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The 'North American shale composite' - Its compilation, major and trace element characteristics

North American shale composite (NASC) major element composition and compilation are presented, together with rare earth element (REE) redeterminations obtained by high precision analytical methods. The major element composition of the NASC compares closely with other average shale compositions, and significant portions of the REE and some other trace elements are contained in minor phases. The uneven REE distribution in NASC powder appears to yield the heterogeneity in analyzed aliquants. REE distributions of detrital sediments may to some extent be dependent on their minor mineral assemblages and the sedimentological factors controlling these assemblages.

Gromet, L. P.↗

Physical and chemical properties of the Martian soil: Review of resources

The chemical and physical properties of Martian surface materials are reviewed from the perspective of using these resources to support human settlement. The resource potential of Martian sediments and soils can only be inferred from limited analyses performed by the Viking Landers (VL), from information derived from remote sensing, and from analysis of the SNC meteorites thought to be from Mars. Bulk elemental compositions by the VL inorganic chemical (x ray fluorescence) analysis experiments have been interpreted as evidence for clay minerals (possibly smectites) or mineraloids (palagonite) admixed with sulfate and chloride salts. The materials contained minerals bearing Fe, Ti, Al, Mg and Si. Martian surface materials may be used in many ways. Martian soil, with appropriate preconditioning, can probably be used as a plant growth medium, supplying mechanical support, nutrient elements, and water at optimal conditions to the plants. Loose Martian soils could be used to cover structures and provide radiation shielding for surface habitats. Martian soil could be wetted and formed into abode bricks used for construction. Duricrete bricks, with strength comparable to concrete, can probably be formed using compressed muds made from martian soil.

Stoker, C. R.↗

Neutron activation analysis of stoney spherules from a marine sediment sample

The identification of extraterrestrial material in samples collected at the surface of the Earth is discussed. Criteria were established for black magnetic spherules which involve the presence of: Fe, Ni, and Co in iron meteoritic ratios, wustite, and Fe-Ni metal while reliable criteria for stoney spherules are not well established. Neutron activation analysis was performed on eight stony spherules separated from the same marine sediment used by Millard and Finkelman. The 22 elements were determined by Compton suppression and triple coincidence gamma counting. It is found that Fe, Mg, Al, Ni, Cr, Co, Ir, and Sc are the best discriminators between chondritic and terrestrial compositions. Three of the spherules have compositions very close to chondrites and of these, two contain 0.5 and 0.25 ppm Ir. The other five spherules contain much less than chondritic concentrations of Ni but this element may be segregated and lost during ablation of the parent meteorite. One of these five low Ni spherules contains 2.9 ppm Ir while the other four contain less than 0.05 ppm Ir.

Millar, H. T., Jr.↗

NanoSIMS Sheds Light on the Origin and Significance of Early Archean Organic Microstructures from the Pilbara of Australia

NanoSIMS was used to characterize sub-micron scale morphology and elemental composition (C, N, S, Si, O) of organic microstructures in Early Archean (3 - 3.4 Ga) charts from the Pilbara of Western Australia. Three categories of structures were analyzed: small spheroids in clusters; spindle-shaped remains; and large spheroids. All are relatively poorly preserved and occur within the chert matrix of the samples. Carbonaceous material in a secondary hydrothermal vein also was analyzed, as an example of non-indigenous organic matter. Comparisons were made of NanoSIMS characteristics of the Archean samples and those from well-preserved, biogenic microfossils in the 0.8 Ga Bitter Springs Formation. The comparisons show that the Pilbara microstructures are generally distinct from material in the hydrothermal vein but similar in morphology and elemental composition to the Bitter Springs microfossils. In addition, the Pilbara structures exhibit a spatial relationship to silicon and oxygen that seemingly reflects silica nucleation on organic surfaces; this argues that the organic frameworks of the Archean structures were present in the sediment during crystallization of the silica matrix. The structures are thus interpreted as being indigenous to the enclosing sediment. While these results are suggestive of Early Archean biogenicity and are consistent with a growing body of data suggesting that life on Earth was well established by 3 to 3.4 Ga, work is continuing to determine the N/C and 13C ratios of individual forms, and this should provide additional insight into the derivation and significance of these ancient organic remains.

Oehler, Dorothy Z.↗

Lunar and Planetary Science XXXV: Mars: Radar, Gamma Ray Spectrometer, and Cratering Mineralogy

The session "Mars: Radar, Gamma Ray Spectrometer, and Cratering Mineralogy" contained the following reports:The Dielectric Properties of Martian Soil Simulant JSC Mars-1 in the Range from 20Hz to 10kHz; Eastern Sahara Geology from Orbital Radar: Potential Analog to Mars On the Dielectric Properties of the Martian-like Surface Sediments; Radar Observations of Recent Mars Landing Sites; Sounding of Subsurface Water Through Conductive Media in Mars Analog Environments Using Transient Electromagnetics and Low Frequency Ground-penetrating Radar; Burial Depth of the Reservoirs of Hydrogen at the Equatorial Latitudes on Mars; Elemental Composition Variations for Large Dusty and Rocky Regions on Mars Using Gamma-Ray Data from the Mars Odyssey Gamma-Ray Spectrometer; The Distribution of Non-Volatile Elements on Mars: Mars Odyssey GRS Results; Using Mars Odyssey GRS Data to Assess Models for the Bulk Composition of Mars; Mars: The Terra Arabia Low Epithermal Neutron Flux Anomaly; The Isidis Basin of Mars: New Results from MOLA, MOC, and THEMIS; Remote Sensing of the Haughton Impact Structure (HIS): A Terrestrial Proof of Concept for Using the Remote Sensing of Martian Craters as a Probe of Subsurface Composition;and Thermal Emission Spectra of Impact Glass and Shocked Deccan Basalt from Lonar Crater, India and Implications for Remote Sensing of Mars.

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Magma-Sediment Hydrothermal Systems on Mars Explored Through Thermochemical Modeling and Analogue Studies

High temperature impact-generated and magmatic hydrothermal systems on Noachian Mars may have produced habitable environments by providing heat, energy, and volatiles necessary to support microbial life. Magmatic hydrothermal systems formed when mafic magma intruded into sedimentary rocks are of primary interest when investigating the habitability of high-temperature aqueous environments on Mars because contact metamorphism favors the alteration of the country rocks and the release of bound fluids in minerals and fluids in ice and pore spaces, and mobilization of bio-essential elements. Magma-sediment hydrothermal systems on Mars are difficult to identify from orbit and only limited in-situ investigations have been performed. Thus, terrestrial analogues need to be investigated. Recent studies focused on a magmatic hydrothermal system characterized by near-neutral Cl-S-CO 2 -rich fluids produced by a mafic dike intruding the Jurassic Entrada sandstone (Colorado Plateau, UT). Chemical and mineralogical changes identified in the dike and in the sediments were attributed to high-temperature metamorphism (> 700 °C), and low-temperature regimes (< 200 °C) when the system cooled down, and became potentially habitable [6]. However, compositional differences exist between the terrestrial dike and basaltic rocks on Mars, making difficult a comparison between secondary minerals and fluid chemistries of terrestrial and Martian systems. Here, we use thermochemical modelling to explore how differences in bulk dike composition will affect reaction pathways, secondary mineralogy, fluid chemistry, and bio-essential element availability.

S Cogliati↗

Reworking and Diagenesis of Martian Soil: Pathway to Murray Formation Sediments?

In Gale crater, the Curiosity Mars rover has climbed over 300 meters of the Murray formation from the base of the Pahrump Hills to the crest of Vera Rubin Ridge. We discuss the possibility that fine-grained mudstone of the Murray formation is a diagenetic product of sediments with a chemical and mineralogical composition similar to present-day martian soil. Typical (low Ca-sulfate) Murray samples have Na2O, Al2O3, SiO2, SO3, TiO2 and FeOT concentrations within 10% (relative) of average martian soil. These oxides constitute ~85% of each sample. The Al/Si and Ti/Si ratios of Murray samples are comparable to average martian soil but distinct from other martian geologic units. Percentage difference in P2O5, Cl, K2O, Cr2O3, MnO, Ni, Zn, Br, and Ge between soil and Murray samples generally exceed 10%, but these elements and oxides amount to less than 4% of the samples. These constituents are highly variable in Murray mudstone and may reflect mobility in fluid interactions. Large discrepancies in MgO and CaO with ~50% lower concentrations in the Murray samples (~2% absolute differences) are indicative of open-system alteration if the Murray mudstone originated from soil-like material. Mineralogically, martian soil is dominated by plagioclase feldspar, pyroxenes, and olivine with minor hematite, magnetite, and Ca-sulfate. In comparison, Murray samples generally have less feldspar and pyroxene, little to no olivine, more iron oxides and Ca-sulfates, and Fe-containing phyllosilicates. If Murray mudstone originated from a Mars soil composition, aqueous alteration could have converted olivine and pyroxenes to iron oxides and phyllosilicates. Intermixed or zoned plagioclase feldspars could have lost a larger portion of calcic constituents, consistent with susceptibility to weathering, resulting in a change from ~An55 (soil) to ~An40 (Murray). This alteration could be consistent with the major element chemistry, including the small decrease in MgO and CaO. A subsequent influx of minor/trace elements and Ca-sulfate, e.g. from groundwater, would be required. In this diagenetic scenario, the bulk of the alteration would have been nearly isochemical, suggesting limited mineral segregation and aqueous alteration during transport from the drainage basin or a significant direct aeolian contribution to the Murray sediments.

Yen, Albert S.↗

Effects of Basalt Composition on a Martian Analogue Magma-Sediment Hydrothermal System Studied Through Thermochemical Modeling

High-temperature hydrothermal systems have been identified on Mars associated with both hypervelocity impacts and magmatic activity on Mars’s early history [1, 2]. These processes may have produced habitable environments by providing heat, energy, and volatile species necessary to support microbial life [3, 4]. Hydrothermal systems formed after the intrusion of mafic magmas in sedimentary rocks are of particular interest when investigating the habitability of high-temperature aqueous environments on Mars [5, 6],because during magma-sediment contact metamorphism bond fluids (e.g. in ice, pore spaces, minerals) are mobilized favoring the alteration of the country rocks and the release of bio-essential elements [7, 8]. The chemistry and mineralogy of these systems on Mars are not well constrained and, for this reason, terrestrial analogues need to be investigated. Costello et al. [5] and Crandall et al. [6] have studied a mafic dike intruding the Jurassic Entrada sandstone (Colorado Plateau, UT). The intrusion has produced a hydrothermal system with Cl-CO2 rich fluids and near-neutral pH, which induced chemical and mineralogical changes in the dike and in the sediments [5, 6]. The system reached temperatures higher than 700 °C around the contact zone [6], but lower temperatures (< 200 °C) were reached as the system cooled down [5] making the environment potentially habitable [6]. However, previous studies do not consider compositional differences between the terrestrial dike and basaltic rocks on Mars [9, 10] making difficult a direct comparison between alteration mineralogy and brine chemistry of terrestrial and martian systems. Here, we use thermochemical modelling to investigate how differences in bulk dike composition will affect secondary mineral assemblages and fluid chemistry.

S Cogliati↗

Source indicators of humic substances and proto-kerogen - Stable isotope ratios, elemental compositions and electron spin resonance spectra

Stable isotope ratios of C, N and H, elemental compositions, and electron spin resonance (ESR) data of humic acids and proto-kerogens from twelve widely varying sampling locations are presented. Humic acids and proto-kerogens from algal sources are more aliphatic and higher in N than those from higher plant sources. Oxygen content appears to represent a measure of maturation, even in Recent sediments, and S content may reflect redox conditions in the environment of deposition. The ESR data indicate that the transformation of humic substances to proto-kerogens in Recent sediments is accompanied by an increase in aromatic character. A combination of stable carbon isotope ratio and H/C ratio may be a simple but reliable source indicator which allows differentiation of marine-derived from terrestrially-derived organic matter. The stable nitrogen isotope ratios are useful indicators of nitrogen nutrient source. Deuterium/hydrogen isotope ratios appear to reflect variations in meteoric waters and are not reliable source indicators.

Stuermer, D. H.↗

Lunar and Planetary Science XXXVI, Part 16

Contents include the folowing: Experimental Study of Fe-, Co- and Ni-partitioning Between Forsterite and low-Co Fe,Ni-Alloys: Implications for Formation of Olivine Condensates in Equilibrium with Primitive Metal. Channels and Fan-like Features on Titan Surface Imaged by the Cassini RADAR. The Oxygen Isotope Similarity of the Earth and Moon: Source Region or Formation Process? The Mn-53-Cr-53 System in CAIs: An Update. Comparative Planetary Mineralogy: Valence State Partitioning of Cr, Fe, Ti, and V Among Crystallographic Sites in Olivine, Pyroxene, and Spinel from Planetary Basalts. CAI Thermal History Constraints from Spinel: Ti Zoning Profiles and Melilite Boundary Clinopyroxenes. Noble Gas Study of New Enstatite SaU 290 with High Solar Gases. A Marine Origin for the Meridiani Planum Landing Site? A Mechanism for the Formation and Evolution of Tharsis as a Consequence of Mantle Overturn: Large Scale Lateral Heterogeneity in a Stably Stratified Mantle. Endolithic Colonization of Fluid Inclusion Trails in Mineral Grains. Microbial Preservation in Sulfates in the Haughton Impact Structure Suggests Target in Search for Life on Mars. Ascraeus Mons Fan-shaped Deposit, Mars: Geological History and Volcano-Ice Interactions of a Cold-based Glacier. Weathering Pits in the Antarctic Dry Valleys: Insolation-induced Heating and Melting, and Applications to Mars. Mineralogy and Petrography of Lunar Mare Regolith Breccia Meteorite MET 01-210. Geological Mapping of Ganymede. A Quantitative Analysis of Plate Motion on Europa: Implications for the Role of Rigid vs. Nonrigid Behavior of the Lithosphere. Comparison of Terrestrial Morphology, Ejecta, and Sediment Transport of Small Craters: Volcanic and Impact Analogs to Mars. An Integrated Study of OMEGA-Identified Mineral Deposits in Eastern Hebes Chasma, Mars. Global Spectral and Compositional Diversity of Mars: A Test of CRISM Global Mapping with Mars Express OMEGA Data. On Origin of Sedna. Processing ISS Images of Titan s Surface. LA-ICP-MS Study of Trace Elements in the Chaunskij Metal.

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Calcium Isotope Constraints on Recycled Carbonates in Subduction-related Magmas

Calcium isotope ratios are readily mass-fractionated by low-temperature depositional processes that can be recorded in sedimentary rocks and, therefore, have the potential to track distinct geochemical signatures of recycled materials in mantle-derived igneous rocks. In this study, I report calcium isotopic compositions for well-characterized lavas from the Central American volcanic arc that exhibit a range of trace element and radiogenic isotope signatures that have been used to indicate variable amounts of subducted marine carbonate and hemipelagic sedimentary rocks, fresh carbonatite lavas from Oldoinyo Lengai Volcano, Tanzania, and an intrusive carbonatite clast erupted 12.8 ka from the Laacher See Volcano, Germany. I observed no calcium isotope evidence for recycled sedimentary rocks in the Central American arc magmas or in the Oldoinyo Lengai carbonatite volcanic rocks. They all exhibit isotopic compositions similar to rocks dominated by a primitive, mantle-like, bulk silicate Earth (BSE) composition. The exception in this work is the calcium isotope composition measured in the intrusive Laacher See carbonatite that is resolvable from BSE (δ^44 Ca = 0.0). Although this calcium isotopic signature might be related to ancient carbonate recycling, the magnitude and relatively light calcium isotopic composition (δ^44 Ca = –0.4) of this carbonatite could also reflect an origin that involved partial melting of altered lithospheric mantle, from which isotopically heavy Ca-bearing fluids have been lost. The decoupled signatures between trace elements and their radiogenic isotopes and those recorded by calcium isotope data are important because they likely reflect different sources and processes, and demonstrate that sediment subduction is not a bulk mixing process.

Ca isotopes↗

Average sedimentary rock rare Earth element patterns and crustal evolution: Some observations and implications from the 3800 Ma ISUA supracrustal belt, West Greenland

Rare earth element (REE) data is given on a set of clastic metasediments from the 3800 Ma Isua Supracrustal belt, West Greenland. Each of two units from the same sedimentary sequence has a distinctive REE pattern, but the average of these rocks bears a very strong resemblance to the REE pattern for the North American Shale Composite (NASC), and departs considerably from previous estimates of REE patterns in Archaean sediments. The possibility that the source area for the Isua sediments resembled that of the NASC is regarded as highly unlikely. However, REE patterns like that in the NASC may be produced by sedimentary recycling of material yielding patterns such as are found at Isua. The results lead to the following tentative conclusions: (1) The REE patterns for Isua Seq. B MBG indicate the existence of crustal materials with fractionated REE and negative Eu anomalies at 3800 Ma, (2) The average Seq. B REE pattern resembles that of the North American Shale Composite (NASC), (3) If the Seq. B average is truly representative of its crustal sources, then this early crust could have been extensively differentiated. In this regard, a proper understanding of the NASC pattern, and its relationship to post-Archaean crustal REE reservoirs, is essential, (4) The Isua results may represent a local effect.

Dymek, R. F.↗

Stable carbon and sulfur isotopes as records of the early biosphere

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

Desmarais, David J.↗

Petrology of Impact-Melt Rocks at the Chicxulub Multiring Basin, Yucatan, Mexico

Compositions and textures of melt rocks from the upper part of the Chicxulub structure are typical of melt rocks at other large terrestrial impact structures. Apart from variably elevated iridium concentrations (less than 1.5 to 13.5 +/- 0.9 ppb) indicating nonuniform dissemination of a meteoritic component, bulk rock and phenocryst compositions imply that these melt rocks were derived exclusively from continental crust and platform-sediment target lithologies. Modest differences in bulk chemistry among samples from wells located approximately 40 km apart suggest minor variations in relative contributions of these target lithologies to the melts. Subtle variations in the compositions of early-formed pyroxene and plagioclase also support minor primary differences in chemistry between the melts. Evidence for pervasive hydrothermal alteration of the porous mesostasis includes albite, K-feldspar, quartz, epidote, chlorite, and other phyllosilicates, as well as siderophile element-enriched sulfides, suggesting the possibility that Chicxulub, like Sudbury, may host important ore deposits.

Schuraytz, Benjamin C.↗

Results and Implications of Mineralogical Models for Chemical Sediments at Meridiani Planum

The Mars Exploration Rover (MER) "Opportunity" has explored chemically-enriched sedimentary outcrops at Meridiani Planum, Mars. In its first year, three different crater sites - Eagle, Fram and Endurance - have been explored. Nineteen high-interest outcrop rocks were investigated by first grinding a hole to reach the interior (using the Rock Abrasion Tool, RAT), and then conducting APXS (alpha particle x-ray spectrometry) analysis, MB (M ssbauer) analysis, and close up imaging (MI, microscopic imager). Sixteen elements and four Fe-bearing minerals were assayed to good accuracy in each sample, producing 380 compositional data points. The Miniature Thermal Emission Spectrometer (Mini- TES) obtained spectra on outcrop materials which provide direct indication of several mineral classes. Preliminary reports on Eagle crater and three RAT samples have been published. Chemical trends and a derived mineralogical model for all RAT d outcrop samples to date has been developed.

Clark, B. C.↗

An Achondritic Micrometeorite from Antarctica: Expanding the Solar System Inventory of Basaltic Asteroids

Micrometeorites with sizes below 1 mm are collected in a diversity of environments such as deep-sea sediments and polar caps. Chemical, mineralogical and isotopic studies indicate that micrometeorites are closely related to primitive carbonaceous chondrites that amount to only approximately 2% of meteorite falls. While thousands of micrometeorites have been studied in detail, no micrometeorite has been found so far with an unambiguous achondritic composition and texture. One melted cosmic spherule has a low Fe/Mn ratio similar to that of eucrites, the most common basaltic meteorite group. Here we report on the texture, mineralogy, Rare Earth Elements (REEs) abundance and oxygen isotopic composition of the unmelted Antarctic micrometeorite 99-21-40 that has an unambiguous basaltic origin.

Gounelle, M.↗

Coordinating Chemical and Mineralogical Analyses of Antarctic Dry Valley Sediments as Potential Analogs for Mars

The Antarctic Dry Valleys (ADV) provide a unique terrestrial analog for Martian surface processes as they are extremely cold and dry sedimentary environments. The surface geology and the chemical composition of the Dry Valleys that are similar to Mars suggest the possible presence of these soil-formation processes on Mars. The soils and sediments from Wright Valley, Antarctica were investigated in this study to examine mineralogical and chemical changes along the surface layer in this region and as a function of depth. Surface samples collected near Prospect Mesa and Don Juan Pond of the ADV were analyzed using visible/near-infrared (VNIR) and mid-IR reflectance spectroscopy and major and trace element abundances.

Patel, S. N.↗

Composition of Impact Melt Debris from the Eltanin Impact Strewn Field, Bellingshausen Sea

The impact of the km-sized Eltanin asteroid into the Bellingshausen Sea produced mm- to cm-sized vesicular impact melt-rock particles found in sediment cores across a large area of the ocean floor. These particles are composed mainly of olivine and glass with minor chromite and traces of NiFe-sulfides. Some particles have inclusions of unmelted mineral and rock fragments from the precursor asteroid. Although all samples of melt rock examined have experienced significant alteration since their deposition in the late Pliocene, a significant portion of these particles have interiors that remain pristine and can be used to estimate the bulk composition of the impact melt. The bulk composition of the melt-rock particles is similar to the composition of basaltic meteorites such as howardites or mesosiderite silicates, with a contribution from seawater salts and a siderophile-rich component. There is no evidence that the Eltanin impact melt contains a significant terrestrial silicate component that might have been incorporated by mixing of the projectile with oceanic crust. If terrestrial silicates were incorporated into the melt, then their contribution must be much less than 10 wt%. Since excess K, Na, and CI are not present in seawater proportions, uptake of these elements into the melt must have been greatest for K and least for CI, producing a K/CI ratio about 4 times that in seawater. After correcting for the seawater component, the bulk composition of the Eltanin impact melt provides the best estimate of the bulk composition of the Eltanin asteroid. Excess Fe in the impact melt, relative to that in howardites, must be from a significant metal phase in the parent asteroid. Although the estimated Fe:Ni:Ir ratios (8:1:4 x 10(exp -5)) are similar to those in mesosiderite metal nodules (10:1:6 x 10(exp -5), excess Co and Au by factors of about 2 and 10 times, respectively, imply a metal component distinct from that in typical mesosiderites. An alternative interpretation, that siderophiles have been highly fractionated from a mesosiderite source, would require loss of about 90% of the original metal from the impact melt and the sediments, and is unsupported by any observational data. More likely, the excess Fe in the melt rocks is 'representative of the amount of metal in the impacting asteroid, which is estimated to be 4+/- 1 wt%.

Kyte, Frank T.↗