■ CONTENTS General Information: Books, Reviews, and Conferences 640 Fundamentals 641 Interaction of Laser Beam with Matter 641 Factors Affecting Laser Ablation and LaserInduced Plasma Formation 642 Influence of Target on the Laser-Induced Plasmas 642 Influence of Laser Parameters on the LaserInduced Plasmas 643 Laser Wavelength (λ) 643 Laser Pulse Duration (τ) 643 Laser Pulse Energy (E) 645 Influence of Ambient Gas on the Laser-Induced Plasmas 645 LIBS Methods 647 Double Pulse LIBS 647 Femtosecond LIBS 651 Resonant LIBS 652 Ranging Approaches 652 Applications 654 Surface Inspection, Depth Profiling, and LIBS Imaging 654 Cultural Heritage 654 Industrial Analysis 655 Environmental Monitoring 656 Biomedical and Pharmaceutical Analysis 658 Security and Forensics 659 Analysis of Liquids and Submerged Solids 660 Space Exploration and Isotopic Analysis 662 Space Exploration 662 Isotopic Analysis 662 Conclusions and Future Outlook 663 Author Information 664 Corresponding Author 664 Notes 664 Biographies 664 Acknowledgments 664 References 664

Laser-induced breakdown spectroscopy.

Scheduled to land in August of 2012, the Mars Science Laboratory (MSL) Mission was initiated to explore the habitability of Mars. This includes both modern environments as well as ancient environments recorded by the stratigraphic rock record preserved at the Gale crater landing site. The Curiosity rover has a designed lifetime of at least one Mars year (∼23 months), and drive capability of at least 20 km. Curiosity’s science payload was specifically assembled to assess habitability and includes a gas chromatograph-mass spectrometer and gas analyzer that will search for organic carbon in rocks, regolith fines, and the atmosphere (SAM instrument); an x-ray diffractometer that will determine mineralogical diversity (CheMin instrument); focusable cameras that can image landscapes and rock/regolith textures in natural color (MAHLI, MARDI, and Mastcam instruments); an alpha-particle x-ray spectrometer for in situ determination of rock and soil chemistry (APXS instrument); a laser-induced breakdown spectrometer to remotely sense the chemical composition of rocks and minerals (ChemCam instrument); an active neutron spectrometer designed to search for water in rocks/regolith (DAN instrument); a weather station to measure modern-day environmental variables (REMS instrument); and a sensor designed for continuous monitoring of background solar and cosmic radiation (RAD instrument). The various payload elements will work together to detect and study potential sampling targets with remote and in situ measurements; to acquire samples of rock, soil, and atmosphere and analyze them in onboard analytical instruments; and to observe the environment around the rover. The 155-km diameter Gale crater was chosen as Curiosity’s field site based on several attributes: an interior mountain of ancient flat-lying strata extending almost 5 km above the elevation of the landing site; the lower few hundred meters of the mountain show a progression with relative age from clay-bearing to sulfate-bearing strata, separated by an unconformity from overlying likely anhydrous strata; the landing ellipse is characterized by a mixture of alluvial fan and high thermal inertia/high albedo stratified deposits; and a number of stratigraphically/geomorphically distinct fluvial features. Samples of the crater wall and rim rock, and more recent to currently active surface materials also may be studied. Gale has a well-defined regional context and strong evidence for a progression through multiple potentially habitable environments. These environments are represented by a stratigraphic record of extraordinary extent, and insure preservation of a rich record of the environmental history of early Mars. The interior mountain of Gale Crater has been informally designated at Mount Sharp, in honor of the pioneering planetary scientist Robert Sharp. The major subsystems of the MSL Project consist of a single rover (with science payload), a Multi-Mission Radioisotope Thermoelectric Generator, an Earth-Mars cruise stage, an entry, descent, and landing system, a launch vehicle, and the mission operations and ground data systems. The primary communication path for downlink is relay through the Mars Reconnaissance Orbiter. The primary path for uplink to the rover is Direct-from-Earth. The secondary paths for downlink are Direct-to-Earth and relay through the Mars Odyssey orbiter. Curiosity is a scaled version of the 6-wheel drive, 4-wheel steering, rocker bogie system from the Mars Exploration Rovers (MER) Spirit and Opportunity and the Mars Pathfinder Sojourner. Like Spirit and Opportunity, Curiosity offers three primary modes of navigation: blind-drive, visual odometry, and visual odometry with hazard avoidance. Creation of terrain maps based on HiRISE (High Resolution Imaging Science Experiment) and other remote sensing data were used to conduct simulated driving with Curiosity in these various modes, and allowed selection of the Gale crater landing site which requires climbing the base of a mountain to achieve its primary science goals. The Sample Acquisition, Processing, and Handling (SA/SPaH) subsystem is responsible for the acquisition of rock and soil samples from the Martian surface and the processing of these samples into fine particles that are then distributed to the analytical science instruments. The SA/SPaH subsystem is also responsible for the placement of the two contact instruments (APXS, MAHLI) on rock and soil targets. SA/SPaH consists of a robotic arm and turret-mounted devices on the end of the arm, which include a drill, brush, soil scoop, sample processing device, and the mechanical and electrical interfaces to the two contact science instruments. SA/SPaH also includes drill bit boxes, the organic check material, and an observation tray, which are all mounted on the front of the rover, and inlet cover mechanisms that are placed over the SAM and CheMin solid sample inlet tubes on the rover top deck.

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Mars Science Laboratory Mission and Science Investigation

Sedimentary rocks at Yellowknife Bay (Gale crater) on Mars include mudstone sampled by the Curiosity rover. The samples, John Klein and Cumberland, contain detrital basaltic minerals, calcium sulfates, iron oxide or hydroxides, iron sulfides, amorphous material, and trioctahedral smectites. The John Klein smectite has basal spacing of similar to 10 angstroms, indicating little interlayer hydration. The Cumberland smectite has basal spacing at both similar to 13.2 and similar to 10 angstroms. The larger spacing suggests a partially chloritized interlayer or interlayer magnesium or calcium facilitating H2O retention. Basaltic minerals in the mudstone are similar to those in nearby eolian deposits. However, the mudstone has far less Fe-forsterite, possibly lost with formation of smectite plus magnetite. Late Noachian/Early Hesperian or younger age indicates that clay mineral formation on Mars extended beyond Noachian time.

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Mineralogy of a Mudstone at Yellowknife Bay, Gale Crater, Mars

Observations by the Mars Science Laboratory Mast Camera (Mastcam) in Gale crater reveal isolated outcrops of cemented pebbles (2 to 40 millimeters in diameter) and sand grains with textures typical of fluvial sedimentary conglomerates. Rounded pebbles in the conglomerates indicate substantial fluvial abrasion. ChemCam emission spectra at one outcrop show a predominantly feldspathic composition, consistent with minimal aqueous alteration of sediments. Sediment was mobilized in ancient water flows that likely exceeded the threshold conditions (depth 0.03 to 0.9 meter, average velocity 0.20 to 0.75 meter per second) required to transport the pebbles. Climate conditions at the time sediment was transported must have differed substantially from the cold, hyper-arid modern environment to permit aqueous flows across several kilometers.

https://science.sciencemag.org/content/sci/340/6136/1068.full.pdf

Martian Fluvial Conglomerates at Gale Crater

Sedimentary rocks examined by the Curiosity rover at Yellowknife Bay, Mars, were derived from sources that evolved from an approximately average martian crustal composition to one influenced by alkaline basalts. No evidence of chemical weathering is preserved, indicating arid, possibly cold, paleoclimates and rapid erosion and deposition. The absence of predicted geochemical variations indicates that magnetite and phyllosilicates formed by diagenesis under low-temperature, circumneutral pH, rock-dominated aqueous conditions. Analyses of diagenetic features (including concretions, raised ridges, and fractures) at high spatial resolution indicate that they are composed of iron- and halogen-rich components, magnesium-iron-chlorine–rich components, and hydrated calcium sulfates, respectively. Composition of a cross-cutting dike-like feature is consistent with sedimentary intrusion. The geochemistry of these sedimentary rocks provides further evidence for diverse depositional and diagenetic sedimentary environments during the early history of Mars.

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Elemental Geochemistry of Sedimentary Rocks at Yellowknife Bay, Gale Crater, Mars.

The ChemCam instrument suite on the Mars Science Laboratory (MSL) rover Curiosity provides remote compositional information using the first laser-induced breakdown spectrometer (LIBS) on a planetary mission, and provides sample texture and morphology data using a remote micro-imager (RMI). Overall, ChemCam supports MSL with five capabilities: remote classification of rock and soil characteristics; quantitative elemental compositions including light elements like hydrogen and some elements to which LIBS is uniquely sensitive (e.g., Li, Be, Rb, Sr, Ba); remote removal of surface dust and depth profiling through surface coatings; context imaging; and passive spectroscopy over the 240–905 nm range. ChemCam is built in two sections: The mast unit, consisting of a laser, telescope, RMI, and associated electronics, resides on the rover’s mast, and is described in a companion paper. ChemCam’s body unit, which is mounted in the body of the rover, comprises an optical demultiplexer, three spectrometers, detectors, their coolers, and associated electronics and data handling logic. Additional instrument components include a 6 m optical fiber which transfers the LIBS light from the telescope to the body unit, and a set of onboard calibration targets. ChemCam was integrated and tested at Los Alamos National Laboratory where it also underwent LIBS calibration with 69 geological standards prior to integration with the rover. Post-integration testing used coordinated mast and instrument commands, including LIBS line scans on rock targets during system-level thermal-vacuum tests. In this paper we describe the body unit, optical fiber, and calibration targets, and the assembly, testing, and verification of the instrument prior to launch.

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Joseph Latino

Papers

The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Body Unit and Combined System Tests