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Shearer, C. K.

Publications and source records attributed to Shearer, C. K..

At least 37 records · Page 2

A New Spinel-Olivine Oxybarometer: Near-Liquidus Partitioning of V between Olivine-Melt, Spinel-Melt, and Spinel-Olivine in Martian Basalt Composition Y980459 as a Function of Oxygen Fugacity

Our research on valence state partitioning began in 2005 with a review of Cr, Fe, Ti, and V partitioning among crystallographic sites in olivine, pyroxene, and spinel [1]. That paper was followed by several on QUE94201 melt composition and specifically on Cr, V, and Eu partitioning between pyroxene and melt [2-5]. This paper represents the continuation of our examination of the partitioning of multivalent V between olivine, spinel, and melt in martian olivine-phyric basalts of Y980459 composition [6, 7]. Here we introduce a new, potentially powerful oxybarometer, V partitioning between spinel and olivine, which can be used when no melt is preserved in the meteorite. The bulk composition of QUE94201 was ideal for our study of martian pyroxene-phyric basalts and specifically the partitioning between pyroxene-melt for Cr, V, and Eu. Likewise, bulk composition Y980459 is ideal for the study of martian olivine-phyric basalts and specifically for olivine-melt, spinel-melt, and spinel-olivine partitioning of V as a function of oxygen fugacity.

Papike, J. J.↗

Sampling South Pole-Aitken Basin: The Moonrise Approach

The South Pole-Aitken basin (SPA) is the largest of the giant impact basins in the inner Solar System, and its location on Earth s Moon makes it the most accessible. Exploration of SPA through direct collection and analysis of representative materials addresses issues as fundamental as the characteristics of the chemical reservoir from which the Moon originated, early differentiation and production of crust and development of global asymmetry, relationships between magmatic activity and internal thermal evolution, and effects of giant impact events on the terrestrial planets. Owing to its great size and superposition relationships with other lunar impact basins, SPA is the oldest and as such anchors the lunar chronology. Moreover, numerous large impact craters and basins are contained within it such that materials (rocks) of the SPA basin contain a record of the early impact chronology, one less likely to have been affected by the large, late nearside basins (e.g., Imbrium). Understanding the early basin chronology is key to deciphering the sequence and effects of early giant impact bombardment of the inner Solar System. That record exists on the Moon, and materials of the SPA basin will allow us to read that record. Knowledge of the early bombardment history will test - and may reshape - a key paradigm relating to early Solar System evolution. Did the planets form with the alignment of today, or was there a major reorientation of the giant planets that led to destabilization of asteroid orbits, and a cataclysmic bombardment of the inner Solar System hundreds of millions of years after accretion of the planets? Implications include understanding environments for early life-supporting habitats on Earth and Mars, and relationships to new observations of extra-solar planetary systems.

Jolliff, B. L.↗

Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt

Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.

Usui, T.↗

Valence State Partitioning of Cr and V Between Pyroxene - Melt: Estimates of Oxygen Fugacity for Martian Basalt QUE 94201

Several studies, using different oxybarometers, have suggested that the variation of fO2 in martian basalts spans about 3 log units from approx. IW-1 to IW+2. The relatively oxidized basalts (e.g., pyroxene-phyric Shergotty) are enriched in incompatible elements, while the relatively reduced basalts (e.g., olivine-phyric Y980459) are depleted in incompatible elements. A popular interpretation of the above observations is that the martian mantle contains two reservoirs; 1) oxidized and enriched, and 2) reduced and depleted. The basalts are thus thought to represent mixing between these two reservoirs. Recently, Shearer et al. determined the fO2 of primitive olivine-phyric basalt Y980459 to be IW+0.9 using the partitioning of V between olivine and melt. In applying this technique to other basalts, Shearer et al. concluded that the martian mantle shergottite source was depleted and varied only slightly in fO2 (IW to IW+1). Thus the more oxidized, enriched basalts had assimilated a crustal component on their path to the martian surface. In this study we attempt to address the above debate on martian mantle fO2 using the partitioning of Cr and V into pyroxene in pyroxene-phyric basalt QUE 94201.

Karner, J. M.↗

Oxygen Fugacity of the Upper Mantle of Mars. Evidence from the Partitioning Behavior of Vanadium in Y980459 (Y98) and other Olivine-Phyric Shergottites

Using partitioning behavior of V between olivine and basaltic liquid precisely calibrated for martian basalts, we determined the redox state of primitive (olivine-rich, high Mg#) martian basalts near their liquidus. The combination of oxidation state and incompatible element characteristics determined from early olivine indicates that correlations between fO2 and other geochemical characteristics observed in many martian basalts is also a fundamental characteristic of these primitive magmas. However, our data does not exhibit the range of fO2 observed in these previous studies.. We conclude that the fO2 for the martian upper mantle is approximately IW+1 and is incompatible-element depleted. It seems most likely (although clearly open to interpretation) that these mantle-derived magmas assimilated a more oxidizing (>IW+3), incompatible-element enriched, lower crustal component as they ponded at the base of the martian crust.

Shearer, C. K.↗

Li, B - Behavior in Lunar Basalts During Shock and Thermal Metamorphism: Implications for H2O in Martian Magmas

Introduction: The water-content of Martian magmas is a topic of debate among researchers. Some Martian basalts are characterized with melt inclusions of biotite, apatite and amphibole; phases typically associated with hydration reactions on Earth [1-3]. However, the H-content of melt inclusions from these basalts is low, and bulk-rock H2O-contents range from a meager 0.013 to 0.035 wt. % in Shergotty [4]. Nonetheless, researchers note that low present-day water contents do not preclude a once hydrous past [5]. Since light lithophile elements (LLE), such as Li and B, partition into aqueous fluids at T > 350 C, workers proposed that Li-B depletions in pyroxene rims of Nakhlite and Shergottite basalts reflect the loss of several weight percent water from Martian magmas during crystallization [6]. Since similar depletions were observed in pyroxene rims from completely dry lunar basalts, it is likely that alternative mechanisms also contribute to the distribution of elements such as Li and B [7]. Given that many Martian basalts have experienced considerable shock pressures (15-45 GPa), it is possible that shock and subsequent thermal metamorphism may have influenced the volatile element records of these basalts [8]. In order to better understand the distribution of Li and B, we are studying the effects of crystal chemistry, shock pressure, and thermal metamorphism in pyroxenes from lunar basalts. Below, we discuss results from experimentally shocked and thermally metamorphosed Apollo 11, 10017 (A-11) and Apollo 17, 75035 (A-17) basalts.

Chaklader, Johny↗

Comparative Planetary Mineralogy: Co, Ni Systematics in Chromite from Planetary Basalts

Spinel is a minor but important phase in planetary basalts because its variable composition often reflects basalt petrogenesis. For example, complicated zoning trends in spinel can give clues to melt evolution [1], and V concentrations in chromite lend insight into magma oxygen fugacity (fO2) conditions [2]. Nickel and Co are two elements that are commonly used as a measure of melt fractionation, and their partitioning between olivine and melt is fairly well understood. Less clear is their partitioning into spinel, although [3] has explored Ni and Co systematics in experimental charges. This study documents Ni and Co behavior in early crystallizing spinel (chromite) from several planetary basalts in an attempt to compare our results with [3], and also gain insight into basalt evolution on the three planets.

Karner, J. M.↗

The Martian Soil as a Geochemical Sink for Hydrothermally Altered Crustal Rocks and Mobile Elements: Implications of Early MER Results

Hydrothermal and aqueous alteration can explain some of the exciting results from the MER team s analyses of the martian soil, including the major elements, mobile elements, and the nickel enrichment. Published results from the five lander missions lead to the following conclusions: 1) The soil appears to be globally mixed and basaltic with only small local variations in chemistry. Relative to martian basaltic meteorites and Gusev rocks the soils are depleted in the fluid-mobile element calcium, but only slightly enriched to somewhat depleted in iron oxide. 2) The presence of olivine in the soils based on M ssbauer data argues that the soil is only partly weathered and is more akin to a lunar regolith than a terrestrial soil. 3) The presence of bromine along with sulfur and chlorine in the soils is consistent with addition of a mobile element component to the soil.

Newsom, H. E.↗

Hydrothermal Alteration at Lonar Crater, India and Elemental Variations in Impact Crater Clays

The role of hydrothermal alteration and chemical transport involving impact craters could have occurred on Mars, the poles of Mercury and the Moon, and other small bodies. We are studying terrestrial craters of various sizes in different environments to better understand aqueous alteration and chemical transport processes. The Lonar crater in India (1.8 km diameter) is particularly interesting being the only impact crater in basalt. In January of 2004, during fieldwork in the ejecta blanket around the rim of the Lonar crater we discovered alteration zones not previously described at this crater. The alteration of the ejecta blanket could represent evidence of localized hydrothermal activity. Such activity is consistent with the presence of large amounts of impact melt in the ejecta blanket. Map of one area on the north rim of the crater containing highly altered zones at least 3 m deep is shown.

Newsom, H. E.↗

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.↗

Hydrothermal Processes and Mobile Element Transport in Martian Impact Craters - Evidence from Terrestrial Analogue Craters

Hydrothermal alteration and chemical transport involving impact craters probably occurred on Mars throughout its history. Our studies of alteration products and mobile element transport in ejecta blanket and drill core samples from impact craters show that these processes may have contributed to the surface composition of Mars. Recent work on the Chicxulub Yaxcopoil-1 drill core has provided important information on the relative mobility of many elements that may be relevant to Mars. The Chicxulub impact structure in the Yucatan Peninsula of Mexico and offshore in the Gulf of Mexico is one of the largest impact craters identified on the Earth, has a diameter of 180-200 km, and is associated with the mass extinctions at the K/T boundary. The Yax-1 hole was drilled in 2001 and 2002 on the Yaxcopoil hacienda near Merida on the Yucatan Peninsula. Yax-1 is located just outside of the transient cavity, which explains some of the unusual characteristics of the core stratigraphy. No typical impact melt sheet was encountered in the hole and most of the Yax-1 impactites are breccias. In particular, the impact melt and breccias are only 100 m thick which is surprising taking into account the considerably thicker breccia accumulations towards the center of the structure and farther outside the transient crater encountered by other drill holes.

Newsom, H. E.↗

A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence

The determination of oxidation conditions for basaltic magmas derived by the melting of planetary mantles is critical to our understanding of the nature and evolution of planetary interiors. Yet, these determinations are compromised in terrestrial and especially extraterrestrial basalts by our analytical and computational methods for estimating oxygen fugacity (fO2). For example, mineralogical barometers (1, 2) can be reduced in effectiveness by subsolidus re-equilibration of mineral assemblages, inversion of mineralogical data to melt characteristics, and deviations of the natural mineral compositions from ideal thermodynamic parameters.

Karner, J. M.↗

Volatile Behavior in Lunar and Terrestrial Basalts During Shock: Implications for Martian Magmas

The amount of water in martian magmas has significant ramifications for the martian atmosphere-hydrosphere cycle. Large D-enrichments have been observed in kaersutitic amphiboles in Zagami, Chassigny and Shergotty meteorites (delta-D values up to 4400 per mil) suggesting that substantial amounts of H escaped Mars in its past. Furthermore, martian meteorites with inclusions of biotite and apatite imply possible origins in a hydrous mantle. However, whether martian magmas ever possessed considerable proportions of water remains controversial and unclear. The H-content of mica and amphibole melt inclusions has been found to be low, while bulk-rock H2O content is also low ranging from 0.013 to 0.035 wt. % in Shergotty. Hydrous martian magmas were considered responsible for light lithophile element (LLE) zoning patterns observed in Nakhlite and Shergottite pyroxenes. Since LLEs, such as Li and B, partition into aqueous fluids at temperatures greater than 350 C, workers interpreted Li-B depletions in pyroxene rims as evidence that supercritical fluid exsolution occurred during magma degassing. In that many martian basalts experienced substantial shock (15-45 GPa) it is possible that the magmatic volatile record preserved in martian basalts has been disturbed. Previous shock experiments suggest that shock processes may effect water content and H/D. To better understand the possible effects of shock on this volatile record, we are studying the redistribution of volatile elements in naturally and experimentally shocked basalts. Here, we report the initial results from shocked basalts associated with the Lonar Crater, India and an experimentally shocked lunar basalt.

Chaklader, Johny↗

Low Abundances of Highly Siderophile Elements in the Lunar Mantle: Evidence for Prolonged Late Accretion

The highly siderophile elements (HSE: including Re, Au, Ir, Os, Ru, Pt, Pd, Rh) are strongly partitioned into metal relative to silicates. In the terrestrial planets these elements are concentrated in metallic cores. Earth s mantle has sufficiently high abundances of the HSE (~0.008 times CI abundances) that it has been hypothesized approximately 0.1-0.5% of the mass of the Earth was added following the last major interaction between the core and mantle [e.g. 1]. The additional material added to the Earth and Moon has been termed a late veneer , and the process has often been termed late accretion [2]. The timing of the dominant late accretionary period of the Earth and Moon is still poorly known. The abundances of HSE in the lunar mantle could provide important constraints on when the late veneer was added. The material that ultimately became the silicate portion of the Moon was likely stripped of most of its HSE prior to and during coalescence of the Moon. Consequently the initial lunar mantle likely had very low concentrations of the HSE. Unlike Earth, the generation of permanent lunar crust by ~4.4 Ga prevented subsequent additions of HSE to the lunar mantle via continued accretion. Thus, if a substantial portion of the late veneer was added after 4.4 Ga, the lunar mantle should have retained very low HSE concentrations. Conversely, if the late veneer was mostly added prior to 4.4 Ga, HSE abundances in the lunar mantle may be roughly similar to abundances in the terrestrial mantle.

Walker, R. J.↗

Oxygen Fugacity of Mare Basalts and the Lunar Mantle Application of a New Microscale Oxybarometer Based on the Valence State of Vanadium

The ability to estimate oxygen fugacities for mare basalts and to extend these observations to the lunar mantle is limited using bulk analysis techniques based on buffering assemblages or the valence state of iron. These limitations are due to reequilibration of mineral assemblages at subsolidus conditions, deviations of mineral compositions from thermodynamic ideality, size requirements, and the limits of the iron valence at very low fO2. Still, these approaches have been helpful and indicate that mare basalts crystallized at fO2 between the iron-w stite buffer (IW) and the ilmenite breakdown reaction (ilmenite = rutile + iron). It has also been inferred from these estimates that the lunar mantle is also highly reduced lying at conditions below IW. Generally, these data cannot be used to determine if the mare basalts become increasingly reduced during transport from their mantle source and eruption at the lunar surface and if there are differences in fO2 among mare basalts or mantle sources. One promising approach to determining the fO2 of mare basalts is using the mean valence of vanadium (2+, 3+, 4+, 5+) determined on spots of a few micrometers in diameter using synchrotron x-ray absorption fine structure (XAFS) spectroscopy. The average valence state of V in basaltic glasses is a function of fO2, temperature, V coordination, and melt composition. Here, we report the initial results of this approach applied to lunar pyroclastic glasses.

Shearer, C. K.↗

Major and Trace Element Variations in Impact Crater Clay from Chicxulub, Lonar, and Mistastin, Implications for the Martian Soil

The catastrophic Chicxulub event should have generated a large hydrothermal system with volatile element mobilization, producing interesting alteration materials and clays. The Yaxcopoil-1 (YAX) drill hole is located in the annular trough, about 70 km southwest of the crater center, in an area where the impactite layers are relatively thin (approx. 100 m thick). We have analyzed samples from the YAX drill core and from other impact craters including Mistastin and Lonar to determine the nature of alteration and trace element mobilization.

Newsom, H. E.↗

Comparative Planetary Mineralogy: V/(Cr+Al) Systematics in Chromites as an Indicator of Relative Oxygen Fugacity

As our contribution to the new "Oxygen in the Solar System" initiative of the Lunar and Planetary Institute and the NASA Cosmochemistry Program, we have been developing oxygen barometers based largely on behavior of V which can occur in four valence states V2+, V3+, V4+, and V5+, and record at least 8 orders of magnitude of fO2. Our first efforts in measuring these valence proportions were by XANES techniques in basaltic glasses from Earth, Moon, and Mars. We now address the behavior of V valence states in chromite in basalts from Earth, Moon, and Mars. We have been looking for a "V in chromite oxybarometer" that works with data collected by the electron microprobe and thus is readily accessible to a large segment of the planetary materials community. This paper describes very early results that will be refined over the next two years.

Papike, J. J.↗

Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update

We have been developing an oxygen barometer based on the valence state of V (V(2+), V(3+), V(4+), and V(5+)) in solar system basaltic glasses. The V valence is determined by synchrotron micro x-ray absorption near edge structure (XANES), which uses x-ray absorption associated with core-electronic transitions (absorption edges) to reveal a pre-edge peak whose intensity is directly proportional to the valence state of an element. XANES has advantages over other techniques that determine elemental valence because measurements can be made non-destructively in air and in situ on conventional thin sections at a micrometer spatial resolution with elemental sensitivities of approx. 100 ppm. Recent results show that fO2 values derived from the V valence technique are consistent with fO2 estimates determined by other techniques for materials that crystallized above the IW buffer. The fO2's determined by V valence (IW-3.8 to IW-2) for the lunar pyroclastic glasses, however, are on the order of 1 to 2.8 log units below previous estimates. Furthermore, the calculated fO2's decrease with increasing TiO2 contents from the A17 VLT to the A17 Orange glasses. In order to investigate these results further, we have synthesized lunar green and orange glasses and examined them by XANES.

Karner, J. M.↗