Laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy are complementary techniques providing respectively chemical and structural information on the sample target. These techniques are ...increasingly used in Earth and Planetary sciences, and often together. LIBS is locally destructive for the target, and the laser-induced effects due to LIBS laser shots on the structure and on the Raman fingerprint of a set of geological samples relevant to Mars exploration are here investigated by Raman spectroscopy and electron microscopy. Experiments show that the structure of samples with low optical absorption coefficients is preserved as well as the structural information carried by Raman spectra. By contrast, minerals with high optical absorption coefficient can be severely affected by LIBS laser shots with local amorphization, melting and/or phase transformation. Thermal modeling shows that the temperature can reach several thousands of degrees at the surface for such samples during a LIBS laser shot, but decreases rapidly with time and in space. In 2020, NASA Mars 2020 mission will send a rover equiped with a combined LIBS/Raman instrument for remote analysis (SuperCam) as well as proximity science instruments at fine scale for X-ray fluorescence called PIXL for Planetary Instrument for X-ray Lithochemistry, and deep UV Raman spectroscopy called SHERLOC for Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals. We discuss the implications of our results for the operation of these instruments and show that (i) the SuperCam analytical footprint for Raman spectroscopy is many times larger than the LIBS crater, minimizing any effects and (ii) SHERLOC and PIXL analysis may be affected if they analyze within a LIBS crater created by SuperCam LIBS.
Display omitted
•Laser-induced heating during LIBS analysis depends on the sample optical properties.•Structure of transparent minerals is not affected by LIBS laser shots.•Opaque minerals can be severely affected by LIBS shots due to absorption.
Visible/short‐wave infrared spectral data from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) show absorptions attributed to hematite at Vera Rubin ridge (VRR), a topographic ...feature on northwest Mt. Sharp. The goals of this study are to determine why absorptions caused by ferric iron are strongly visible from orbit at VRR and to improve interpretation of CRISM data throughout lower Mt. Sharp. These goals are achieved by analyzing coordinated CRISM and in situ spectral data along the Curiosity Mars rover's traverse. VRR bedrock within areas that have the deepest ferric absorptions in CRISM data also has the deepest ferric absorptions measured in situ. This suggests strong ferric absorptions are visible from orbit at VRR because of the unique spectral properties of VRR bedrock. Dust and mixing with basaltic sand additionally inhibit the ability to measure ferric absorptions in bedrock stratigraphically below VRR from orbit. There are two implications of these findings: (1) Ferric absorptions in CRISM data initially dismissed as noise could be real, and ferric phases are more widespread in lower Mt. Sharp than previously reported. (2) Patches with the deepest ferric absorptions in CRISM data are, like VRR, reflective of deeper absorptions in the bedrock. One model to explain this spectral variability is late‐stage diagenetic fluids that changed the grain size of ferric phases, deepening absorptions. Curiosity's experience highlights the strengths of using CRISM data for spectral absorptions and associated mineral detections and the caveats in using these data for geologic interpretations and strategic path planning tools.
Plain Language Summary
Satellites orbiting Mars map the composition of the planet's surface, tell us about past environments, and guide rovers to interesting locations on the surface. The Curiosity rover investigated a ridge named Vera Rubin ridge where indications of the mineral hematite (Fe2O3) was suggested from orbital data. In this paper, we investigate why the hematite detection on the ridge was so clear from orbit and what the implications are for how the hematite formed. We found several factors influence the orbital data, but the biggest reason hematite at Vera Rubin ridge was so easily detected from orbit was because the bedrock there was unique. Water had interacted with rocks at the ridge sometime after they were deposited, and this interaction affected the properties of the hematite and made it more visible from orbit. Curiosity's data help us reinterpret the orbital data over Mt. Sharp and reveal hematite is probably present in most of the bedrock there. Furthermore, there are other areas with particularly clear hematite detections that likely formed in a similar manner as Vera Rubin ridge. We end this paper with a discussion of lessons learned from this experience for using orbital data to guide rovers in the future.
Key Points
Areas on Vera Rubin ridge with deep ferric absorptions from orbit also have deep ferric absorptions in Curiosity spectral data sets
Ferric phases are more widespread on Mt. Sharp than originally reported. Diagenesis deepened ferric absorptions in several locations
Combining orbital and in situ observations enhances planetary exploration
The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity was sent to Gale crater ...to study a sequence of ∼3.5 Ga old sedimentary rocks that, based on orbital visible and near- to short-wave infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence in the lower slopes of Mount Sharp in Gale crater preserves a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate, based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with instruments to examine the sedimentology and identify compositional changes in the stratigraphy. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer. CheMin measures loose sediment samples scooped from the surface and drilled rock powders, and the XRD provides quantitative mineralogy to a detection limit of ∼1 wt.% for crystalline phases. Curiosity has traversed >20 km since landing and has primarily been exploring an ancient lake environment fed by streams and groundwater. Of the 19 drilled rock samples analyzed by CheMin as of sol 2300 (January 2019), 15 are from fluvio-lacustrine deposits that comprise the Bradbury and Murray formations. Most of these samples were drilled from units that did not have a clear mineralogical signature from orbit. Results from CheMin demonstrate an astounding diversity in the mineralogy of these rocks that signifies geochemical variations in source rocks, transportation mechanisms, and depositional and diagenetic fluids. Most detrital igneous minerals are basaltic, but the discovery in a few samples of abundant silicate minerals that usually crystallize from evolved magmas on Earth remains enigmatic. Trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH in lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions in the lake waters themselves and/or in diagenetic fluids. Perhaps one of the biggest mysteries revealed by CheMin is the high abundance of X-ray amorphous materials (15–73 wt.%) in all samples drilled or scooped to date. CheMin has analyzed three modern eolian sands, which have helped constrain sediment transport and mineral segregation across the active Bagnold Dune Field. Ancient eolian sandstones drilled from the Stimson formation differ from modern eolian sands in that they contain abundant magnetite but no olivine, suggesting that diagenetic processes led to the alteration of olivine to release Fe(II) and precipitate magnetite. Fracture-associated halos in the Stimson and the Murray formations are evidence for complex aqueous processes long after the streams and lakes vanished from Gale crater. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.
Both the source of methane on Mars and the mechanism for transmission from the subsurface to the atmosphere are not fully understood. Previous seepage simulations have invoked relatively shallow ...subsurface sources to explain observed methane signatures on Mars. We propose that barometric‐pressure pumping through fracture networks could be an effective mechanism for methane transport from the deep subsurface on Mars. Using atmospheric pressure data gathered by Curiosity as input, we simulate methane gas transport from depths of 200 m to the surface. Even with such a deep source, our model reproduces the observed seasonality of methane, and the simulated surface methane fluxes fall within the range of previous estimates derived from atmospheric observations. Because 200 m is the likely minimum hospitable depth for living methanogenic microbes, our fracture network model indirectly reinvigorates the possibility of a microbial source of methane on Mars.
Plain Language Summary
The existence of methane on Mars is a topic of significant interest because of its potential association with subsurface microbial life. Measurements of methane in the atmosphere of Mars indicate that its abundance fluctuates over time. Although the source of methane is unknown, it most likely comes from below the surface of Mars; however, the range of depths of potential methane sources is not well constrained. If methane is currently being produced by living microbes, it would have to be at depths of at least 200 m in order to support life. Nearly all prior modeling work in this area has considered relatively slow, inefficient methane transport mechanisms, which limits the methane sources to the shallow martian subsurface. In this paper, we describe and model a mechanism capable of transporting significant quantities of methane to the atmosphere from depths capable of supporting living methane‐producing microorganisms. We also find that the methane seepage pattern generated by our model is highly seasonal, and closely follows the pattern of atmospheric methane concentrations measured by the Curiosity rover.
Key Points
Atmospheric pressure fluctuations on Mars can produce significant methane seepage from potentially habitable depths (up to 200 m)
Modeled surface methane seepage patterns are highly seasonal and coincide with rover measurements of elevated concentrations at Gale crater
Magnitude and timing of modeled surface flux is comparable to existing plume estimates, supporting a model of localized surface releases
Understanding deformation in ice shelves is necessary to evaluate the response of ice shelves to thinning. We study microseismicity associated with ice shelf deformation using nine broadband ...seismographs deployed near a rift on the Ross Ice Shelf. From December 2014 to November 2016, we detect 5,948 icequakes generated by rift deformation. Locations were determined for 2,515 events using a least squares grid‐search and double‐difference algorithms. Ocean swell, infragravity waves, and a significant tsunami arrival do not affect seismicity. Instead, seismicity correlates with tidal phase on diurnal time scales and inversely correlates with air temperature on multiday and seasonal time scales. Spatial variability in tidal elevation tilts the ice shelf, and seismicity is concentrated while the shelf slopes downward toward the ice front. During especially cold periods, thermal stress and embrittlement enhance fracture along the rift. We propose that thermal stress and tidally driven gravitational stress produce rift seismicity with peak activity in the winter.
Plain Language Summary
In Antarctica, large bodies of floating ice called ice shelves help prevent ice on land from sliding into the ocean. To predict how Antarctica might respond to climate change, we need to understand how ice shelves interact with the environment, including the atmosphere and the ocean. The largest ice shelf, the Ross Ice Shelf, is over 500,000 km2 in area, making it the largest body of floating ice in the world. In this study, we deployed nine seismographs, the same instruments used to study earthquakes, to monitor vibrations and cracking within the Ross Ice Shelf over a 2‐year period. During that time, the instruments detected nearly 6,000 fracture events along a 120‐km‐long crack in the ice shelf. We compared the timing of the cracking to air temperature data, ocean wave activity, and tides to see whether these factors influenced the crack's behavior. We found that fracture occurs most frequently just after high tide during winter and when the air is very cold. We also found that fracture at the rift is not triggered by ocean waves. This work demonstrates that Antarctic ice shelves are very sensitive to the environment and highlights the need to continue studying them.
Key Points
2,515 icequakes associated with rift deformation on the Ross Ice Shelf are located using a double‐difference location algorithm
Icequake timing correlates with tidal phase diurnally and inversely correlates with air temperature on multiday and seasonal time scales
Ocean swell, infragravity waves, and a significant tsunami arrival are not correlated with increased rift activity
ChemCam is a remote sensing instrument suite on board the “Curiosity” rover (NASA) that uses Laser-Induced Breakdown Spectroscopy (LIBS) to provide the elemental composition of soils and rocks at the ...surface of Mars from a distance of 1.3 to 7 m, and a telescopic imager to return high resolution context and micro-images at distances greater than 1.16 m. We describe five analytical capabilities: rock classification, quantitative composition, depth profiling, context imaging, and passive spectroscopy. They serve as a toolbox to address most of the science questions at Gale crater. ChemCam consists of a Mast-Unit (laser, telescope, camera, and electronics) and a Body-Unit (spectrometers, digital processing unit, and optical demultiplexer), which are connected by an optical fiber and an electrical interface. We then report on the development, integration, and testing of the Mast-Unit, and summarize some key characteristics of ChemCam. This confirmed that nominal or better than nominal performances were achieved for critical parameters, in particular power density (>1 GW/cm
2
). The analysis spot diameter varies from 350 μm at 2 m to 550 μm at 7 m distance. For remote imaging, the camera field of view is 20 mrad for 1024×1024 pixels. Field tests demonstrated that the resolution (∼90 μrad) made it possible to identify laser shots on a wide variety of images. This is sufficient for visualizing laser shot pits and textures of rocks and soils. An auto-exposure capability optimizes the dynamical range of the images. Dedicated hardware and software focus the telescope, with precision that is appropriate for the LIBS and imaging depths-of-field. The light emitted by the plasma is collected and sent to the Body-Unit via a 6 m optical fiber. The companion to this paper (Wiens et al.
this issue
) reports on the development of the Body-Unit, on the analysis of the emitted light, and on the good match between instrument performance and science specifications.
•A petrological classification is proposed adapting Earth classifications to Mars.•The classification involves the characterization of texture and chemistry.•The classification highlights the various ...categories of rocks analyzed by Curiosity.•Composition of in-place sedimentary rocks contrasts with that of igneous float rocks.
Rocks analyzed by the Curiosity rover in Gale crater include a variety of clastic sedimentary rocks and igneous float rocks transported by fluvial and impact processes. To facilitate the discussion of the range of lithologies, we present in this article a petrological classification framework adapting terrestrial classification schemes to Mars compositions (such as Fe abundances typically higher than for comparable lithologies on Earth), to specific Curiosity observations (such as common alkali-rich rocks), and to the capabilities of the rover instruments. Mineralogy was acquired only locally for a few drilled rocks, and so it does not suffice as a systematic classification tool, in contrast to classical terrestrial rock classification. The core of this classification involves (1) the characterization of rock texture as sedimentary, igneous or undefined according to grain/crystal sizes and shapes using imaging from the ChemCam Remote Micro-Imager (RMI), Mars Hand Lens Imager (MAHLI) and Mastcam instruments, and (2) the assignment of geochemical modifiers based on the abundances of Fe, Si, alkali, and S determined by the Alpha Particle X-ray Spectrometer (APXS) and ChemCam instruments. The aims are to help understand Gale crater geology by highlighting the various categories of rocks analyzed by the rover. Several implications are proposed from the cross-comparisons of rocks of various texture and composition, for instance between in place outcrops and float rocks. All outcrops analyzed by the rover are sedimentary; no igneous outcrops have been observed. However, some igneous rocks are clasts in conglomerates, suggesting that part of them are derived from the crater rim. The compositions of in-place sedimentary rocks contrast significantly with the compositions of igneous float rocks. While some of the differences between sedimentary rocks and igneous floats may be related to physical sorting and diagenesis of the sediments, some of the sedimentary rocks (e.g., potassic rocks) cannot be paired with any igneous rocks analyzed so far. In contrast, many float rocks, which cannot be classified from their poorly defined texture, plot on chemistry diagrams close to float rocks defined as igneous from their textures, potentially constraining their nature.
Laser‐induced breakdown spectroscopy (LIBS) is an active analytical technique that makes use of a laser pulse to analyze materials of interest at a distance by creating a plasma, which emits photons ...at characteristic emission line wavelengths. We validate the technique for planetary exploration under vacuum conditions. We review the capability and advantages of the LIBS technique for lunar regolith analysis at 1.5 m distance from a lunar rover, and we characterize its potential for the detection of resources for future exploration, such as the determination of regolith water content. The limits of detection determined for the major elements (typically <1 wt %) help to determine regolith parent material such as feldspathic highland rocks, rocks from the ancient magmatic high magnesian suite (Mg‐suite), Fe‐rich mare basalts or potassium, rare earth element, and phosphorus‐rich (KREEP‐rich) samples. Compositional parameters commonly used to classify lunar regoliths such as TiO2, Al2O3, and K2O abundances are readily determined by LIBS. Certain elements support regolith analysis: For example, Ba and Zr can be used to confirm KREEP‐like composition, while quantifying the Ni and Co content can be used to infer the amount of meteoritic material. Finally, it is shown that the ice content of lunar soil produces strong H emissions with the LIBS techniques at the 25 wt % H2O level, while measurements on altered basalts give a limit of detection of about 1 wt % for H2O content. This demonstrates that the 5.6 wt % water content detected by the recent LCROSS experiment should be easily detectable and quantifiable by LIBS analysis.
Key Points
Validation of LIBS technique for planetary exploration under vacuum conditions
LODs for major and minor elements are useful to determine lunar regolith sources
LIBS limit of detection for water content is about 1 wt %
PDF
