Studies of a Lacustrine-Volcanic Mars Analog Field Site with Mars-2020-like Instruments

On the upcoming Mars‐2020 rover two remote sensing instruments, Mastcam‐Z and SuperCam, and two microscopic proximity science instruments, SHERLOC and PIXL, will collect compositional (mineralogy, chemistry, and organics) data essential for paleoenvironmental reconstruction. The synergies between and limitations of these instruments were evaluated via study of a Mars analog field site in the Mojave Desert, using instruments approximating the data that will be returned by Mars‐2020. A ground truth dataset was generated for comparison to validate the results. The site consists of a succession of clay‐rich mudstones of lacustrine origin, interbedded tuffs, a carbonate‐silica travertine deposit, and gypsiferous mudstone strata. The major geological units were mapped successfully using simulated Mars‐2020 data. Simulated Mastcam‐Z data identified unit boundaries and Fe‐bearing weathering products. Simulated SuperCam passive shortwave infrared and green Raman data were essential in identifying major mineralogical composition and changes in lacustrine facies at distance; this was possible even with spectrally downsampled passive IR data. LIBS and simulated PIXL data discriminated and mapped major element chemistry. Simulated PIXL revealed mm‐scale zones enriched in zirconium, of interest for age dating. SHERLOC‐like data mapped sulfate and carbonate at sub‐mm scale; silicates were identified with increased laser pulses/spot or by averaging of hundreds of spectra. Fluorescence scans detected and mapped varied classes of organics in all samples, characterized further with follow‐on spatially targeted deep‐UV Raman spectra. Development of dedicated organics spectral libraries is needed to aid interpretation. Given these observations, the important units in the outcrop would be sampled and cached for sample return

Interfacial Reactions of Ozone with Surfactant Protein B in a Model Lung Surfactant System

Oxidative stresses from irritants such as hydrogen peroxide and ozone (O_3) can cause dysfunction of the pulmonary surfactant (PS) layer in the human lung, resulting in chronic diseases of the respiratory tract. For identification of structural changes of pulmonary surfactant protein B (SP-B) due to the heterogeneous reaction with O_3, field-induced droplet ionization (FIDI) mass spectrometry has been utilized. FIDI is a soft ionization method in which ions are extracted from the surface of microliter-volume droplets. We report structurally specific oxidative changes of SP-B_(1−25) (a shortened version of human SP-B) at the air−liquid interface. We also present studies of the interfacial oxidation of SP-B_(1−25) in a nonionizable 1-palmitoyl-2-oleoyl-sn-glycerol (POG) surfactant layer as a model PS system, where competitive oxidation of the two components is observed. Our results indicate that the heterogeneous reaction of SP-B_(1−25) at the interface is quite different from that in the solution phase. In comparison with the nearly complete homogeneous oxidation of SP-B_(1−25), only a subset of the amino acids known to react with ozone are oxidized by direct ozonolysis in the hydrophobic interfacial environment, both with and without the lipid surfactant layer. Combining these experimental observations with the results of molecular dynamics simulations provides an improved understanding of the interfacial structure and chemistry of a model lung surfactant system subjected to oxidative stress

The Fourth Positive System of Carbon Monoxide in the Hubble Space Telescope Spectra of Comets

The rich structure of the Fourth Positive System (A-X) of carbon monoxide accounts for many of the spectral features seen in long slit HST-STIS observations of comets 153P/Ikeya-Zhang, C/2001 Q4 (NEAT), and C/2000 WM1 (LINEAR), as well as in the HST-GHRS spectrum of comet C/1996 B2 Hyakutake. A detailed CO fluorescence model is developed to derive the CO abundances in these comets by simultaneously fitting all of the observed A-X bands. The model includes the latest values for the oscillator strengths and state parameters, and accounts for optical depth effects due to line overlap and self-absorption. The model fits yield radial profiles of CO column density that are consistent with a predominantly native source for all the comets observed by STIS. The derived CO abundances relative to water in these comets span a wide range, from 0.44% for C/2000 WM1 (LINEAR), 7.2% for 153P/Ikeya-Zhang, 8.8% for C/2001 Q4 (NEAT) to 20.9% for C/1996 B2 (Hyakutake). The subtraction of the CO spectral features using this model leads to the first identification of a molecular hydrogen line pumped by solar HI Lyman-beta longward of 1200A in the spectrum of comet 153P/Ikeya-Zhang. (Abridged)Comment: 12 pages, 11 figures, ApJ accepte

ChemCam Investigation of the Last Four MSL Drill Sites in the Murray Formation, Gale Crater, Mars

This study utilizes ChemCam data for outcrop surfaces, drill hole walls, tailings, and dump piles in the Middle Murray Formation to investigate chemical variations with depth in the drill holes and pos-sible effects of the drilling and sample processing. This work is a continuation of similar work on drill sites at Yellowknife Bay [1], the Pahrump Hills [2], and the Stimson Formation [3]

Studies of a Lacustrine-Volcanic Mars Analog Field Site with Mars-2020-like Instruments

On the upcoming Mars‐2020 rover two remote sensing instruments, Mastcam‐Z and SuperCam, and two microscopic proximity science instruments, SHERLOC and PIXL, will collect compositional (mineralogy, chemistry, and organics) data essential for paleoenvironmental reconstruction. The synergies between and limitations of these instruments were evaluated via study of a Mars analog field site in the Mojave Desert, using instruments approximating the data that will be returned by Mars‐2020. A ground truth dataset was generated for comparison to validate the results. The site consists of a succession of clay‐rich mudstones of lacustrine origin, interbedded tuffs, a carbonate‐silica travertine deposit, and gypsiferous mudstone strata. The major geological units were mapped successfully using simulated Mars‐2020 data. Simulated Mastcam‐Z data identified unit boundaries and Fe‐bearing weathering products. Simulated SuperCam passive shortwave infrared and green Raman data were essential in identifying major mineralogical composition and changes in lacustrine facies at distance; this was possible even with spectrally downsampled passive IR data. LIBS and simulated PIXL data discriminated and mapped major element chemistry. Simulated PIXL revealed mm‐scale zones enriched in zirconium, of interest for age dating. SHERLOC‐like data mapped sulfate and carbonate at sub‐mm scale; silicates were identified with increased laser pulses/spot or by averaging of hundreds of spectra. Fluorescence scans detected and mapped varied classes of organics in all samples, characterized further with follow‐on spatially targeted deep‐UV Raman spectra. Development of dedicated organics spectral libraries is needed to aid interpretation. Given these observations, the important units in the outcrop would be sampled and cached for sample return

In situ identification of Palaeoarchaean biosignatures using co-located Perseverance rover analyses: perspectives for in situ Mars science and sample return

The NASA Mars 2020 Perseverance rover is currently exploring Jezero crater, a Noachian locality that once hosted a delta–lake system with high habitability and biosignature preservation potential. Perseverance conducts detailed appraisals of rock targets using a synergistic payload capable of geological characterisation from kilometre to micron scales. The highest-resolution textural and chemical information will be provided by correlated WATSON (imaging), SHERLOC (deep-UV Raman and fluorescence spectroscopy) and PIXL (X-ray lithochemistry) analyses, enabling the distributions of organic and mineral phases within rock targets to be comprehensively established. Herein, we analyse Palaeoarchaean microbial mats from the ~3.42 Ga Buck Reef Chert (Barberton greenstone belt) – considered astrobiological analogues for a putative Martian biosphere – following a WATSON–SHERLOC–PIXL protocol identical to that conducted by Perseverance on Mars during each sampling activities. Correlating deep-UV Raman and fluorescence spectroscopic mapping with X-ray elemental mapping, we show that the Perseverance payload has the capability to detect thermally and texturally mature organic materials of biogenic origin and can highlight organic–mineral interrelationships and elemental co-location at fine spatial scales. We also show that the Perseverance protocol obtains very similar results to high-performance laboratory imaging, Raman spectroscopy and µXRF instruments. This is encouraging for the prospect of detecting micro-scale organic-bearing textural biosignatures on Mars using the correlative micro-analytical approach enabled by WATSON, SHERLOC and PIXL; indeed, laminated, organic-bearing samples such as those studied herein are considered plausible biosignatures for a potential Noachian–Hesperian biosphere and would make compelling targets for sampling during the mission

Warm Gas in the Inner Disks around Young Intermediate Mass Stars

The characterization of gas in the inner disks around young stars is of particular interest because of its connection to planet formation. In order to study the gas in inner disks, we have obtained high-resolution K-band and M-band spectroscopy of 14 intermediate mass young stars. In sources that have optically thick inner disks, i.e. E(K-L)>1, our detection rate of the ro-vibrational CO transitions is 100% and the gas is thermally excited. Of the five sources that do not have optically thick inner disks, we only detect the ro-vibrational CO transitions from HD 141569. In this case, we show that the gas is excited by UV fluorescence and that the inner disk is devoid of gas and dust. We discuss the plausibility of the various scenarios for forming this inner hole. Our modeling of the UV fluoresced gas suggests an additional method by which to search for and/or place stringent limits on gas in dust depleted regions in disks around Herbig Ae/Be stars

Mars Hand Lens Imager (MAHLI) Efforts and Observations at the Rocknest Eolian Sand Shadow in Curiosity's Gale Crater Field Site

The Mars Science Laboratory (MSL) mission is focused on assessing the past or present habitability of Mars, through interrogation of environment and environmental records at the Curiosity rover field site in Gale crater. The MSL team has two methods available to collect, process and deliver samples to onboard analytical laboratories, the Chemistry and Mineralogy instrument (CheMin) and the Sample Analysis at Mars (SAM) instrument suite. One approach obtains samples by drilling into a rock, the other uses a scoop to collect loose regolith fines. Scooping was planned to be first method performed on Mars because materials could be readily scooped multiple times and used to remove any remaining, minute terrestrial contaminants from the sample processing system, the Collection and Handling for In-Situ Martian Rock Analysis (CHIMRA). Because of this cleaning effort, the ideal first material to be scooped would consist of fine to very fine sand, like the interior of the Serpent Dune studied by the Mars Exploration Rover (MER) Spirit team in 2004 [1]. The MSL team selected a linear eolian deposit in the lee of a group of cobbles they named Rocknest (Fig. 1) as likely to be similar to Serpent Dune. Following the definitions in Chapter 13 of Bagnold [2], the deposit is termed a sand shadow. The scooping campaign occurred over approximately 6 weeks in October and November 2012. To support these activities, the Mars Hand Lens Imager (MAHLI) acquired images for engineering support/assessment and scientific inquiry

Time Resolved Studies of Interfacial Reactions of Ozone with Pulmonary Phospholipid Surfactants Using Field Induced Droplet Ionization Mass Spectrometry

Field induced droplet ionization mass spectrometry (FIDI-MS) comprises a soft ionization method to sample ions from the surface of microliter droplets. A pulsed electric field stretches neutral droplets until they develop dual Taylor cones, emitting streams of positively and negatively charged submicrometer droplets in opposite directions, with the desired polarity being directed into a mass spectrometer for analysis. This methodology is employed to study the heterogeneous ozonolysis of 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) at the air−liquid interface in negative ion mode using FIDI mass spectrometry. Our results demonstrate unique characteristics of the heterogeneous reactions at the air−liquid interface. We observe the hydroxyhydroperoxide and the secondary ozonide as major products of POPG ozonolysis in the FIDI-MS spectra. These products are metastable and difficult to observe in the bulk phase, using standard electrospray ionization (ESI) for mass spectrometric analysis. We also present studies of the heterogeneous ozonolysis of a mixture of saturated and unsaturated phospholipids at the air−liquid interface. A mixture of the saturated phospholipid 1,2-dipalmitoyl-sn-phosphatidylglycerol (DPPG) and unsaturated POPG is investigated in negative ion mode using FIDI-MS while a mixture of 1,2-dipalmitoyl-sn-phosphatidylcholine (DPPC) and 1-stearoyl-2-oleoyl-sn-phosphatidylcholine (SOPC) surfactant is studied in positive ion mode. In both cases FIDI-MS shows the saturated and unsaturated pulmonary surfactants form a mixed interfacial layer. Only the unsaturated phospholipid reacts with ozone, forming products that are more hydrophilic than the saturated phospholipid. With extensive ozonolysis only the saturated phospholipid remains at the droplet surface. Combining these experimental observations with the results of computational analysis provides an improved understanding of the interfacial structure and chemistry of a surfactant layer system when subject to oxidative stress