample variabilities are as great within a few meters as between lander locations (4500 km apart), implying the existence of a universal Martian regolith component of constant average composition. The nature of the source materials for the regolith fines must be mafic to ultramafic.

Clark, B. C.↗

Trace element content of chondritic cosmic dust: Volatile enrichments, thermal alterations, and the possibility of contamination

Trace element abundances in 51 chondritic Interplanetary Dust Particles (IDP's) were measured by Synchrotron X-Ray Fluorescence (SXRF). The data allow us to determine an average composition of chondritic IDP's and to examine the questions of volatile loss during the heating pulse experienced on atmospheric entry and possible element addition due to contamination during atmospheric entry, stratospheric residence, and curation.

Flynn, G. J.↗

A Miniature Mineralogical Instrument for In-Situ Characterization of Ices and Hydrous Minerals at the Lunar Poles

Lunar missions over the past few years have provided new evidence that water may be present at the lunar poles in the form of cold-trapped ice deposits, thereby rekindling interest in sampling the polar regions. Robotic landers fitted with mineralogical instrumentation for in-situ analyses could provide unequivocal answers on the presence of crystalline water ice and/or hydrous minerals at the lunar poles. Data from Lunar Prospector suggest that any surface exploration of the lunar poles should include the capability to drill to depths of more than 40 cm. Limited data on the lunar geotherm indicate temperatures of approximately 245-255 K at regolith depths of 40 cm, within a range where water may exist in the liquid state as brine. A relevant terrestrial analog occurs in Antarctica, where the zeolite mineral chabazite has been found at the boundary between ice-free and ice-cemented regolith horizons, and precipitation from a regolith brine is indicated. Soluble halogens and sulfur in the lunar regolith could provide comparable brine chemistry in an analogous setting. Regolith samples collected by a drilling device could be readily analyzed by CheMin, a mineralogical instrument that combines X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques to simultaneously characterize the chemical and mineralogical compositions of granular or powdered samples. CheMin can unambiguously determine not only the presence of hydrous alteration phases such as clays or zeolites, but it can also identify the structural variants or types of clay or zeolite present (e.g., well-ordered versus poorly ordered smectite; chabazite versus phillipsite). In addition, CheMin can readily measure the abundances of key elements that may occur in lunar minerals (Na, Mg, Al, Si, K, Ca, Fe) as well as the likely constituents of lunar brines (F, Cl, S). Finally, if coring and analysis are done during the lunar night or in permanent shadow, CheMin can provide information on the chemistry and structure of any crystalline ices that might occur in the regolith samples.

Sarrazin, P.↗

Detection Limit of Smectite by Chemin IV Laboratory Instrument: Preliminary Implications for Chemin on the Mars Science Laboratory Mission

The CheMin instrument on the Mars Science Laboratory (MSL) is an miniature X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of detecting the mineralogical and elemental compositions of rocks, outcrops and soils on the surface of Mars. CheMin uses a microfocus-source Co X-ray tube, a transmission sample cell, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. CRISM and OMEGA have identified the presence of phyllosilicates at several locations on Mars including the four candidate MSL landing sites. The objective of this study was to conduct preliminary studies to determine the CheMin detection limit of smectite in a smectite/olivine mixed mineral system.

Archilles, Cherie↗

Effects of Kapton Sample Cell Windows on the Detection Limit of Smectite: Implications for CheMin on the Mars Science Laboratory Mission

The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity is an X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of providing the mineralogical and chemical compositions of rocks and soils on the surface of Mars. CheMin uses a microfocus X-ray tube with a Co target, transmission geometry, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. CheMin has two different window materials used for sample cells -- Mylar and Kapton. Instrument details are provided elsewhere. Fe/Mg-smectite (e.g., nontronite) has been identified in Gale Crater, the MSL future landing site, by CRISM spectra. While large quantities of phyllosilicate minerals will be easily detected by CheMin, it is important to establish detection limits of such phases to understand capabilities and limitations of the instrument. A previous study indicated that the (001) peak of smectite at 15 Ang was detectable in a mixture of 1 wt.% smectite with olivine when Mylar is the window material for the sample cell. Complications arise when Kapton is the window material because Kapton itself also has a diffraction peak near 15 Ang (6.8 deg 2 Theta). This study presents results of mineral mixtures of smectite and olivine to determine smectite detection limits for Kapton sample cells. Because the intensity and position of the smectite (001) peak depends on the hydration state, we also analyzed mixtures with "hydrated" and "dehydrated"h smectite to examine the effects of hydration state on detection limits.

Achilles, C. N.↗

X-Ray Diffraction Reference Intensity Ratios of Amorphous and Poorly Crystalline Phases: Implications for CheMin on the Mars Science Laboratory

The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity is an X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of providing the mineralogical and chemical compositions of rocks and soils on the surface of Mars. CheMin uses a microfocus X-ray tube with a Co target, transmission geometry, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. Piezoelectric vibration of the cell is used to randomize the sample to reduce preferred orientation effects. Instrument details are provided in [1, 2, 3]. Analyses of rock and soil samples by the Mars Exploration Rovers (MER) show nanophase ferric oxide (npOx) is a significant component of the Martian global soil [4] and is thought to be one of the major contributing phases that the Curiosity rover will encounter if a soil sample is analyzed in Gale Crater. Because of the nature of this material, npOx will likely contribute to an X-ray amorphous or short-order component of a XRD pattern measured by the CheMin instrument.

Morris, R. V.↗

Analysis of CO2 Composite Spray Cleaning System Results

In a previous study, the cleaning efficiency of a CO2 composite cleaning system for particulate removal was tested. The study covered particles from spores to fluorescent particles of different sizes as well as a variety of substrate surfaces, including aluminum, titanium, stainless steel, and nitinol. Particles were deposited using aerosol (dry) and droplet (wet) deposition. Results from the previous study show that the CO2 composite spray system is capable of cleaning to sterility for aerosol deposited spores and is capable of cleaning a minimum of a 4-log reduction for droplet deposited spores. This minimum 4-log reduction matches current Planetary Protection dry heat microbial reduction requirements. In this paper we will present new data to further correlate the cleaning efficiency with how contamination was introduced to the surface, the surface roughness, and particle size. Possible causes for such correlations will be discussed.

Chung, Shirley↗

Feasibility of Ultraviolet Light Emitting Diodes as an Alternative Light Source for Photocatalysis

The objective of this study was to determine whether ultraviolet light emitting diodes (UV-LEDs) could serve as an alternative photon source efficiently for heterogeneous photocatalytic oxidation (PCO). An LED module consisting of 12 high-power UV-A LEDs was designed to be interchangeable with a UV-A fluorescent black light blue (BLB) lamp in a Silica-Titania Composite (STC) packed bed annular reactor. Lighting and thermal properties were characterized to assess the uniformity and total irradiant output. A forward current of (I(sub F)) 100 mA delivered an average irradiance of 4.0 m W cm(exp -2), which is equivalent to the maximum output of the BLB, but the irradiance of the LED module was less uniform than that of the BLB. The LED- and BLB-reactors were tested for the oxidization of 50 ppmv ethanol in a continuous flow-through mode with 0.94 sec space time. At the same irradiance, the UV-A LED reactor resulted in a lower PCO rate constant than the UV-A BLB reactor (19.8 vs. 28.6 nM CO2 sec-I), and consequently lower ethanol removal (80% vs. 91%) and mineralization efficiency (28% vs. 44%). Ethanol mineralization increased in direct proportion to the irradiance at the catalyst surface. This result suggests that reduced ethanol mineralization in the LED- reactor could be traced to uneven irradiance over the photocatalyst, leaving a portion of the catalyst was under-irradiated. The potential of UV-A LEDs may be fully realized by optimizing the light distribution over the catalyst and utilizing their instantaneous "on" and "off' feature for periodic irradiation. Nevertheless, the current UV-A LED module had the same wall plug efficiency (WPE) of 13% as that of the UV-A BLB. These results demonstrated that UV-A LEDs are a viable photon source both in terms of WPE and PCO efficiency.

Levine, Langanf H.↗

Heterogeneous Outgassing Regions Identified on Active Centaur 29P/Schwassmann–Wachmann 1

Centaurs are transitional objects between primitive trans-Neptunian objects and Jupiter-family comets. Their compositions and activities provide fundamental clues regarding the processes affecting the evolution of and interplay between these small bodies. Here we report observations of centaur 29P/Schwassmann–Wachmann 1 (29P) with the James Webb Space Telescope (JWST). We identified localized jets with heterogeneous compositions driving the outgassing activity. We employed the NIRSpec mapping spectrometer to study the fluorescence emissions of CO and obtain a definitive detection of CO 2 for this target. The exquisite sensitivity of the instrument also enabled carbon and oxygen isotopic signatures to be probed. Molecular maps reveal complex outgassing distributions, such as jets and anisotropic morphology, which indicate that 29P’s nucleus is dominated by active regions with heterogeneous compositions. These distributions could reflect that it has a bilobate structure with compositionally distinct components or that strong differential erosion takes place on the nucleus. As there are no missions currently planning to visit a centaur, these observations demonstrate JWST’s unique capabilities in characterizing these objects.

Sara Faggi↗

Apollo 15 X-ray fluorescence experiment

The X-ray fluorescence spectrometer, carried in the SIM bay of the command service module was employed principally for compositional mapping of the lunar surface while in lunar orbit, and secondarily, for X-ray astronomical observations during the trans-earth coast. The lunar surface measurements involved observations of the intensity and characteristics energy distribution of the secondary or fluorescent X-rays produced by the interaction of solar X-rays with the lunar surface. The astronomical observations consisted of relatively long periods of measurements of X-rays from pre-selected galactic sources such as Cyg-X-1 and Sco X-1 as well as from the galactic poles.

Adler, I.↗

First-results from the Perseverance SHERLOC Investigation: Aqueous Alteration Processes and Implications for Organic Geochemistry in Jezero Crater, Mars

The Perseverance rover landed in Jezero crater, a site selected to fulfill the Mars-2020 mission goals of characterizing the geology of habitable environments and searching for signs of life while collecting samples for return to Earth [1]. Jezero hosted an open-basin lake during the late Noachian/early Hesperian (~3.7 Ga) [1-2], has units associated with the largest carbonate deposit identified on Mars [3-4], and has a well-preserved delta with clay and carbonate-bearing sediments, well-suited to preservation of organics [1,3-4]. Investigating the nature of organics and aqueous environments within their geologic con-text allows us to understand important aqueous processes and determine habitability within Jezero crater. Previous in situ landed measurements of organics could not resolve their spatial and mineralogical con-text [5-6]. Although Martian meteorites lack geological context, the spatial distribution of organic compounds in Martian meteorites have allowed recognition of an association between aqueous processes and organics [7-8]. Here, we show for the first time in-situ associations between carbonate-forming ultramafic alteration process, later stage aqueous sulfate and perchlorate formation, and organics on the Martian surface. Methodology and geological context: We use the Perseverance rover’s SHERLOC instrument (Scanning Habitable Environments with Raman and Lumines-ence of Organics and Chemicals), a deep-ultraviolet fluorescence and Raman scattering spectrometer capable of mapping the organic and mineral composition with a spatial resolution of 100 μm resolution to report the presence of organics and aqueously formed minerals at Jezero crater [9]. These spectral detections were compared with co-located images obtained with the autofocus context imager (ACI) and the WATSON camera for textural analysis [9]. As of writing, the Per-severance rover has abraded five targets that were measured with the SHERLOC instrument. The five targets are located in two different orbitally-identified geological units within the floor of Jezero crater; the Crater Floor Fractured Rough unit (CF-Fr) and the Séítah region within the Crater Floor Fractured 1 unit (CF-F1) [10]. In orbital infrared spectroscopic data, the CF-Fr unit is associated with pyroxene spectral signatures and minor alteration, while the Séítah region is associated with olivine and minor Mg-rich carbonates and clays [3-4,10]. Carbonation of ultramafic protolith recorded within Jezero crater: All scans of abraded targets within the Séítah region reveal strong peaks at 1080–1090 cm−1 consistent with carbonate and peak singlets or doublets at 820–840 cm−1 attributed to olivine (Fig. 1), consistent with orbital infrared observations. Our detailed micron-scale petrographic and spectroscopic evidence shows that these carbonates formed through carbonation of an ultramafic protolith. The supporting observations include: (1) Carbonate cation compositions match those of olivine, suggesting mixed Fe- and Mg-olivine gave rise to mixed Fe- and Mg-carbonates, similar to observations of ultramafic systems on Earth and within Martian meteorites [3-4,7-8]. (2) The ob-served carbonates co-occur with hydrated materials, gypsum, and potentially aqueously-formed phases, amorphous silicates and phosphate. (3) The spectral and textural variation of olivine and carbonate dominated zones and olivine-carbonate mixtures within both primary grains and interstitial zones are expected for carbonated ultramafic protoliths. (4) These mineral associations and textures closely resemble those observed within the ALH84001 and Nakhlite meteorites attributed to olivine carbonation on Mars [6-7]. Taken together, micron-scale SHERLOC documentation of these phenomena bridge previous orbital and meteorite observations and demonstrate in-situ regionally extensive (~106 km2) ultramafic alteration resulting in geo-logical deposition of carbonates. Furthermore, we observe that olivine carbonation was involved in preserving and possibly synthesizing organics, which makes this environment potentially habitable, as previously suggested in [1,3-4] (Fig. 1). Late-stage aqueous perchlorate and sulfate in Jezero crater: An abrasion target within the CF-Fr unit contains combinations of high intensity 950-955 cm−1 peaks and minor 1090-1095 cm−1 and 1150-1155 cm−1 peaks that are spectral fits to anhydrous perchlorate (Fig. 1). Some spectra show a combination of 950-955 cm−1 peaks with equally strong 1010-1020 cm−1 peaks, low intensity broad features at 1120 cm−1, and occasional broad 3450 cm−1 hydration (-OH) features, indicating a mixture of Ca-sulfate and perchlorate that is minimally hydrated (Fig. 1). The detections of per-chlorates within Jezero crater differ from previous measurements (e.g. Phoenix lander, Curiosity rover, Tissint meteorite [7,11]) because they are observed to be intimately related to aqueous processes including sulfate formation, they present as a secondary white void-fill occurring within the interior of the rock, and they are found to likely be Na-perchlorate. implications for their formation: Three different types of organics embedded within three different lithologies were observed within the abraded targets. Organics associated with low intensity ~340 nm fluorescence were widespread within targets with no apparent association to particular minerals (Fig. 1). Organics associated with ~305 nm and ~275 nm fluorescence correlated with sulfates within the Bellegarde target in the CF-Fr unit, while organics associated with high intensity ~340 nm fluorescence correlated with carbonate, phosphate, and amorphous silicate mixtures within the Garde target in the Séítah region (Fig. 1). Although assignment of fluorescence signatures to specific organic compounds is not conclusive, ~340 nm fluorescence is generally more consistent with 2-ring aromatic organics, ~275 nm fluorescence is more consistent with 1-ring aromatic organics, and ~305 nm fluorescence can be created by either 2- or 1-ring aromatics [12]. These observations indicate that the strongest fluorescence signatures interpreted as organics were found in materials associated with aqueous processes, i.e. sulfate- and carbonate-bearing materials, suggesting both brines and ultramafic carbonation aqueous environments were capable of preserving organics on ancient Mars. In Martian meteorites, simple aromatic organics proposed to have been synthesized through aqueous processes can be found within minerals associated with olivine carbonation and in spatial association with perchlorate and sulfate materials [7-8], similar to SHERLOC observations. Hence, we advance an abiotic aqueous synthesis origin for the organics although we cannot rule out the presence of organics from meteoritic in-fall or putative organic biosignatures. Detailed analyses will be required upon return of these materials to Earth.

E L Scheller↗

The Effects of Surface Roughness on the NEAR XRS Elemental Results: Monte-Carlo Modeling

The objective of the NEAR-Shoemaker X-ray Gamma-Ray Spec1roscopy ("XGRS") investigation was to determine the elemental composition of the near-Earth asteroid 433 Eros. The X-ray Spectrometer (XRS) system measured the characteristic fluorescence of six major elements (Mg, Al, Si, S, Ca, Fe) in the 1-10 keV energy range excited by the interaction of solar X-rays with the upper 100 microns of the surface of 433 Eros. Various investigators, using both laboratory experiments and computer simulations have established that X-ray fluorescent line ratios can be influenced by small-scale surface roughness at high incidence or emission angles. The effect on the line ratio is specific to the geometry, excitation spectrum, and composition involved, In general, however, the effect is only substantial for ratios of lines with a significant energy difference between them: Fe/Si and Ca/Si are much more likely to be affected than AI/Si or Mg/Si. We apply a Monte-Carlo code to the specific geometry and spectrum of a major NEAR XRS solar flare observation, using an H chondrite composition as the substrate. The seventeen most abundant elements were included in the composition model, from oxygen to titanium.

Lin, Lucy F.↗

Metal etching composition

The present invention is directed to a chemical etching composition for etching metals or metallic alloys. The composition includes a solution of hydrochloric acid, phosphoric acid, ethylene glycol, and an oxidizing agent. The etching composition is particularly useful for etching metal surfaces in preparation for subsequent fluorescent penetrant inspection.

Otousa, Joseph E.↗

Fine-scale traverses in cumulate rocks, Stillwater Complex: A lunar analogue study

The objective was to document finite-scale compositional variations in cumulate rocks from the Stillwater Complex in Montana and to interpret these data in the context of planetary magma fractionation processes such as those operative during the formation of the Earth's Moon. This research problem involved collecting samples in the Stillwater Complex and analyzing them by electron microprobe, X-ray fluorescence (XRF), and instrumental neutron activation analysis (INAA). The electron microprobe is used to determine the compositions of cumulus and intercumulus phases in the rocks, the XRF is used to determine the bulk-rock major element and trace element (Y, Sr, Rb, Zr, Ni, and Cr) abundances, and the INAA lab. is used to determine the trace element (Sc, Co, Cr, Ni, Ta, Hf, U, Th, and the REE) abundances of mineral separates and bulk rocks.

Elthon, Donald↗

Calibration of the SHERLOC Deep Ultraviolet Fluorescence–Raman Spectrometer on the Perseverance Rover

We describe the wavelength calibration of the spectrometer for the scanning of habitable environments with Raman and luminescence for organics and chemicals (SHERLOC) instrument onboard NASA’s Perseverance Rover. SHERLOC utilizes deep ultraviolet Raman and fluorescence (DUV R/F) spectroscopy to enable analysis of samples from the Martian surface. SHERLOC employs a 248.6 nm deep ultraviolet laser to generate Raman-scattered photons and native fluorescence emission photons from near-surface material to detect and classify chemical and mineralogical compositions. The collected photons are focused on a charge-coupled device and the data are returned to Earth for analysis. The compact DUV R/F spectrometer has a spectral range from 249.9 nm to 353.6 nm (200 cm1 to 12, 000 cm1) (with a spectral resolution of 0.296 nm (40 cm1)). The compact spectrometer uses a custom design to project a high-resolution Raman spectrum and a low-resolution fluorescence spectrum on a single charge-coupled device. The natural spectral separation enabled by deep ultraviolet excitation enables wavelength separation of the Raman/fluorescence spectra. The SHERLOC spectrometer was designed to optimize the resolution of the Raman spectral region and the wavelength range of the fluorescence region. The resulting illumination on the charge-coupled device is curved, requiring a segmented, nonlinear wavelength calibration in order to understand the mineralogy and chemistry of Martian materials.

Kyle Uckert↗

X-ray fluorescence experiment

The X-ray fluorescence spectrometer, carried in the scientific instrument module bay of the command and service module, was used for orbital mapping of the lunar surface composition and X-ray galactic observations during transearth coast. The lunar surface measurements involved observations of the intensity and characteristic energy distribution of the secondary or fluorescent X-rays produced by the interaction of solar X-rays with the lunar surface. The astronomical observations consisted of relatively long periods of X-ray measurement of preselected galactic sources such as Cygnus (Cyg X-1) and Scorpius (Sco X-1).

Adler, I.↗

Lunar composition from Apollo orbital measurements

An X-ray spectrometer carried in the Service Module of the Apollo 15 and 16 spacecraft were employed for compositional mapping of the lunar surface. The surface measurements involved observations of the intensity and characteristic energy distribution of the fluorescent X-rays produced by the interaction of the solar X-rays with the lunar surface as well as naturally occurring gamma-rays and cosmic ray produced gamma-rays. A large scale compositional map of approximately twenty percent of the lunar surface was obtained for the first time. It was possible to demonstrate differences between the highlands and the mare and to learn something about the composition of the moon's hidden side. Results obtained from the X-ray experiment and the gamma-ray experiment are consistent with those obtained from lunar sample analysis.

Adler, I.↗