Askival: An altered feldspathic cumulate sample in Gale crater.

Askival is a light-toned, coarsely crystalline float rock, which was identified near the base of Vera Rubin Ridge in Gale crater. We have studied Askival, principally with the ChemCam instrument but also using APXS compositional data and MAHLI images. Askival and an earlier identified sample, Bindi, represent two rare examples of feldspathic cumulate float rocks in Gale crater with >65% relict plagioclase. Bindi appears unaltered whereas Askival shows textural and compositional signatures of silicification, along with alkali remobilization and hydration. Askival likely experienced multiple stages of alteration, occurring first through acidic hydrolysis of metal cations, followed by deposition of silica and possible phyllosilicates at low T and neutral-alkaline pH. Through laser-induced breakdown spectroscopy compositional analyses and normative calculations, we suggest that an assemblage of Fe-Mg silicates including amphibole and pyroxene, Fe phases, and possibly Mg-rich phyllosilicate are present. Thermodynamic modeling of the more pristine Bindi composition predicts that amphibole and feldspar are stable within an upper crustal setting. This is consistent with the presence of amphibole in the parent igneous rocks of Askival and suggests that the paucity of amphiboles in other known Martian samples reflects the lack of representative samples of the Martian crust rather than their absence on Mars.

OrganiCam: a lightweight time-resolved laser-induced luminescence imager and Raman spectrometer for planetary organic material characterization.

OrganiCam is a laser-induced luminescence imager and spectrometer designed for standoff organic and biosignature detection on planetary bodies. OrganiCam uses a diffused laser beam (12° cone) to cover a large area at several meters distance and records luminescence on half of its intensified detector. The diffuser can be removed to record Raman and fluorescence spectra from a small spot from 2 m standoff distance. OrganiCam's small size and light weight makes it ideal for surveying organics on planetary surfaces. We have designed and built a brassboard version of the OrganiCam instrument and performed initial tests of the system.

The Curiosity Rover's Exploration of Glen Torridon, Gale Crater, Mars: An Overview of the Campaign and Scientific Results.

The Mars Science Laboratory rover, Curiosity, explored the clay mineral-bearing Glen Torridon region for 1 Martian year between January 2019 and January 2021, including a short campaign onto the Greenheugh pediment. The Glen Torridon campaign sought to characterize the geology of the area, seek evidence of habitable environments, and document the onset of a potentially global climatic transition during the Hesperian era. Curiosity roved 5 km in total throughout Glen Torridon, from the Vera Rubin ridge to the northern margin of the Greenheugh pediment. Curiosity acquired samples from 11 drill holes during this campaign and conducted the first Martian thermochemolytic-based organics detection experiment with the Sample Analysis at Mars instrument suite. The lowest elevations within Glen Torridon represent a continuation of lacustrine Murray formation deposits, but overlying widespread cross bedded sandstones indicate an interval of more energetic fluvial environments and prompted the definition of a new stratigraphic formation in the Mount Sharp group called the Carolyn Shoemaker formation. Glen Torridon hosts abundant phyllosilicates yet remains compositionally and mineralogically comparable to the rest of the Mount Sharp group. Glen Torridon samples have a great diversity and abundance of sulfur-bearing organic molecules, which are consistent with the presence of ancient refractory organic matter. The Glen Torridon region experienced heterogeneous diagenesis, with the most striking alteration occurring just below the Siccar Point unconformity at the Greenheugh pediment. Results from the pediment campaign show that the capping sandstone formed within the Stimson Hesperian aeolian sand sea that experienced seasonal variations in wind direction.

Compositionally and density stratified igneous terrain in Jezero crater, Mars.

Before Perseverance, Jezero crater's floor was variably hypothesized to have a lacustrine, lava, volcanic airfall, or aeolian origin. SuperCam observations in the first 286 Mars days on Mars revealed a volcanic and intrusive terrain with compositional and density stratification. The dominant lithology along the traverse is basaltic, with plagioclase enrichment in stratigraphically higher locations. Stratigraphically lower, layered rocks are richer in normative pyroxene. The lowest observed unit has the highest inferred density and is olivine-rich with coarse (1.5 millimeters) euhedral, relatively unweathered grains, suggesting a cumulate origin. This is the first martian cumulate and shows similarities to martian meteorites, which also express olivine disequilibrium. Alteration materials including carbonates, sulfates, perchlorates, hydrated silicates, and iron oxides are pervasive but low in abundance, suggesting relatively brief lacustrine conditions. Orbital observations link the Jezero floor lithology to the broader Nili-Syrtis region, suggesting that density-driven compositional stratification is a regional characteristic.

Origin of Life on Mars: Suitability and Opportunities.

Although the habitability of early Mars is now well established, its suitability for conditions favorable to an independent origin of life (OoL) has been less certain. With continued exploration, evidence has mounted for a widespread diversity of physical and chemical conditions on Mars that mimic those variously hypothesized as settings in which life first arose on Earth. Mars has also provided water, energy sources, CHNOPS elements, critical catalytic transition metal elements, as well as B, Mg, Ca, Na and K, all of which are elements associated with life as we know it. With its highly favorable sulfur abundance and land/ocean ratio, early wet Mars remains a prime candidate for its own OoL, in many respects superior to Earth. The relatively well-preserved ancient surface of planet Mars helps inform the range of possible analogous conditions during the now-obliterated history of early Earth. Continued exploration of Mars also contributes to the understanding of the opportunities for settings enabling an OoL on exoplanets. Favoring geochemical sediment samples for eventual return to Earth will enhance assessments of the likelihood of a Martian OoL.

Origin and composition of three heterolithic boulder- and cobble-bearing deposits overlying the Murray and Stimson formations, Gale Crater, Mars.

Heterolithic, boulder-containing, pebble-strewn surfaces occur along the lower slopes of Aeolis Mons ("Mt. Sharp") in Gale crater, Mars. They were observed in HiRISE images acquired from orbit prior to the landing of the Curiosity rover. The rover was used to investigate three of these units named Blackfoot, Brandberg, and Bimbe between sols 1099 and 1410. These unconsolidated units overlie the lower Murray formation that forms the base of Mt. Sharp, and consist of pebbles, cobbles and boulders. Blackfoot also overlies portions of the Stimson formation, which consists of eolian sandstone that is understood to significantly postdate the dominantly lacustrine deposition of the Murray formation. Blackfoot is elliptical in shape (62 × 26 m), while Brandberg is nearly circular (50 × 55 m), and Bimbe is irregular in shape, covering about ten times the area of the other two. The largest boulders are 1.5-2.5 m in size and are interpreted to be sandstones. As seen from orbit, some boulders are light-toned and others are dark-toned. Rover-based observations show that both have the same gray appearance from the ground and their apparently different albedos in orbital observations result from relatively flat sky-facing surfaces. Chemical observations show that two clasts of fine sandstone at Bimbe have similar compositions and morphologies to nine ChemCam targets observed early in the mission, near Yellowknife Bay, including the Bathurst Inlet outcrop, and to at least one target (Pyramid Hills, Sol 692) and possibly a cap rock unit just north of Hidden Valley, locations that are several kilometers apart in distance and tens of meters in elevation. These findings may suggest the earlier existence of draping strata, like the Stimson formation, that would have overlain the current surface from Bimbe to Yellowknife Bay. Compositionally these extinct strata could be related to the Siccar Point group to which the Stimson formation belongs. Dark, massive sandstone blocks at Bimbe are chemically distinct from blocks of similar morphology at Bradbury Rise, except for a single float block, Oscar (Sol 516). Conglomerates observed along a low, sinuous ridge at Bimbe consist of matrix and clasts with compositions similar to the Stimson formation, suggesting that stream beds likely existed nearly contemporaneously with the dunes that eventually formed the Stimson formation, or that they had the same source material. In either case, they represent a later pulse of fluvial activity relative to the lakes associated with the Murray formation. These three units may be local remnants of infilled impact craters (especially circular-shaped Brandberg), decayed buttes, patches of unconsolidated fluvial deposits, or residual mass-movement debris. Their incorporation of Stimson and Murray rocks, the lack of lithification, and appearance of being erosional remnants suggest that they record erosion and deposition events that post-date the exposure of the Stimson formation.

A Series of Cyanide-Bridged Binuclear Complexes.

A series of cyanide-bridged binuclear complexes, ('S(3)')Ni-CN-M[Tp(tBu)] ('S(3)' = bis(2-mercaptophenyl)sulfide, Tp(tBu) = hydrotris(3-tert-butylpyrazolyl)borate, M = Fe (2-Fe), Co (2-Co), Ni (2-Ni), Zn (2-Zn)) was prepared by the coupling of K[('S(3)')Ni(CN)] with [Tp(tBu)]MX. The isostructural series of complexes was structurally and spectroscopically characterized. A similar coupling strategy was used to synthesize the anionic copper(I) analogue, Et4N{('S3')Ni-CN-Cu[Tp(tBu)]}, 2-Cu.An alternative synthesis was devised for the preparation of the linkages isomers of 2-Zn, i.e. of cyanide-bridged linkage isomers. X-ray diffraction, (13)C NMR and IR spectral studies established that isomerization to the more stable Ni-CN-Zn isomer occurs. DFT computational results buttressed the experimental observations indicating that the cyanide-bridged isomer is ca. 5 kcal/mol more stable than its linkage isomer.

"Standoff Biofinder" for Fast, Noncontact, Nondestructive, Large-Area Detection of Biological Materials for Planetary Exploration.

UNLABELLED: We developed a prototype instrument called the Standoff Biofinder, which can quickly locate biological material in a 500 cm(2) area from a 2 m standoff distance with a detection time of 0.1 s. All biogenic materials give strong fluorescence signals when excited with UV and visible lasers. In addition, the luminescence decay time of biogenic compounds is much shorter (<100 ns) than the micro- to millisecond decay time of transition metal ions and rare-earth ions in minerals and rocks. The Standoff Biofinder takes advantage of the short lifetime of biofluorescent materials to obtain real-time fluorescence images that show the locations of biological materials among luminescent minerals in a geological context. The Standoff Biofinder instrument will be useful for locating biological material during future NASA rover, lander, and crewed missions. Additionally, the instrument can be used for nondestructive detection of biological materials in unique samples, such as those obtained by sample return missions from the outer planets and asteroids. The Standoff Biofinder also has the capacity to detect microbes and bacteria on space instruments for planetary protection purposes. KEY WORDS: Standoff Biofinder-Luminescence-Time-resolved fluorescence-Biofluorescence-Planetary exploration-Planetary protection-Noncontact nondestructive biodetection. Astrobiology 16, 715-729.

Next generation laser-based standoff spectroscopy techniques for Mars exploration.

In the recent Mars 2020 Rover Science Definition Team Report, the National Aeronautics and Space Administration (NASA) has sought the capability to detect and identify elements, minerals, and most importantly, biosignatures, at fine scales for the preparation of a retrievable cache of samples. The current Mars rover, the Mars Science Laboratory Curiosity, has a remote laser-induced breakdown spectroscopy (LIBS) instrument, a type of quantitative elemental analysis, called the Chemistry Camera (ChemCam) that has shown that laser-induced spectroscopy instruments are not only feasible for space exploration, but are reliable and complementary to traditional elemental analysis instruments such as the Alpha Particle X-Ray Spectrometer. The superb track record of ChemCam has paved the way for other laser-induced spectroscopy instruments, such as Raman and fluorescence spectroscopy. We have developed a prototype remote LIBS-Raman-fluorescence instrument, Q-switched laser-induced time-resolved spectroscopy (QuaLITy), which is approximately 70 000 times more efficient at recording signals than a commercially available LIBS instrument. The increase in detection limits and sensitivity is due to our development of a directly coupled system, the use of an intensified charge-coupled device image detector, and a pulsed laser that allows for time-resolved measurements. We compare the LIBS capabilities of our system with an Ocean Optics spectrometer instrument at 7 m and 5 m distance. An increase in signal-to-noise ratio of at least an order of magnitude allows for greater quantitative analysis of the elements in a LIBS spectrum with 200-300 µm spatial resolution at 7 m, a Raman instrument capable of 1 mm spatial resolution at 3 m, and bioorganic fluorescence detection at longer distances. Thus, the new QuaLITy instrument fulfills all of the NASA expectations for proposed instruments.

Modeling the Raman spectrum of graphitic material in rock samples with fluorescence backgrounds: accuracy of fitting and uncertainty estimation.

We propose a robust technique called Savitzky-Golay second-derivative (SGSD) fitting for modeling the in situ Raman spectrum of graphitic materials in rock samples such as carbonaceous chondrite meteorites. In contrast to non-derivative techniques, with assumed locally linear or nth-order polynomial fluorescence backgrounds, SGSD produces consistently good fits of spectra with variable background fluorescence of any slowly varying form, without fitting or subtracting the background. In combination with a Monte Carlo technique, SGSD calculates Raman parameters (such as peak width and intensity) with robust uncertainties. To explain why SGSD fitting is more accurate, we compare how different background subtraction techniques model the background fluorescence with the wide and overlapping peaks present in a real Raman spectrum of carbonaceous material. Then, the utility of SGSD is demonstrated with a set of real and simulated data compared to commonly used linear background techniques. Researchers may find the SGSD technique useful if their spectra contain intense background interference with unknown functional form or wide overlapping peaks, and when the uncertainty of the spectral data is not well understood.