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Partially Chloritized Smectites: Analogues of Smectites at Gale Crater, Mars

Characterizing the structure and composition of phyllosilicates is important for interpreting the aqueous history of Mars and identifying potential habitable environments. Smectites and chlorites are the most dominant clay types on Mars, and there is evidence of the presence of smectite/chlorite intergrades. Smectite has been detected at Gale Crater, Mars, via orbital observations and in-situ measurements, in abundances up to approximately 25 weight percentage of bulk rock. John Klein (JK) and Cumberland (CB) were analyzed by the Chemistry and Mineralogy (CheMin) and Samples Analysis at Mars (SAM) evolved gas analysis experiment (EGA) instruments, onboard Mars Science Laboratory (MSL), Curiosity, to distinguish clay mineralogy. John Klein has a collapsed 2:1 smectite with a d-spacing of 10 Angstroms, whereas Cumberland smectite did not fully collapse and has a d-spacing of approximately 13.2 Angstroms. It has been suggested that partial chloritization or ‘pillaring’ could be responsible for the expanded Cumberland smectite because pillaring inhibits the collapse of smectites down to 10 Angstrom, even under the desiccating conditions on the martian surface. Clay minerals have been detected in ancient fluvio-lacustrine rocks throughout Curiosity’s traverse and catalog the changes of the lake water chemistry and diagenetic conditions at Gale Crater, Mars. Investigating clay minerals is important for identifying them on the Martian surface, in particular as Curiosity proceeds into the upcoming Clay-bearing Unit.

Tu, V. M.↗

In situ analysis of planetary surfaces for organic materials.

Discussion of the possibility of investigating the physical, chemical, and biological state of other planets in the hope of encountering one or more that is presently in a state prior to or just after the evolution of living systems. It may then be possible to observe the chemistry at and near the surface, evaluate the sources of energy available, and search for the presence or absence of living systems, and their degree of similarity to terrestrial ones. The mass spectrometry technique is considered to be the most appropriate. A system consisting of a series of sample ovens which can be consecutively attached to the gas stream of a small gas chromatograph which is in turn connected to a mass spectrometer via a carrier gas separator has been developed for the exploration of the surface of Mars.

Biemann, K.↗

Trade Study of Five In-Situ Propellant Production System for a Mars Sample Return Mission

One of the goals of NASA''s HEDS enterprise is to establish a long-term human presence on Mars at a fraction of the cost of employing today''s technology. The most direct method of reducing mission cost is to reduce the launch mass of the spacecraft. If the propellants for the return phase of the mission are produced on Mars, the total spacecraft mass could be reduced significantly. An interim goal is a Mars Sample Return (MSR) mission, which is proposed to demonstrate the feasibility of in-situ propellant production (ISPP). Five candidate ISPP systems for producing two fuels and oxygen from the Martian atmosphere are considered in this design trade-off study:(1) Zirconia cell with methanol synthesis, (2) Reverse water gas shift (RWGS) with water electrolysis and methanol synthesis, (3) Sabatier process for methane production with water electrolysis, (4) Sabatier process with water electrolysis and partial methane pyrolysis, and (5) Sabatier/RWGS combination with water electrolysis. These systems have been the subject of numerous previous analytical studies and laboratory demonstrations. In this investigation, the systems are objectively compared on the basis of thermochemical performance models using a commonly used chemical plant analysis software package. The realistic effects of incomplete chemical conversion and gas phase separator performance are included in these models. This study focuses on the chemical processing and product separation subsystems. The CO2 compression upstream of the chemical plane and the liquefaction/storage components are not included here.

Green, S. T.↗

Preliminary Design of Robotic Control Software for Mars Sample Return - Capture, Containment, and Return System

The Mars Sample Return (MSR) campaign aims to acquire and return to Earth a set of Mars samples for investigation in terrestrial laboratories. Mars 2020 has collected an adequate number of samples and deposited them in sealed sample tubes at a designated Martian depot. Sample tubes will be placed in cylindrical containers called Orbiting Samples (OS) by the Perseverance Rover, and later brought to Earth by the Earth Return Orbiter (ERO) and the MSR - Capture, Containment, and Return System (CCRS). Robot Software (RSW) is a set of software processes for commanding and monitoring the avionics that controls robotic mechanisms designed to sterilize and install OS into Earth Entry System (EES) for return to Earth. This paper describes a preliminary design of RSW including motion modes, architecture, and finite state machine. Additionally, software engineering procedures and testing of RSW is provided. A preliminary performance analysis is presented and the paper concludes with future work and a discussion of design decisions.

MSR↗

Mineralogical, Elemental, and Tomographic Reconnaissance Investigation for CLPS (METRIC): A Payload Designed for Exploration of Terrestrial Planetary Bodies

Geological materials (indeed, all solid objects) are characterized by their crystal structure, elemental composition, and morphology. The Mineralogical, Elemental, and Tomographic Reconnaissance Investigation for CLPS (METRIC) instrument suite quantifies all three. These measurements address fundamental science questions (e.g., the origin and evolution of planetary bodies) and support the human exploration of space (e.g., the characterization of regolith for ISRU and the constraint of its geotechnical properties). METRIC comprises an X-ray Diffraction/X-ray Fluorescence instrument (XRD: mineral structure and XRF: elemental composition), an X-ray micro-Computed Tomography instrument (XCT: 3D internal micromorphology), and a hyperspectral imaging infrared spectrometer (IRS) to provide local/regional mineralogic context for these measurements. METRIC XRD/F draws heritage from the highly successful Mars Science Laboratory CheMin instrument. The METRIC XRD/F employs two separate sample cells, one optimized for XRD and one for XRF, resulting in more rapid XRD analysis (tens of minutes vs. tens of hours for CheMin) and an orders-of-magnitude improvement in XRF detection. XCT has not been deployed in space, so the METRIC XCT represents a new capability for solar system exploration. The XCT uses the same basic high-TRL components as METRIC XRD/F, decreasing its development cost for flight. The METRIC IRS is a derivative of the NASA Earth Science Technology Office funded Hyperspectral Thermal Imager instrument and utilizes the NASA Technology Transfer Program to incorporate a commercial-of-the-shelf infrared camera ruggedized for space by NASA Marshall Space Flight Center. The IRS spectral range (8–14 µm) and resolution (10.8 cm -1 ) are tailored to quantify mineralogy in rocks using their characteristic Reststrahlen bands and to characterize mineralogy of soils using the position of the Christensen Feature. The METRIC payload is currently designed for deployment to the Moon on a Commercial Lunar Payload Services (CLPS) mission, where the XRD/F and XCT would be located on a lander and the IRS would be on deployed on a companion rover to evaluate the mineralogical diversity of the landing site. A pneumatic drill designed by Honeybee Robotics would excavate regolith up to 50 cm below the lander and deliver multiple aliquots of regolith to the XRD/F and XCT. The METRIC payload could also be deployed on a rover. In this case, a sample handling system on a robotic arm could scoop regolith and/or drill rocks and deliver powder to the XRD/F and XCT located in the rover’s interior. Alternatively, METRIC instruments could be used singly or in combination on human space missions. The XRD/F and XCT could be used to characterize samples in a rover or in a science laboratory within a habitat. These data could help astronauts identify resource-enriched rocks and regolith and triage geologic samples to return samples of high interest for analysis in terrestrial laboratories. The IRS could be attached to a human-navigated rover to collect mineralogical data along a traverse and identify high-priority science samples.

E. B. Rampe↗

Low-temperature formation of magnetic iron oxides

Elemental analysis and magnetic measurements of the surface of Mars have indicated the presence of an iron oxide with a considerable magnetic moment. Identification of the oxide phase(s) is an important subject as this may be used to identify the process of weathering on the martian surface as well as the composition of the Mars regolith itself. Consequently, interest was in evidence of new formation of strongly magnetic phases (e.g., magnetite, maghemite, feroxyhyte) in terrestrially derived Mars sample analogs. Within the group of Mars sample analogs derived from low-temperature weathering of basalts in Arctic regions, evidence of magnetic oxides formed at the outermost weathering rind was never observed. However, in one instance where the weathering products accumulating in a crack of a basaltic stone were investigated, evidence of magnetite was found. The experimental details are presented.

Koch, Chr. Bender↗

Advanced Curation: Solving Current and Future Sample Return Problems

Advanced Curation is a wide-ranging and comprehensive research and development effort at NASA Johnson Space Center that identifies and remediates sample related issues. For current collections, Advanced Curation investigates new cleaning, verification, and analytical techniques to assess their suitability for improving curation processes. Specific needs are also assessed for future sample return missions. For each need, a written plan is drawn up to achieve the requirement. The plan draws while upon current Curation practices, input from Curators, the analytical expertise of the Astromaterials Research and Exploration Science (ARES) team, and suitable standards maintained by ISO, IEST, NIST and other institutions. Additionally, new technologies are adopted on the bases of need and availability. Implementation plans are tested using customized trial programs with statistically robust courses of measurement, and are iterated if necessary until an implementable protocol is established. Upcoming and potential NASA missions such as OSIRIS-REx, the Asteroid Retrieval Mission (ARM), sample return missions in the New Frontiers program, and Mars sample return (MSR) all feature new difficulties and specialized sample handling requirements. The Mars 2020 mission in particular poses a suite of challenges since the mission will cache martian samples for possible return to Earth. In anticipation of future MSR, the following problems are among those under investigation: What is the most efficient means to achieve the less than 1.0 ng/sq cm total organic carbon (TOC) cleanliness required for all sample handling hardware? How do we maintain and verify cleanliness at this level? The Mars 2020 Organic Contamination Panel (OCP) predicts that organic carbon, if present, will be present at the "one to tens" of ppb level in martian near-surface samples. The same samples will likely contain wt% perchlorate salts, or approximately 1,000,000x as much perchlorate oxidizer as organic carbon. The chemical kinetics of this reaction are poorly understood at present under the conditions of cached or curated martian samples. Among other parameters, what is the maximum temperature allowed during storage in order to preserve native martian organic compounds for analysis? What is the best means to collect headspace gases from cached martian (and other) samples? This gas will contain not only martian atmosphere but also off-gassed volatiles from the cached solids.

Fries, M.↗

Simulations of Coupled Shoulder Ablation of A Conceptual Aeroshell

The current study explores coupled numerical simulations of flow dynamics and material response affect ablation of the shoulder region of an entry capsule used in space missions like the Mars Sample Return (MSR) project. A new computational tool named Ares, developed at NASA Ames Research Center, is applied to carry out the coupled simulations by interconnecting well-established US3D (flow solver) and Icarus (material response solver), and the material considered is three-dimensional mid-density carbon phenolic (3MDCP). Particularly, this work extends the uncoupled analysis of Shrestha et al. 2022 by incorporating the coupling mechanism across the ablating surface between fluid and the capsule geometry. For simplicity, an axisymmetric geometry of the entry system is considered. A few mission-relevant parametric studies such as angles of orientation of the material layers with respect to the streamwise direction, backshell boundary conditions, and alternation of convective heat-transfer coefficients are investigated to essentially explore Ares capability with the primary focus on shoulder location.

Coupled Ablation Modeling↗

Mars Rover Sample Return: A sample collection and analysis strategy for exobiology

For reasons defined elsewhere it is reasonable to search for biological signatures, both chemical and morphological, of extinct life on Mars. Life on Earth requries the presence of liquid water, therefore, it is important to explore sites on Mars where standing bodies of water may have once existed. Outcrops of layered deposits within the Valles Marineris appear to be ancient lake beds. Because the outcrops are well exposed, relatively shallow core samples would be very informative. The most important biological signature to detect would be organics, microfossils, or larger stromato-like structures, although the presence of cherts, carbonates, clays, and shales would be significant. In spite of the limitations of current robotics and pattern recognition, and the limitations of rover power, computation, Earth communication bandwidth, and time delays, a partial scenario was developed to implement such a scientific investigation. The rover instrumentation and the procedures and decisions and IR spectrometer are described in detail. Preliminary results from a collaborative effort are described, which indicate the rover will be able to autonomously detect stratification, and hence will ease the interpretation burden and lead to greater scientific productivity during the rover's lifetime.

Sims, M. H.↗

Scientific Highlights and Status of the Mars Science Laboratory Mission, Years 9 through 12

We present the scientific highlights and status from years 9-12 of NASA’s Mars Science Laboratory mission, with its Curiosity rover. A thermochemolysis-based sample analysis revealed a variety of organic molecules preserved in clay mineral-rich lake/lake margin deposits of the Glen Torridon region. The stratigraphically higher clay-sulfate mineral transition on Aeolis Mons was found to be associated with a lithological change from lacustrine to dry aeolian depositional environments. Water intermittently returned to the surface after the increase in aridity, including during the deposition of wave ripple strata which indicate a climate capable of sustaining an ice-free lake in the early Hesperian. The overlying Mg sulfate-bearing unit has both poly- and monohydrated Mg sulfates and is also enriched in iron carbonate of a purity consistent with chemical sedimentation and therefore atmospheric sequestration. A channel-incised canyon within Gediz Vallis and distal alluvial deposits recorded numerous fluvial and debris flow events after the deposition, lithification, and erosion of the clay- and sulfate-bearing units. Bright clasts found in Gediz Vallis canyon are composed of native sulfur. The investigation of the modern atmosphere and environment focused on the influence of the crater and mountain topography and captured high-altitude noctilucent and iridescent clouds. Radiation monitoring now spans an 11-year solar cycle. Rover systems and science instruments remain capable of addressing mission scientific objectives. All ten scientific instruments continue to return high-value data despite degradation of the Chemistry and Camera instrument’s high-voltage system, loss of multispectral imaging capability, and loss of active neutron spectroscopy. The mission has mitigated the loss of redundant brakes on two arm joints, additional wheel wear, and highly reduced capability of the redundant flight computer. Efficiency improvements in rover energy utilization and operations staffing have allowed the mission team to maintain a high level of productivity despite declining rover power generation and funding.

Mars↗

Sample Handling and Processing on Mars for Future Astrobiology Missions

In most analytical investigations, there is a need to process complex field samples for the unique detection of analytes especially when detecting low concentration organic molecules that may identify extraterrestrial life. Sample processing for analytical instruments is time, resource and manpower consuming in terrestrial laboratories. Every step in this laborious process will have to be automated for in situ life detection. We have developed, and are currently demonstrating, an automated wet chemistry preparation system that can operate autonomously on Earth and is designed to operate under Martian ambient conditions. This will enable a complete wet chemistry laboratory as part of future missions. Our system, namely the Automated Sample Processing System (ASPS) receives fines, extracts organics through solvent extraction, processes the extract by removing non-organic soluble species and delivers sample to multiple instruments for analysis (including for non-organic soluble species).

Beegle, Luther↗

Contemporary Impact Analysis Methodology for Planetary Sample Return Missions

Development of an Earth entry vehicle and the methodology created to evaluate the vehicle's impact landing response when returning to Earth is reported. NASA's future Mars Sample Return Mission requires a robust vehicle to return Martian samples back to Earth for analysis. The Earth entry vehicle is a proposed solution to this Mars mission requirement. During Earth reentry, the vehicle slows within the atmosphere and then impacts the ground at its terminal velocity. To protect the Martian samples, a spherical energy absorber called an impact sphere is under development. The impact sphere is composed of hybrid composite and crushable foam elements that endure large plastic deformations during impact and cause a highly nonlinear vehicle response. The developed analysis methodology captures a range of complex structural interactions and much of the failure physics that occurs during impact. Numerical models were created and benchmarked against experimental tests conducted at NASA Langley Research Center. The postimpact structural damage assessment showed close correlation between simulation predictions and experimental results. Acceleration, velocity, displacement, damage modes, and failure mechanisms were all effectively captured. These investigations demonstrate that the Earth entry vehicle has great potential in facilitating future sample return missions.

Perino, Scott V.↗

Mission Design Overview for Mars 2003/2005 Sample Return Mission

In May 2003, a new and exciting chapter in Mars exploration will begin with the launch of the first of three spacecraft that will collectively contribute toward the goal of delivering samples from the Red Planet to Earth. This mission is called Mars Sample Return (MSR) and will utilize both the 2003 and 2005 launch opportunities with an expected sample return in October 2008. NASA and CNES are major partners in this mission. The baseline mission mode selected for MSR is Mars orbit rendezvous (MOR), analogous in concept to the lunar orbit rendezvous (LOR) mode used for Apollo in the 1960s. Specifically, MSR will employ two NASA-provided landers of nearly identical design and one CNES-provided orbiter carrying a NASA payload of rendezvous sensors, orbital capture mechanisms, and an Earth entry vehicle (EEV). The high-level concept is that the landers will launch surface samples into Mars orbit, and the orbiter will retrieve the samples in orbit and then carry them back to Earth. The first element to depart for Mars will be one of the two landers. Currently, it is proposed that an intermediate class launch vehicle, such as the Boeing Delta 3 or Lockheed Martin Atlas 3A, will launch this 1800-kg lander from Cape Canaveral during the May 2003 opportunity. The lander will utilize a Type-1 transfer trajectory with an arrival at Mars in mid-December 2003. Landing will be aided by precision approach navigation and a guided hypersonic entry to achieve a touchdown accuracy of 10 km or better. Although the exact landing site has not yet been determined, it is estimated that lander resource constraints will limit the site to between 15 degrees north and south latitudes. Following touchdown, the lander will deploy a six-wheeled, 60-kg rover carrying an extensive suite of instruments designed to aid in the analysis of the local terrain and collection of core samples from selected rocks. The surface mission is currently designed around a concept called the surface traverse. Each traverse will involve the rover exploring a selected area of terrain up to 100 meters from the lander, the collection of rock core samples, and the delivery of the samples from the traverse back to a sample canister on the lander. Planning estimates indicate that up to three traverses may be possible during the expected 90-sol lifetime of the lander. The canister that will receive the samples from the rover will be attached to the top stage of a small solid-fueled rocket mounted to the deck of the lander. This rocket is called the Mars Ascent Vehicle (MAV) and consists of three stages weighing a total of about 140 kg. After the conclusion of the surface mission, the MAV will lift-off and insert the sample canister into a near-circular orbit with an altitude of about 600 km and inclination of 45 degrees. The sample canister will wait in this orbit until it is retrieved by the orbiter sometime in early 2007. In August 2005, the second lander and a CNES-provided orbiter weighing 2700 kg will depart for Mars. Currently, it is proposed that a single Ariane 5 provided by CNES will launch both of these two elements onto a Type-2 transfer trajectory. Although the orbiter and lander will be launched together, they will separate shortly after injection and will fly to Mars as two independent spacecraft. However, both spacecraft will perform a maneuver between 10 and 15 days after launch so that their arrival times at Mars differ by between 12 and 24 hours. This scheme will reduce the operational complexity at the encounter date. A set of four 60-kg surface probes will ride piggyback on the orbiter to Mars. These CNES-provided probes are called Netlanders and will serve as surface stations for scientific investigations independent of the Mars Sample Return goals. Starting approximately one month prior to arrival at Mars, the orbiter will begin to release the Netlanders one at a time. Each release cycle will take several days, and will include time for precision navigation to execute one or two maneuvers that will target the Netlanders to their proper landing site. All four deployment cycles will be completed prior to 10 days before arrival. Both the orbiter and lander will arrive in late-July 2006. Upon arrival, the lander will perform a precision landing and surface mission similar in concept to the one that was executed during the 2003 opportunity. Although the landing site for the 2005 opportunity has not been selected, it is expected to be different from the 2003 site to enhance the diversity of the collected samples. The orbiter's arrival at Mars will be highlighted by the first use of aerocapture to insert a spacecraft into a capture orbit around another planet. The choice of aerocapture, as opposed to a propulsive orbit insertion, was considered mission enabling due to a reduction of over 2000 m/s in mission AV. Aerocapture will be targeted to produce a 250 km x 1400 km capture orbit with an inclination of 45 degrees. Current analysis indicates that achieving this goal will require approximately six minutes of flight deep in the atmosphere with a targeted periapsis of approach of about 43 km. After factoring into account the penalty for carrying a heat shield to survive aerocapture, the net savings compared to a propulsive orbital insertion amounts to several hundred kilograms.

Lee, Wayne J.↗

The In-Space Soldering Investigation: To Date Analysis of Experiments Conducted on the International Space Station

Soldering is a well established joining and repair process that is of particular importance in the electronics industry. Still, internal solder joint defects such as porosity are prevalent and compromise desired properties such as electrical/thermal conductivity and fatigue strength. Soldering equipment resides aboard the International Space Station (ISS) and will likely accompany Exploration Missions during transit to, as well as on, the moon and Mars. Unfortunately, detrimental porosity appears to be enhanced in lower gravity environments. To this end, the In-Space Soldering Investigation (ISSI) is being conducted in the Microgravity Workbench Area (MWA) aboard the ISS as "Saturday Science" with the goal of promoting our understanding of joining techniques, shape equilibrium, wetting phenomena, and microstructural development in a microgravity environment. The work presented here will focus on direct observation of melting dynamics and shape determination in comparison to ground-based samples, with implications made to processing in other low-gravity environments. Unexpected convection effects, masked on Earth, will also be shown as well as the value of the ISS as a research platform in support of Exploration Missions.

Grugel, Richard N.↗

Calibration of the MSL/ChemCam/LIBS Remote Sensing Composition Instrument

The ChemCam instrument suite on board the 2011 Mars Science Laboratory (MSL) Rover, Curiosity, will provide remote-sensing composition information for rock and soil samples within seven meters of the rover using a laser-induced breakdown spectroscopy (LIBS) system, and will provide context imaging with a resolution of 0.10 mradians using the remote micro-imager (RMI) camera. The high resolution is needed to image the small analysis footprint of the LIBS system, at 0.2-0.6 mm diameter. This fine scale analytical capability will enable remote probing of stratigraphic layers or other small features the size of "blueberries" or smaller. ChemCam is intended for rapid survey analyses within 7 m of the rover, with each measurement taking less than 6 minutes. Repeated laser pulses remove dust coatings and provide depth profiles through weathering layers, allowing detailed investigation of rock varnish features as well as analysis of the underlying pristine rock composition. The LIBS technique uses brief laser pulses greater than 10 MW/square mm to ablate and electrically excite material from the sample of interest. The plasma emits photons with wavelengths characteristic of the elements present in the material, permitting detection and quantification of nearly all elements, including the light elements H, Li, Be, B, C, N, O. ChemCam LIBS projects 14 mJ of 1067 nm photons on target and covers a spectral range of 240-850 nm with resolutions between 0.15 and 0.60 nm FWHM. The Nd:KGW laser is passively cooled and is tuned to provide maximum power output from -10 to 0 C, though it can operate at 20% degraded energy output at room temperature. Preliminary calibrations were carried out on the flight model (FM) in 2008. However, the detectors were replaced in 2009, and final calibrations occurred in April-June, 2010. This presentation describes the LIBS calibration and characterization procedures and results, and details plans for final analyses during rover system thermal testing, planned for early March.

Wiens, R. C.↗

Processing of Lunar Soil Simulant for Space Exploration Applications

NASA's long-term vision for space exploration includes developing human habitats and conducting scientific investigations on planetary bodies, especially on Moon and Mars. To reduce the level of up-mass processing and utilization of planetary in-situ resources is recognized as an important element of this vision. Within this scope and context, we have undertaken a general effort aimed primarily at extracting and refining metals, developing glass, glass-ceramic, or traditional ceramic type materials using lunar soil simulants. In this paper we will present preliminary results on our effort on carbothermal reduction of oxides for elemental extraction and zone refining for obtaining high purity metals. In additions we will demonstrate the possibility of developing glasses from lunar soil simulant for fixing nuclear waste from potential nuclear power generators on planetary bodies. Compositional analysis, x-ray diffraction patterns and differential thermal analysis of processed samples will be presented.

Sen, Subhayu↗

A Miniature Laser Desorption/Ionization Time-of-Flight Mass Spectrometer for in Situ Analysis of Mars Surface Composition and Identification of Hazard in Advance of Future Manned Exploration

Future landed missions to Mars will be guided by two strategic directions: (1) sample return to Earth, for comprehensive compositional analyses, as recommended by the 2011 NRC Planetary Decadal Survey; and (2) preparation for human exploration in the 2030s and beyond, as laid out by US space policy. The resultant mission architecture will likely require high-fidelity in situ chemical/organic sample analyses within an extremely constrained resource envelope. Both science goals (e.g., MEPAG Goal 1, return sample selection, etc.) as well as identification of any potential toxic and biological hazards to humans, must be addressed. Over the past several years of instrument development, we have found that the adaptable, compact, and highly capable technique of laser desorption/ionization time-of-flight mass spectrometry (LD-TOF-MS) has significant potential to contribute substantially to these dual objectives. This concept thus addresses Challenge Area 1: instrumentation and Investigation Approaches.

Getty, S. A.↗

Effect of Solution pH and Chloride Concentration on Akaganeite Precipitation: Implications for Akaganeite Formation on Mars

Akaganeite (Beta-FeOOH, chloride-containing Fe(III) (hydr)oxide) has been recently discovered on the surface of Mars by the Mars Science Laboratory Curiosity rover in Yellowknife Bay, Gale Crater, Mars [1] and from orbit by the Mars Reconnaissance Orbiter in Robert Sharp crater and Antoniadi basin [2]. However, the mechanism and aqueous environmental conditions of akaganeite formation (e.g., pH and chloride concentration) remain unknown. We have investigated formation of akaganeite through Fe(III) hydrolysis at variable initial pH and chloride concentrations. The formed Fe(III) precipitates were characterized by instruments similar to instruments on Mars robotic spacecraft. Syntheses were performed through hydrolysis of Fe(III) perchlorate with addition of Na cloride (Fe/Cl ratio between 0.5 and 5) and at initial pH of 1.5, 2, 4, 6 and 8 at 90degC. X-ray diffraction analysis revealed formation of akaganeite alone or in mixture with goethite, hematite and ferrihydrite at all initial pHs and Fe/Cl ratio between 0.5 and 2 while akaganeite precipitated only at pH 1.5 and Fe/Cl greater than2. Chloride content of akaganeite was affected by initial pH and decreased from 20-60 mg/g at pH 1.5 to less than 0.1 mg/g at pH 8. The synthesized akaganeite samples were also characterized by Mössbauer and infrared spectroscopy and volatiles were analysed by thermal and evolved gas analysis. The obtained characterization data will be compared to published data from rover and orbital missions [1-3] to determine martian akaganeite composition, crystallinity and formation conditions.

Peretyazhko, T. A.↗