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The Mineralogy, Geochemistry, and Redox State of Multivalent Cations During the Crystallization of Primitive Shergottitic Liquids at Various (f)O2. Insights into the (f)O2 Fugacity of the Martian Mantle and Crustal Influences on Redox Conditions of Martian Magmas.

The (f)O2 [oxygen fugacity] of crystallization for martian basalts has been estimated in various studies to range from IW-1 to QFM+4 [1-3]. A striking geochemical feature of the shergottites is the large range in initial Sr isotopic ratios and initial epsilon(sup Nd) values. Studies by observed that within the shergottite group the (f)O2 [oxygen fugacity] of crystallization is highly correlated with these chemical and isotopic characteristics with depleted shergottites generally crystallizing at reduced conditions and enriched shergottites crystallizing under more oxidizing conditions. More recent work has shown that (f)O2 [oxygen fugacity] changed during the crystallization of these magmas from one order of magnitude in Y980459 (Y98) to several orders of magnitude in Larkman Nunatak 06319. These real or apparent variations within single shergottitic magmas have been attributed to mixing of a xenocrystic olivine component, volatile loss-water disassociation, auto-oxidation during crystallization of mafic phases, and assimilation of an oxidizing crustal component (e.g. sulfate). In contrast to the shergottites, augite basalts such as NWA 8159 are highly depleted yet appear to be highly oxidized (e.g. QFM+4). As a first step in attempting to unravel petrologic complexities that influence (f)O2 [oxygen fugacity] in martian magmas, this study explores the effect of (f)O2 [oxygen fugacity] on the liquid line of descent (LLD) for a primitive shergottite liquid composition (Y98). The results of this study will provide a fundamental basis for reconstructing the record of (f)O2 [oxygen fugacity] in shergottites and other martian basalts, its effect on both mineral chemistries and valence state partitioning, and a means for examining the role of crystallization (and other more complex processes) on the petrologic linkages between olivine-phyric and pyroxene-plagioclase shergottites.

Shearer, C. K.↗

Long-lifetime Martian orbit selection using a time-dependent model of the Martian atmosphere

A mathematical model of the time-dependent Martian atmosphere has been developed in order to accurately calculate the effects of aerodynamic drag on a low altitude satellite. The time-dependent properties of the model include solar activity effects, dust storm effects, seasonal and diurnal variations, and annual motion effects. Position effects are accounted for through Martian latitude and longitude. Expected values of mass density, temperature, scale height, and the estimated standard deviation of the mass density are provided. An example of the use of the model in selecting an orbit for the Mars Geochemical/Climatology Orbiter is given.

Culp, R. D.↗

Insights into the Martian Regolith from Martian Meteorite Northwest Africa 7034

Everything we know about sedimentary processes on Mars is gleaned from remote sensing observations. Here we report insights from meteorite Northwest Africa (NWA) 7034, which is a water-rich martian regolith breccia that hosts both igneous and sedimentary clasts. The sedimentary clasts in NWA 7034 are poorly-sorted clastic siltstones that we refer to as protobreccia clasts. These protobreccia clasts record aqueous alteration process that occurred prior to breccia formation. The aqueous alteration appears to have occurred at relatively low Eh, high pH conditions based on the co-precipitation of pyrite and magnetite, and the concomitant loss of SiO2 from the system. To determine the origin of the NWA 7034 breccia, we examined the textures and grain-shape characteristics of NWA 7034 clasts. The shapes of the clasts are consistent with rock fragmentation in the absence of transport. Coupled with the clast size distribution, we interpret the protolith of NWA 7034 to have been deposited by atmospheric rainout resulting from pyroclastic eruptions and/or asteroid impacts. Cross-cutting and inclusion relationships and U-Pb data from zircon, baddelleyite, and apatite indicate NWA 7034 lithification occurred at 1.4-1.5 Ga, during a short-lived hydrothermal event at 600-700 C that was texturally imprinted upon the submicron groundmass. The hydrothermal event caused Pb-loss from apatite and U-rich metamict zircons, and it caused partial transformation of pyrite to submicron mixtures of magnetite and maghemite, indicating the fluid had higher Eh than the fluid that caused pyrite-magnetite precipitation in the protobreccia clasts. NWA 7034 also hosts ancient 4.4 Ga crustal materials in the form of baddelleyites and zircons, providing up to a 2.9 Ga record of martian geologic history. This work demonstrates the incredible value of sedimentary basins as scientific targets for Mars sample return missions, but it also highlights the importance of targeting samples that have not been overprinted by metamorphic processes, which is the case for NWA 7034.

McCubbin, Francis M.↗

Light Lithophile Elements in Natural and Experimental Phases in Martian Basalts: Implications for the Degassing of Water from Martian Magmas

Lentz et al. argued that zoning trends in light lithophile elements (LLE) in pyroxene in Shergotty and Zagami are evidence for the degassing of magmatic water. We tested this inference by obtaining: additional LLE analyses of Shergotty and Zagami pyroxene; analyses of Pasamonte pyroxene; and silicate and phosphate partition coefficients for B and Li for martian magma and mineral compositions.

Herd, C. D. K.↗

Formation of Martian Gullies by the Action of Liquid Water Flowing Under Current Martian Environmental Conditions

Images from the Mars Orbiter Camera (MOC) on the Mars Global Surveyor (MGS) spacecraft show geologically young small-scale features resembling terrestrial water-carved gullies. An improved understanding of these features has the potential to reveal important information about the hydrological system on Mars, which is of general interest to the planetary science community as well as the field of astrobiology and the search for life on Mars. The young geologic age of these gullies is often thought to be a paradox because liquid water is unstable at the Martian surface. Current temperatures and pressures are generally below the triple point of water (273 K, 6.1 mbar) so that liquid water will spontaneously boil and/or freeze. We therefore examine the flow of water on Mars to determine what conditions are consistent with the observed features of the gullies.

Heldmann, J. L.↗

Age of Martian Air: Time Scales for Martian Atmospheric Transport

The mean time since air in the Martian atmosphere was in the low-latitude boundary layer is examined using simulations of an idealized “mean age” tracer with the MarsWRF general circulation model. The spatial distribution and seasonality of the mean age in low- and mid-latitudes broadly follow contours of the mean meridional circulation, with the mean age increasing from 0 at the surface to a maximum of 60–100 sols in the upper atmosphere. Substantially older mean ages (exceeding 300 sols) are found in polar regions, with oldest ages in the lower atmosphere (10–100 Pa), above a near-surface layer with very young ages (around 20 sols). The annual maximum ages occur around the equinoxes, and the age in the polar lower atmosphere decreases during the autumn to winter transition. This autumn-winter decrease in age occurs because of mixing of polar and mid-latitude air when the polar vortex exhibits an annulus of high potential vorticity (PV) with a local minimum near the pole. There is no autumn-winter decrease and old ages persist throughout autumn and winter in simulations with CO2 phase changes disabled, and thus no latent heating, where there is a monopolar vortex (i.e., a monotonic increase in PV from equator to pole) forms. The altitudinal and seasonal variations in the mean age indicates similar variations in the transport of dust into polar regions and the mixing of polar air (with, e.g., low water vapor and high ozone concentrations during winter) into mid-latitudes.

Waugh, D. W.↗

Cemented Volcanic Soils, Martian Spectra and Implications for the Martian Climate

Cemented soils formed via reactions with salts are studied here and provide information about the climate when they formed. Spectroscopic and microprobe studies have been performed on cemented volcanic crusts in order to learn about the composition of these materials, how they formed, and what they can tell us about climatic interactions with surface material on Mars to form cemented soils. These crusts include carbonate, sulfate and opaline components that may all be present in cemented soil units on Mars.

Bishop, J. L.↗

40 Years of Collecting Martian Meteorites

This year marks the 40th anniversary of the first Martian meteorite found in Antarctica by ANSMET, ALH 77005. Since then, an additional 14 Martian meteorites have been found by the ANSMET team making for a total of 15 Martian meteorites in the Antarctic collection at Johnson Space Center. Of the 15 meteorites, some have been paired so the 15 meteorites actually represent a total of approximately 9 separate meteorites. The first Martian meteorite found by ANSMET was ALH 77005 (482.500 g), a lherzolitic shergottite. When collected, this meteorite was split as a part of the joint expedition with the National Institute of Polar Research (NIPR) Japan. Originally classified as an "achondrite-unique", it was re-classified as a Martian lherzolitic shergottites in 1982 [1]. This meteorite has been allocated to ~125 scientists for research and there are 181.964 g remaining at Johnson Space Center (JSC). Two years later, one of the most significant Martian meteorites of the collection at JSC was found at Elephant Moraine, EET 79001 (7942.000 g), a shergottite. This meteorite is the largest in the Martian collection at JSC and was the largest stony meteorite sample collected during the 1979 season. In addition to its size, this meteorite is of particular interest because it contains a linear contact separating two different igneous lithologies, basaltic and olivine-phyric. EET 79001 has glass inclusions that contain chemical compositions that are proportionally identical to the Martian atmosphere, as measured by the Viking spacecraft [2]. This discovery helped scientists to identify where the "SNC" meteorite suite had originated, and that we actually possessed Martian samples. This meteorite has been allocated to ~195 scientists for research and there are 5304.770 g of sample is available. Five years later, ANSMET found ALH 84001 (1930.900 g), the only Martian orthopyroxenite. This meteorite was initially classified as a diogenite but was reclassified as being a Martian meteorite in 1993 [3,4]. ALH 84001 is known as the "Life on Mars" meteorite, sparked debate about whether it contained evidence of Martian life [5] and significantly influenced the field of astrobiol-ogy. This sample has been allocated to 173 scientists for research and has 1426.694 g remaining at JSC. In 1988, another lherzolitic shergottite was found, LEW 88516, (13.203 g). This meteorite wasn't recognized in the field as an achondrite until it was broken during processing 2 years later. LEW 88516 has been allocated to 43 scientists for research and 5.351 g of this meteorite remains at JSC. Six years later a basaltic shergottite was found in the Queen Alexandra Range, QUE 94201 (12.020 g). This meteorite was believed to be of terrestrial origin until maskelynite was seen in a thin section. QUE 94201 has been allocated to 57 scientists for research and there are 3.629 g of this meteorite left at JSC. In 2003, the NASA Mars Exploration Program joined the ANSMET team with the hopes of finding another Martian mete-orite. During this expedition, MIL 03346 (715.200 g) was found. This meteorite is a nakhlite. MIL 03346 has been allocated to 98 scientists for research and there are 579.046 g of this sample remaining at JSC. Six years later, 3 more meteorites that have been paired with MIL 03346 were found, MIL 090030 (452.630 g), 090032 (532.190 g ) and 090136 (170.980 g). MIL 090030 has been allocated to 21 scientists for research and has 434.420 g remaining at JSC, MIL 090032 has been allocated to 21 scientists for re-search and has 508.710 g remaining at JSC and MIL 090136 has been allocated to 14 scientists for research and has 156.790 g remaining at JSC. During the 2004 expedition, 2 identical meteorites where found together on the ice, RBT 04261 (78.763 g) and RBT 04262 (204.600 g). These paired meteorites are olivine-phyric shergottites. RBT 04261 has been allocated to 33 scientists for research and has 32.335 g remaining at JSC. RBT 04262 has been allocated to 46 scientists for research and has 171.886 g remaining. In 2006, another olivine-phyric shergottite was found, LAR 06319 (78.572 g). This meteorite has 61.414 g remaining at JSC and has been allocated to 39 scientists for research. During the 2012 season, 3 more olivine-phyric shergottites were found at Larkman Nunatak, LAR 12011 (701.170 g), LAR 12095 (133.132 g) and LAR 12240 (57.596 g). LAR 12011 is paired with LAR 06319 and LAR 12095 and LAR 12240 are paired with each other. LAR 12011 has been allocated to 43 scientists for research and there are 685.778 g of LAR 12011 remaining at JSC. LAR 12095 has been allocated to 18 scientists for research and has 119.744 g remaining at JSC. LAR 12240 has been allocated to 10 scientists for research and has 52.231 g remaining at JSC. Martian meteorites are the only samples available from Mars because no mission has returned samples from there to date. All Martian meteorites are crustal rocks with most of them being crystallized magmas, so they are an important source for under-standing Martian geological history and volcanism. The ANSMET program has greatly contributed to the scientific community by collecting these meteorites

Funk, R. C.↗

Evidence from Olivine-Hosted Melt Inclusions that the Martian Mantle has a Chondritic D/H Ratio and that Some Young Basalts have Assimilated Old Crust

Magmatic degassing of volatile elements affects the climate and near-surface environment of Mars. Telescopic and meteorite studies have revealed that the Martian atmosphere and near-surface materials have D/H ratios ~5-6 times terrestrial values [e.g., 1, 2]. Such high D/H ratios are interpreted to result from the preferential loss of H relative to heavier D from the Martian atmosphere, assuming that the original Martian water inventory had a D/H ratio similar to terrestrial values and to H in primitive meteorites [e.g., 1, 3]. However, the primordial Martian D/H ratio has, until now, not been well constrained. The uncertainty over the Martian primordial D/H ratio has arisen both from the scarcity of primitive Martian meteorites and as a result of contamination by terrestrial and, perhaps, Martian surface waters that obscure the signature of the Martian mantle. This study reports a comprehensive dataset of magmatic volatiles and D/H ratios in Martian primary magmas based on low-contamination, in situ ion microprobe analyses of olivine-hosted melt inclusions from both depleted [Yamato 980459 (Y98)] and enriched [Larkman Nunatak 06319 (LAR06)] Martian basaltic meteorites. Analyses of these primitive melts provide definitive evidence that the Martian mantle has retained a primordial D/H ratio and that young Martian basalts have assimilated old Martian crust.

Usui, Tomohiro↗

Hydrogen Isotopic Composition of Apatite in Northwest Africa 7034: A Record of the "Intermediate" H-Isotopic Reservoir in the Martian Crust?

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has a H-isotopic composition that is intermediate (δD of 1000-2000per mille) between an isotopically light mantle (Delta D is less than 275per mille [10]) and an isotopically heavy atmosphere (δD of 2500-6100per mille [11, 12]). Apatites in NWA 7034 occur in a number of lithologic domains, however apatites across all lithologic domains have been affected by a Pb-loss event at about 1.5 Ga before present [5], so they are unlikely to have retained a primary composition and are more likely to have equilibrated with fluids within the martian crust that may or may not have exchanged with the martian atmosphere. Equilibration of apatite with crustal fluids is further supported by the chlorine-rich compositions exhibited by apatites in NWA 7034 in comparison to apatites from other martian meteorites (Figure 1; [13]). Cl is more hydrophilic than F, which promotes formation of Cl-rich apatite compositions in fluid-rich systems [e.g., 14, 15-17].

McCubbin, F. M.↗

Prospects for Chronological Studies of Martian Rocks and Soils

Chronological information about Martian processes comes from two sources: Crater-frequency studies and laboratory studies of Martian meteorites. Each has limitations that could be overcome by studies of returned Martian rocks and soils. Chronology of Martian volcanism: The currently accepted chronology of Martian volcanic surfaces relies on crater counts for different Martian stratigraphic units [1]. However, there is a large inherent uncertainty for intermediate ages near ~2 Ga ago. The effect of differing preferences for Martian cratering chronologies [1] is shown in Fig. 1. Stoeffler and Ryder [2] summarized lunar chronology, upon which Martian cratering chronology is based. Fig. 2 shows a curve fit to their data, and compares to it a corresponding lunar curve from [3]. The radiometric ages of some lunar and Martian meteorites as well as the crater-count delimiters for Martian epochs [4] also are shown for comparison to the craterfrequency curves. Scaling the Stoeffler-Ryder curve by a Mars/Moon factor of 1.55 [5] places Martian shergottite ages into the Early Amazonian to late Hesperian epochs, whereas using the lunar curve of [3] and a Mars/Moon factor ~1 consigns the shergottites to the Middle-to-Late Amazonian, a less probable result. The problem is worsened if a continually decreasing cratering rate since 3 Ga ago is accepted [6]. We prefer the adjusted St ffler-Ryder curve because it gives better agreement with the meteorite ages (Fig.

Nyquist, L. E.↗

A First Look at Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric C02 by the Phoenix Lander

Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars. The isotopic composition of the martian atmosphere has been measured using a number of different methods (Table 1), however a precise value (<1%) has yet to be achieved. Given the elevated 13C values measured in carbonates in martian meteorites it has been supposed that the martian atmosphere was enriched in delta(sup 13)C. This was supported by measurements of trapped CO2 gas in EETA 79001[2] which showed elevated delta(sup 13)C values (Table 1). More recently, Earth-based spectroscopic measurements of the martian atmosphere have measured the martian CO2 to be depleted in delta(sup 13)C relative to CO2 in the terrestrial atmosphere. The spectroscopic measurements performed by Krasnopolsky et al. were reported with approx.2% uncertainties which are much smaller than the Viking measurements, but still remain very large in comparison to the magnitude of carbon and oxygen isotope fractionations under martian surface conditions. The Thermal Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander included a magnetic sector mass spectrometer (EGA) which had the goal of measuring the isotopic composition of martian atmospheric CO2 to within 0.5%. The mass spectrometer is a miniature magnetic sector instrument intended to measure both the martian atmosphere as well as gases evolved from heating martian soils. Ions produced in the ion source are drawn out by a high voltage and focused by a magnetic field onto a set of collector slits. Four specific trajectories are selected to cover the mass ranges, 0.7 - 4, 7 - 35, 14 - 70, and 28 - 140 Da. Using four channels reduces the magnitude of the mass scan and provides simultaneous coverage of the mass ranges. Channel electron multiplier (CEM) detectors that operate in the pulse counting mode detect the ion beams.

Niles, P.B.↗