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Phyllosilicates detected throughout the Noachian terrains of Mars provide ample evidence of water-rock interactions in its geologic past, and characterizing their formation would elucidate past environmental conditions on the martian surface. Previous work suggests that ferric smectite may have been deposited in the Noachian as ferroan (Fe2+) smectite and then subsequently oxidized after formation. This is further supported by the detection of trioctahedral saponite at the base of the stratigraphic section in Gale crater by CheMin and the gradual transition to dioctahedral ferric smectite up section. A better understanding of the dissolution behavior of saponites would therefore help us better interpret past water-rock interactions at Gale crater. However, smectite structures and compositions are variable and complex, and very few saponite dissolution rates exist in the literature. To further understand past water-rock interactions at Gale crater, we are reporting our results to date from dissolution experiments of Fe- and Mg- saponites under a range of conditions.

Analyses of X-ray diffraction (XRD) patterns taken by the CheMin instrument on the Curiosity Rover in Gale crater have documented the presence of clay minerals interpreted as smectites and a suite of amorphous to short-range order materials termed X-ray amorphous materials. These X-ray amorphous materials are commonly ironrich and aluminum poor and likely some of them are weathering products rather than primary glasses due to the presence of volatiles. Outstanding questions remain regarding the chemical composition and mineral structure of these X-ray amorphous materials and the smectites present at Gale crater and what they indicate about environmental conditions during their formation. To gain a better understanding of the mineral transitions that occur within ferromagnesian parent materials, we have investigated the development of secondary clay minerals and shortrange order materials in two soil chronosequences with varying climates developing on ultramafic bedrock. Field Sites: We investigated soil weathering within two field locations, the Klamath Mountains of Northern California, and the Tablelands of Newfoundland, Canada. Both sites possess age dated or correlated recently deglaciated soils and undated but substantially older soils. In the Klamath mountains the Trinity Ultramafic Body was deglaciated roughly 15,000 years bp while in the Tablelands a moraine was dated to about 17,600 years bp. The Klamath Mountains feature a seasonally wet and dry climate while the Tablelands are wet year-round with saturated soil conditions observed during sampling and standing water observed within 3 of 4 soil pit sampling locations.

One of the most exciting endeavors in modern space exploration is extended human exploration of the Moon and Mars. We have entered a new phase in the human venture where we seek to expand our "...presence deeper into space and to the Moon for sustainable long-term exploration and utilization". With this endeavor come new challenges. Among them is the requirement for In Situ Resource Utilization (ISRU) methods to supplement or replace materials transported from Earth. The energy required to leave Earth's gravity well is immense, as is well illustrated by the nearly 3000 metric ton Saturn V required to deliver a payload of less than 50 metric tons to the Moon during the Apollo era. Much of this mass is propellant. Launch vehicles from Earth into space are generally 85 to 95% propellant (oxidizer + fuel) by mass. Potential ascent vehicles from Mars would also need to be approximately 80% propellant by mass to return to Earth. ISRU of fuel reactants could exchange delivered fuel mass directly for payload mass on the order of several metric tons. Devices like MOXIE are being designed to address the oxidizer component. However, 40% of the propellant mass in an ascent vehicle is the fuel reactant, and ISRU of this component has not been addressed for Mars or the Moon. Toward addressing this need, we have begun to develop and optimize methods to generate and recover fuel components, including H2, from Lunar and Martian relevant materials as potential in situ resources for future extended human missions. Hydrogen is an ideal resource to target. Not only can H2 be used directly as part of a propellant, it can also be used as a component in other fuels, such as methane. It is useful agriculturally for fixing nitrogen and can be oxidized to produce heat and water.

Recent work suggests that the mineralogical sequence of the Murray formation at Gale crater may have resulted from diagenetic alteration after sedimentation, or deposition in a stratified lake with oxic surface and anoxic bottom waters. Fe-containing clay minerals are common both at Gale crater, and throughout the Noachian-aged terrains on Mars. These clay minerals are primarily ferric (Fe3+), and previous work suggests that these ferric clay minerals may result from alteration of ferrous (Fe2+) smectites that were oxidized after deposition. The detection of trioctahedral smectites at Gale crater by CheMin suggests Fe2+ smectite was also deposited during the early Hesperian. However, due to their sensitivity to oxygen, Fe2+ smectites are difficult to analyze on Earth and very few saponite dissolution rates exist in the literature. To the best of our knowledge, no experiments have measured the dissolution rates of ferrous saponites under oxidizing and reducing conditions. In order to better understand the characteristics of water-rock interaction at Gale crater, particularly the oxidation state, we report our results to date on ongoing syntheses of ferrous and magnesium saponites and dissolution experiments of natural saponite under ambient conditions. Future experiments will include the dissolution of synthetic ferric, ferrous, and magnesium saponites under oxidizing and anoxic conditions at a range of pH values.

Recent analyses of X-ray diffraction (XRD) data from the CheMin instrument using the FULLPAT program have documented the presence of X-ray amorphous materials at multiple sites within Gale Crater, Mars. These materials are believed to be to be iron-rich based on chemical data, and at least some of them are believed to be weathering products based on volatile contents. However, the characteristics of these proposed Fe-rich weathering products remain poorly understood. To better understand these X-ray amorphous materials on Mars, we are 1) examining weathering products formed on Fe-rich parent material in terrestrial soils across a range of climatic conditions, and 2) performing burial experiments of Fe- and Mg- rich olivine in these soils. We describe each of these approaches below.

Abundant evidence for liquid water exists at Gale crater, Mars. However, the characteristics of past water remain an area of active research. The first exposures of the Murray formation in Gale crater, Mars (Fig. 1) were studied with four samples analyzed using CheMin: Buckskin, Telegraph Peak, Mojave, and Confidence Hills. Analyses indicate differences in mineralogy and chemistry between the samples which have been attributed to changes in pH and oxidation state of depositional and diagenetic environments. Recent work also suggests that hydrothermal fluids may have been present based on the presence of Se, Zn, Pb, and other elements.

Seeking the signs of life on Mars is often considered the "first among equal" objectives for any potential Mars Sample Return (MSR) campaign. Among the geological settings considered to have the greatest potential for recording evidence of ancient life or its pre-biotic chemistry on Mars are lacustrine (and marine, if ever present) sedimentary depositional environments. This potential, and the possibility of returning samples that could meaningfully address this objective, have been greatly enhanced by investigations of an ancient redox stratified lake system in Gale crater by the Curiosity rover.

Highly promising locales for biosignature prospecting on Mars are ancient hydrothermal deposits, formed by the interaction of surface water with heat from volcanism or impacts. On Earth, they occur throughout the geological record (to at least approx. 3.5 Ga), preserving robust mineralogical, textural and compositional evidence of thermophilic microbial activity. Hydrothermal systems were likely present early in Mars' history, including at two of the three finalist candidate landing sites for M2020, Columbia Hills and NE Syrtis Major. Hydrothermal environments on Earth's surface are varied, constituting subaerial hot spring aprons, mounds and fumaroles; shallow to deep-sea hydrothermal vents (black and white smokers); and vent mounds and hot-spring discharges in lacustrine and fluvial settings. Biological information can be preserved by rapid, spring-sourced mineral precipitation, but also could be altered or destroyed by postdepositional events. Thus, field observations need to be followed by detailed laboratory analysis to verify potential biosignatures. See Attachment

Investigations with the CheMin Xray Diffractometer (XRD) onboard the Curiosity rover in Gale Crater demonstrate that all rock and soil samples measured to date contain approximately 15-70 weight percentage X-ray amorphous materials. The diffuse scattering hump from the X-ray amorphous materials in CheMin XRD patterns can be fit with a combination of allophane, ferrihydrite, and rhyolitic and basaltic glass. Because of the iron-rich nature of Mars' surface, Fe-rich poorly-crystalline phases, such as hisingerite, may be present in addition to allophane.

The 2011 Visions & Voyages Planeary Science Decadal Survey identified making significant progress toward the return of samples from Mars as the highest priority goal for flagship missions in next decade. Numerous scientific objectives have been identified that could be advanced through the potential return and analysis of martian rock, regolith, and atmospheric samples. The analysis of returned martian samples would be particularly valuable in in-creasing our understanding of Early Mars. There are many outstanding gaps in our knowledge about Early Mars in areas such as potential astrobiology, geochronology, planetary evolution (including the age, context, and processes of accretion, differentiation, magmatic, and magnetic history), the history of water at the martian surface, and the origin and evolution of the martian atmosphere. Here we will discuss scientific objectives that could be significantly advanced by Mars sample return.

Water flowing through sediments at Gale Crater, Mars created environments that were likely habitable, and sampled basin-wide hydrological systems. However, many questions remain about these environments and the fluids that generated them. Measurements taken by the Mars Science Laboratory Curiosity of multiple fracture zones can help constrain the environments that formed them because they can be compared to nearby associated parent material (Figure 1). For example, measurements of altered fracture zones from the target Greenhorn in the Stimson sandstone can be compared to parent material measured in the nearby Big Sky target, allowing constraints to be placed on the alteration conditions that formed the Greenhorn target from the Big Sky target. Similarly, CheMin measurements of the powdered < 150 micron fraction from the drillhole at Big Sky and sample from the Rocknest eolian deposit indicate that the mineralogies are strikingly similar. The main differences are the presence of olivine in the Rocknest eolian deposit, which is absent in the Big Sky target, and the presence of far more abundant Fe oxides in the Big Sky target. Quantifying the changes between the Big Sky target and the Rocknest eolian deposit can therefore help us understand the diagenetic changes that occurred forming the Stimson sedimentary unit. In order to interpret these aqueous changes, we performed reactive transport modeling of 1) the formation of the Big Sky target from a Rocknest eolian deposit-like parent material, and 2) the formation of the Greenhorn target from the Big Sky target. This work allows us to test the relationships between the targets and the characteristics of the aqueous conditions that formed the Greenhorn target from the Big Sky target, and the Big Sky target from a Rocknest eolian deposit-like parent material.

The Mars 2020 rover will collect carefully selected samples of rock and regolith as it explores a potentially habitable ancient environment on Mars. Using the drill, rock cores and regolith will be collected directly into ultraclean sample tubes that are hermetically sealed and, later, deposited on the surface of Mars for potential return to Earth by a subsequent mission. Thorough characterization of any contamination of the samples at the time of their analysis will be essential for achieving the objectives of Mars returned sample science (RSS). We refer to this characterization as contamination knowledge (CK), which is distinct from contamination control (CC). CC is the set of activities that limits the input of contaminating species into a sample, and is specified by requirement thresholds. CK consists of identifying and characterizing both potential and realized contamination to better inform scientific investigations of the returned samples. Based on lessons learned by other sample return missions with contamination-sensitive scientific objectives, CC needs to be "owned" by engineering, but CK needs to be "owned" by science. Contamination present at the time of sample analysis will reflect the sum of contributions from all contamination vectors up to that point in time. For this reason, understanding the integrated history of contamination may be crucial for deciphering potentially confusing contaminant-sensitive observations. Thus, CK collected during the Mars sample return (MSR) campaign must cover the time period from the initiation of hardware construction through analysis of returned samples in labs on Earth. Because of the disciplinary breadth of the scientific objectives of MSR, CK must include a broad spectrum of contaminants covering inorganic (i.e., major, minor, and trace elements), organic, and biological molecules and materials.

The mass-normalized dissolution rates measured in this study demonstrate that hisingerite and Fe-substituted allophane dissolve rapidly, much faster than crystalline phyllosilicates such as nontronite and kaolinite that have similar compositions. In addition, hisingerite dissolves more rapidly than allophane. Future work will focus on measuring dissolution rates at other pH values, so that dissolution rate laws for allophane and hisingerite can be derived. Results will be used to interpret data from Gale Crater. These initial experiments suggest that, if the liquid water present in Gale Crater was highly acidic, it was likely present for only a short time, allowing some amorphous soil-material similar to allophane to persist. Further experiments will enable us to constrain the timescales over which liquid water was present in Gale Crater and provide insight into its pH. This information is essential to assessing the potential habitability of ancient Mars.

The Returned Sample Science Board (RSSB) was established in 2015 by NASA to provide expertise from the planetary sample community to the Mars 2020 Project. The RSSB's first task was to address the effect of heating during acquisition and storage of samples on scientific investigations that could be expected to be conducted if the samples are returned to Earth. Sample heating may cause changes that could ad-versely affect scientific investigations. Previous studies of temperature requirements for returned mar-tian samples fall within a wide range (-73 to 50 degrees Centigrade) and, for mission concepts that have a life detection component, the recommended threshold was less than or equal to -20 degrees Centigrade. The RSSB was asked by the Mars 2020 project to determine whether or not a temperature requirement was needed within the range of 30 to 70 degrees Centigrade. There are eight expected temperature regimes to which the samples could be exposed, from the moment that they are drilled until they are placed into a temperature-controlled environment on Earth. Two of those - heating during sample acquisition (drilling) and heating while cached on the Martian surface - potentially subject samples to the highest temperatures. The RSSB focused on the upper temperature limit that Mars samples should be allowed to reach. We considered 11 scientific investigations where thermal excursions may have an adverse effect on the science outcome. Those are: (T-1) organic geochemistry, (T-2) stable isotope geochemistry, (T-3) prevention of mineral hydration/dehydration and phase transformation, (T-4) retention of water, (T-5) characterization of amorphous materials, (T-6) putative Martian organisms, (T-7) oxidation/reduction reactions, (T-8) (sup 4) He thermochronometry, (T-9) radiometric dating using fission, cosmic-ray or solar-flare tracks, (T-10) analyses of trapped gasses, and (T-11) magnetic studies.

The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.

Phosphate mobility has been postulated as an indicator of early aqueous activity on Mars. In addition, rock surfaces analyzed by the Mars Exploration Rover Spirit are consistent with the loss of a phosphate- containing mineral To interpret phosphate alteration behavior on Mars, we performed column dissolution experiments leaching the primary phases Durango fluorapatite, San Carlos olivine, and basalt glass (Stapafjell Volcano, courtesy of S. Gislason, University of Iceland) [3,4]) with acidic solutions. These phases were chosen to represent quickly dissolving phases likely present in Columbia Hills. Column dissolution experiments are closer to natural dissolution conditions than batch experiments, although they can be difficult to interpret. Acidic solutions were used because the leached layers on the surfaces of these rocks have been interpreted as resulting from acid solutions [5].

Sample return from Mars offers the promise of data from Martian materials that have previously only been available from meteorites. Return of carefully selected samples may yield more information about the history of water and possible habitability through Martian history. Here we propose that samples collected from Mars should include depth profiles of material across the interface between weathered material on the surface of Mars into unweathered parent rock material. Such profiles have the potential to yield chemical kinetic data that can be used to estimate the duration of water and information about potential habitats on Mars.

Phosphorus is an essential nutrient for terrestrial life, and therefore may be important in characterizing habitability on Mars. In addition, phosphate mobility on Mars has been postulated as an indicator of early aqueous activity [1]. Rock surfaces analyzed by the Spirit Mars Exploration Rover indicate elemental concentrations consistent with the loss of a phosphate-containing mineral [2], and the highly altered Paso Robles deposit contains ~5% P2O5, modeled as 8-10 % phosphate [3]. Depending on the pH of the solution, phosphate can exist as one of four charge states, which can affect its solubility, reactivity and mobility. Phosphate may therefore prove a useful and interesting tracer of alteration conditions on Mars. Acid vapor weathering has been previously studied as a potentially important process on Mars [4-6], and Paso Robles may have been formed by reaction of volcanic vapors with phosphate-bearing rock [3, 7]. Here we present preliminary results of acid vapor reactions in a Parr vessel [6] using fluorapatite, olivine and glass as single phases and in a mixture.