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Mineralogical Trends Over the Clay-Sulfate Transition in Gale Crater from the Mars Science Laboratory CheMin Instrument

The Mars Science Laboratory Curiosity rover landed in Gale crater in 2012 to explore a sedimentary sequence in lower Aeolis Mons (informally known as Mount Sharp)that shows changes in mineralogy from orbital visible/near-infrared reflectance spectroscopy[1]. Sedimentary layers with spectral signatures of hydrated Mg sulfate overly layers with signatures of Fe/Mg smectite, a mineralogical stratigraphy that is seen in other ancient sedimentary rocks across Mars[e.g., 2-4]. Curiosity recently completed its campaign in a valley with a strong orbital signature of smectite, named Glen Torridon. Mineralogical measurements by the CheMin X-ray diffractometer(XRD), complemented by evolved gas analyses by the Sample Analysis at Mars (SAM) instrument suite, allowed the identification of abundant Fe3+-bearing dioctahedral smectite (i.e., nontronite) in Glen Torridon [5-6]. Curiosity left Glen Torridon in February 2021 and began traversing through a “clay-sulfate transition” zone on the way to the pediment and the sulfate unit[e.g., 7]. This clay-sulfate transition is defined in orbital reflectance spectroscopy as having a weak signature of hydrated Mg sulfate. Curiosity has drilled five outcrops over the traverse through the clay-sulfate transition and delivered the rock powders to CheMin for mineralogical analysis. Here, we report on the mineral assemblages of those five targets derived from CheMin XRD patterns and discuss mineralogical trends as the rover approaches the sulfate unit.

Mars↗

Synthesis of Ti Oxides at Reducing Conditions: Implications for Beamline Standards and Cosmochemistry

These initial experiments demonstrate the great potential for synthesizing customized compounds for use as standards, or in buffering experiments at reducing conditions. We are also investigating Cr and V oxides, as well as compounds containing these elements such as FeV2O4 and FeCr2O4. Oxygen fugacity exerts a major control on mineral major element chemistry and elemental valence of minerals in any plane-tary compositional system [1]. For Earth, Fe is multivalent ranging from nearly Fe0 at low fO2 in the deep mantle to Fe2+ to Fe3+ at high low fO2. For solar nebular and meteoritic materials fO2 ranges from near IW to ~10 log fO2 units below the IW buffer [1]. Phases in CAIs, for example, contain no Fe2+, but may contain Ti4+, Ti3+, or Ti2+, and Cr3+ or Cr2+, and V3+ or V2+ [1,2,3]. De-tailed study of inclusions may reveal important differences in fO2 thus reflecting different environments in the solar nebula [4]. XANES, FEG-SEM, and TEM can reveal such variations in micro and nano samples such as Stardust and cosmic dust particles [5], but successful application to reduced conditions depends upon the availability of well characterized standards. Acquiring appropriate standards for reduced phases that contain Ti3+ or Ti2+, Cr3+ or Cr2+, and V3+ or V2+ can be a challenge. Here we report our preliminary results at synthesizing reduced Ti bearing standards, and focus on the preliminary characterization.

Righter, K.↗

Electron Beam Damage in Apatite: Limitations for SKα Measurements of S6+/∑S

In magmatic systems, the availabil- ity of excess oxygen that can react with multivalent elements such as Fe and S to change their charge (oxi- dation of Fe2+ to Fe3+ or reduction of S6+ to S2-) is characterized by a parameter called the oxygen fugacity (ƒO2). The ƒO2 controls the availability of these ions and consequently the minerals—and the chemistry of those minerals—that crystallize from a melt. Mineral mode and chemistry control how magmas evolve, and given that ƒO2 varies by many orders of magnitude on different planets [2], understanding the ƒO2 of a mag- ma is critical to relating observations about a magma to the body on which it forms. The mineral apatite was long thought to only incor- porate S6+ in a coupled substitution for P5+, but recently natural apatites with S2- were identified in lunar mare basalts that crystallized at low ƒO2 [3]. This suggests that apatite can be used as a monitor of ƒO2 assuming that one can 1) measure S6+/∑S (S6+ over total sulfur), and 2) determine some partitioning relationship be- tween apatite and melt for S6+ and S2-. The most common method for measuring S6+/∑S is X-ray Absorption Near-Edge Spectroscopy (XANES), but given the limited access to synchrotron facilities, it is wise to explore the potential of other methods for measuring S6+/∑S. One such possible method relies upon the shift in energy of the sulfur K-α peak on the electron microprobe. However, apatite is subject to well-documented beam damage [4, 5], so it is neces- sary to evaluate under what conditions can reliable S6+ ethod.

de Chizelle, J. Kuhn↗

Experimental Acid Weathering of Fe-Bearing Mars Analog Minerals and Rocks: Implications for Aqueous Origin of Hematite-Bearing Sediments in Meridiani Planum, Mars

A working hypothesis for Meridiani evaporite formation involves the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [1, 2]. However, there are no reported experimental studies for the formation of jarosite and gray hematite (spherules), which are characteristic of Meridiani rocks from Mars analog precursor minerals. A terrestrial analog for hematite spherule formation from basaltic rocks under acidic hydrothermal conditions has been reported [3], and we have previously shown that the hematite spherules and jarosite can be synthetically produced in the laboratory using Fe3+ -bearing sulfate brines under hydrothermal conditions [4]. Here we expand and extend these studies by reacting Mars analog minerals with sulfuric acid to form Meridiani-like rock-mineral compositions. The objective of this study is to provide environmental constraints on past aqueous weathering of basaltic materials on Mars.

Golden, D. C.↗

Magnetite in Martian Meteorite Mil 03346 and Gusev Adirondack Class Basalt: Moessbauer Evidence for Variability in the Oxidation State of Adirondack Lavas

The Moessbauer spectrometers on the Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) have returned information on the oxidation state of iron, the mineralogical composition of Fe-bearing phases, and the distribution of Fe among oxidation states and phases [1,2,3]. To date, ~100 and ~85 surface targets have been analyzed by the Spirit and Opportunity spectrometers, respectively. Twelve component subspectra (8 doublets and 4 sextets) have been identified and most have been assigned to mineralogical compositions [4]. Two sextet subspectra result from the opaque and strongly magnetic mineral magnetite (Fe3O4 for the stoichiometric composition), one each for the crystallographic sites occupied by tetrahedrally-coordinated Fe3+ and by octahedrally-coordinated Fe3+ and Fe2+. At Gusev crater, the percentage of total Fe associated with magnetite for rocks ranges from 0 to ~ 35% (Fig. 1) [3]. The range for soils (~5 to ~12% of total Fe from Mt, with one exception) is narrower. The ubiquitous presence of Mt in soil firmly establishes the phase as the strongly magnetic component in martian soil

Morris, R. V.↗

Magnetite in Martian Meteorite Mil 03346 and Gusev Adirondack Class Basalt: Mossbauer Evidence for Variability in the Oxidation State of Adirondack Lavas

The Moessbauer spectrometers on the Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) have returned information on the oxidation state of iron, the mineralogical composition of Fe-bearing phases, and the distribution of Fe among oxidation states and phases [1,2,3]. To date, approx.100 and approx.85 surface targets have been analyzed by the Spirit and Opportunity spectrometers, respectively. Twelve component subspectra (8 doublets and 4 sextets) have been identified and most have been assigned to mineralogical compositions [4]. Two sextet subspectra result from the opaque and strongly magnetic mineral magnetite (Fe3O4 for the stoichiometric composition), one each for the crystallographic sites occupied by tetrahedrally-coordinated Fe3+ and by octahedrally-coordinated Fe3+ and Fe2+. At Gusev crater, the percentage of total Fe associated with magnetite for rocks ranges from 0 to approx. 35% (Fig. 1) [3]. The range for soils (approx.5 to approx.12% of total Fe from Mt, with one exception) is narrower. The ubiquitous presence of Mt in soil firmly establishes the phase as the strongly magnetic component in martian soil [4,5].

Morris, R. V.↗

An Overview of Moessbauer Mineralogy at Gusev Crater, Mars

The Mars Exploration Rover (MER) Spirit landed on the plains of Gusev Crater on 4 January 2004 [1]. The scientific objective of the Moessbauer (MB) spectrometer on Spirit is to provide quantitative information about the distribution of Fe among its oxidation and coordination states, identification of Fe-bearing phases, and relative distribution of Fe among those phases. The speciation and distribution of Fe in Martian rock and soil constrains the primary rock types, redox conditions under which primary minerals crystallized, the extent of alteration and weathering, the type of alteration and weathering products, and the processes and environmental conditions for alteration and weathering.We discuss the Fe-bearing phases detected by Spirit s MB instrument during its first 540 sols of exploration [2,3]. Spirit roved eastward across the plains from its landing site to the Columbia Hills during the first approx.150 sols. Rocks are unweathered to weakly weathered olivine basalt, with olivine, pyroxene (Ol > Px), magnetite (Mt), and minor hematite (Hm) and nanophase ferric oxide (npOx) as their primary Fe-bearing minerals. Soils are generally similar basaltic materials, except that the proportion of npOx is much higher (up to approx.40%). NpOx is an oct-Fe3+ alteration product whose concentration is highest in fine-grained soils and lowest in rock interiors exposed by grinding with the Rock Abrasion Tool (RAT). Spirit explored the lower slopes of the Columbia Hills (West Spur) during sols approx.150-320. West Spur rocks are highly altered, even for interior surfaces exposed by grinding (Fe3+/FeT approx.0.56-0.84). High concentrations of npOx, Hm, and Mt are present. One rock (Clovis) contains significant quantities of goethite (alpha-FeOOH; approx.40% of total Fe). The detection of goethite is very significant because it is a mineralogical marker for aqueous alteration.

Klingelhoefer, G.↗

Biogeochemical Activity of Siderophilic Cyanobacteria: Implications for Paleobiogeochemistry

Understanding the patterns of iron oxidation by cyanobacteria (CB) has tremendous importance for paleobiogeochemistry, since cyanobacteria are presumed to have been involved in the global oxidation of ferrous iron during the Precambrian (Cloud, 1973). B.K. Pierson (1999, 2000) first proposed to study iron deposition in iron-depositing hot springs (ID HS) as a model for Precambrian Fe(2+) oxidation. However, neither the iron-dependent physiology of individual species of CB inhabiting iron-depositing hot springs nor their interactions with minerals enriched with iron have been examined thoroughly. Such study could shed light on ancient iron turnover. Cyanobacterial species isolated from ID HS demonstrate elevated tolerance to colloidal Fe(3+) (= 1 mM), while a concentration of 0.4 mM proved toxic for mesophilic Synechocystis PCC 6803. Isolates from ID HS require 0.4-0.6 mM Fe3+ for maximal growth while the iron requirement for Synechocystis is approximately one order of magnitude lower. We have also demonstrated that thick polysaccharide sheaths around cells of CB isolated from ID HS serve as repositories for precipitated iron. The growth of the mesophilic cyanobacteria Phromidium aa in iron-saturated (0.6 mM) DH medium did not lead to iron precipitation on its filament surfaces. However, a 14.3 fil.2 culture, isolated from an ID HS and incubated under the same conditions, was covered with dense layer of precipitated iron. Our results, taken together with Pierson s data concerning the ability of Fe2+ to stimulate photosynthesis in natural CB mats in ID HS, suggest that CB inhabiting ID HS may constitute a new group of the extremophiles - siderophilic CB. Our recent experiments have revealed for the first time that CB isolates from ID HS are also capable of biodeterioration - the etching of minerals, in particular glasses enriched with Fe, Al, Ti, O, and Si. Thus, Precambrian siderophilic cyanobacteria and their predecessors could have been involved not only in iron deposition but also in the global release of elements. The ability of siderophilic CB to participate in iron turnover make them appropriate candidates for biotechnological processes.

Brown, Igor I.↗

Comparative Planetary Mineralogy: Valence State Partitioning of Cr, Fe, Ti, and V Among Crystallographic Sites in Olivine, Pyroxene, and Spinel from Planetary Basalts

We have considered the valence-state partitioning of Cr, Fe, Ti, and V over crystallographic sites in olivine, pyroxene, and spinel from planetary basalts. The sites that accommodate these cations are the M2 site (6-8 coordinated) and M1 site (6 coordinated) in pyroxene, the M2 site (6-8 coordinated) and M1 site (6 coordinated) in olivine, and the tetrahedral and octahedral sites in spinel. The samples we studied are basalts from Earth, Moon, and Mars, which have fO2 conditions that range from IW-2 (Moon) to IW+6 (Earth) with Mars somewhere between at IW to IW+2. In this range of fO2 the significant elemental valences are (from low to high fO2) Ti4+, V3+, Fe2+, Cr2+, Cr3+, V3+, V4+, and Fe3+. V2+ and Ti3+ play a minor role in the phases considered for the Moon, and are probably in very low concentrations. V5+ plays a minor role in these phases in terrestrial basalts because it is probably in lower abundance than V4+ and it has an ionic radii that is so small (0.054 nm, 6- coordinated,[1]) that it is almost at the lower limit for octahedral coordination. The role of Cr2+ in the Moon is significant, as Sutton et al. [2] found that lunar olivine contains mostly Cr2+ while coexisting pyroxene contains mostly Cr3+. Hanson one vacancy only accommodates one V4+. Thus more vacancies are required in V4+ substitutions into olivine. In the Moon V3+ is much more abundant than V4+ [7, 8]. Thus in lunar chromite V3+ follows Cr3+, whereas in Earth V4+ (which is much greater in abundance than V3+) follows Ti4+ (eg in ulv spinel). We could go on in this vein for some time but space limitations do not permit us to do so.

Papike, J. J.↗

Modeling Water-Rock Reactions Beneath the Greenheugh Pediment, Gale Crater, Mars

The Mars Science Laboratory Curiosity rover has been exploring the clay rich Glen Torridon unit in Gale crater since sol 2300 of the mission [1]. As identified in orbital data [2], this clay rich area [3] in the Murray formation is overlain with the Greenheugh Pediment unit to the south, which is part of the Stimson Formation [4]. Curiosity acquired the drill sample Hutton in the Upper Murray formation 2 – 3 meters below the Greenheugh Pediment [5,6]. This study uses thermochemical modelling to investigate the hypothesis for alteration in the Murray formation below the Greenheugh Pediment. Specifically, if the contact between the Greenheugh Pediment and Murray sediments was a conduit for diagenetic fluids (a low water/rock scenario) or if subaerial weathering altered the Murray sediments before cementation began (a high water/rock scenario) [6]. Here, we report on preliminary modeling where we have reacted the chemical composition for the Hutton drill sample with Gale Portage Water (GPW) at 25 °C, 50 °C and 200 °C, for 10% Fe3+/Fetot of the host rock.

SMR Turner↗

Water Contents of the Mantle Beneath the Rio Grande Rift: FTIR Analysis of Kilbourne Hole Peridotite Xenoliths

Although nominally anhydrous mantle minerals contain only trace amounts of water, they are the main reservoir of water in the mantle. Added up at the scale of the Earth's mantle, these trace amounts of water represent oceans worth in mass]. Mantle xenoliths from Kilbourne Hole in southern New Mexico are ideal to study mantle water distribution in a rift tectonic setting as they come from a recently‐erupted maar in the middle of the Rio Grande Rift. Eleven lherzolites, one harzburgite, and one dunite are being analyzed for water contents by FTIR. The xenoliths will also be analyzed for major and trace element composition, Fe3+/Summation (Fe) ratios, and characterized petrologically. Olivines exhibit variable water contents with less water at the rims compared to the cores. This is probably due to H loss during decompression and xenolith transport by the host magma. Mantle water contents appear to have been primarily preserved in the core of the olivines, based on diffusion modeling of the typically plateau-shaped water content profiles across these grains. Water concentrations are in equilibrium between clino- and orthopyroxene, but olivine concentrations are typically not in equilibrium with those of either pyroxene. Lherzolites analyzed so far have water contents of 2‐12 ppm H2O in olivines, 125‐165 ppm H2O in orthopyroxenes, and 328‐447 ppm H2O in clinopyroxenes. These water contents are similar to, but with a narrower range, than those for the respective minerals in other continental peridotite xenoliths. The lherzolites have bulk-rock (BR) Al2O3 contents that range between 3.17 and 3.78 wt%, indicating similar degrees of partial melting, which could explain the narrow range of their pyroxene water contents. Primitive mantle normalized rare earth element (REE) profiles of the bulk lherzolites vary from light REE depleted to flat, with no significant differences between, nor relation to, their mineral water contents. Consequently, the metasomatic agents that enriched LREEs in these lherzolites were most likely water-poor. The harzburgite and the dunite have lower weight percent Al2O3 compared to the lherzolites (2.11% and 0.34% respectively) indicating higher degrees of melting. Their olivine water contents, however, are similar to those of the lherzolites. Moreover, no correlations are observed between pyroxene water contents and indices of melting or metasomatism between the lherzolite group, the harzburgite, and the dunite, although the latter has the lowest pyroxene water contents. More samples will be analyzed to determine if the water contents are controlled by melting, metasomatism, or a combination of the two in the Kilbourne Hole mantle.

Schaffer, Lillian A.↗

The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity

The intrinsic oxygen fugacity (fO2) imposed on a magma has the ability to influence the crystallization sequence of the melt, as well as the composition of the resulting minerals. fO2 is an easily controlled parameter in the lab, either through gas-mixing equilibria or with a solid-state buffer assemblage. In nature, the fO2 of a closed system is imposed on the system internally through multivalent equilibria involving the phenocryst-melt assemblage. This results in a characteristic oxidation state. The physical parameter used to quantify oxidation state is oxygen fugacity. Iron is the only major rock forming element in basaltic melts to exist in multiple valence states and, therefore, it is commonly used to assess fO2. Traditional methods to quantify fO2 utilize the ferric content of glasses or coexisting Fe-Ti oxides. However, many rocks, such as the Martian meteorites, do not contain the necessary phases or have oxides which have suffered reequilibration, thereby rendering them unmeasureable by current techniques. For these rocks, new methods, utilizing other phases are needed. Mafic minerals have Fe(3+)/SigmaFe ratios that are a function of two factors: 1) crystal chemistry and 2) their intrinsic fO2 during crystallization. Olivine and orthopyroxene, for example, have steric constraints on the extent to which Fe(3+) can be incorporated in their structures, and may not record changes in magmatic fO2 in a way that can easily be measured. The chemistry of clinopyroxene, however, allows for extensive incorporation of Fe(3+) in its crystal structure, making it a potentially useful oxybarometer. To date, there have been few, if any, systematic experimental studies of the variation of the Fe(3+)/SigmaFe ratio as a function of fO2 in clinopyroxene. This study seeks to address this lack of data.

McCanta, M. C.↗

Geochemistry of approximately 1.9 Ga sedimentary rocks from northeastern Labrador, Canada

Fifty-eight rock chips from fifteen samples of sedimentary rocks from the Ramah Group (approximately 1.9 Ga) in northeastern Labrador, Canada, were analyzed for major and minor elements, including C and S, to elucidate weathering processes on the Earth's surface about 1.9 Ga ago. The samples come from the Rowsell Harbour, Reddick Bight, and Nullataktok Formations. Two rock series, graywackes-gray shales of the Rowsell Harbour, Reddick Bight and Nullataktok Formations, and black shales of the Nullataktok Formation, are distinguishable on the basis of lithology, mineralogy, and major and trace element chemistry. The black shales show lower concentrations than the graywackes-gray shales in TiO2 (0.3-0.7 wt% vs. 0.7-1.8 wt%), Al2O3 (9.5-20.1 wt% vs. 13.0-25.0 wt%), and sigma Fe (<1 wt% vs. 3.8-13.9 wt% as FeO). Contents of Zr, Th, U, Nb, Ce, Y, Rb, Y, Co, and Ni are also lower in the black shales. The source rocks for the Ramah Group sediments were probably Archean gneisses with compositions similar to those in Labrador and western Greenland. The major element chemistry of source rocks for the Ramah Group sedimentary rocks was estimated from the Al2O3/TiO2 ratios of the sedimentary rocks and the relationship between the major element contents (e.g., SiO2 wt%) and Al2O3/TiO2 ratios of the Archean gneisses. This approach is justified, because the Al/Ti ratios of shales generally retain their source rock values; however, the Zr/Al, Zr/Ti, and Cr/Ni ratios fractionate during the transport of sediments. The measured SiO2 contents of shales in the Ramah Group are generally higher than the estimated SiO2 contents of source rocks by approximately 5 wt%. This correction may also have to be applied when estimating average crustal compositions from shales. Two provenances were recognized for the Ramah Group sediments. Provenance I was comprised mostly of rocks of bimodal compositions, one with SiO2 contents approximately 45 wt% and the other approximately 65 wt%, and was the source for most sedimentary rocks of the Ramah Group, except for black shales of the Nullataktok Formation. The black shales were apparently derived from Provenance II that was comprised mostly of felsic rocks with SiO2 contents approximately 65 wt%. Comparing the compositions of the Ramah Group sedimentary rocks and their source rocks, we have recognized that several major elements, especially Ca and Mg, were lost almost entirely from the source rocks during weathering and sedimentation. Sodium and potassium were also leached almost entirely during the weathering of the source rocks. However, significant amounts of Na were added to the black shales and K to all the rock types during diagenesis and/or regional metamorphism. The intensity of weathering of source rocks for the Ramah Group sediments was much higher than that of typical Phanerozoic sediments, possibly because of a higher PCO2 in the Proterozoic atmosphere. Compared to the source rock values, the Fe3+/Ti ratios of many of the graywackes and gray shales of the Ramah Group are higher, the Fe2+/Ti ratios are lower, and the sigma Fe/Ti ratios are the same. Such characteristics of the Fe geochemistry indicate that these sedimentary rocks are comprised of soils formed by weathering of source rocks under an oxygen-rich atmosphere. The atmosphere about 1.9 Ga was, therefore, oxygen rich. Typical black shales of Phanerozoic age exhibit positive correlations between the organic C contents and the concentrations of S, U, and Mo, because these elements are enriched in oxygenated seawater and are removed from seawater by organic matter in sediments. However, such correlations are not found in the Ramah Group sediments. Black shales of the Ramah Group contain 1.7-2.8 wt% organic C, but are extremely depleted in sigma Fe (<1 wt% as FeO), S (<0.3 wt%), U (approximately l ppm), Mo (<5 ppm), Ni (<2 ppm), and Co (approximately 0 ppm). This lack of correlation, however, does not imply that the approximately 1.9 Ga atmosphere-ocean system was anoxic. Depletion of these elements from the Ramah Group sediments may have occurred during diagenesis.

Non-NASA Center↗