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All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

The ilmenite/titano-magnetite assemblage - Kinetics of re-equilibration

The petrogenesis of igneous and metamorphic rocks is a function of several parameters. Of these, temperature and pressure are of particular importance. Information concerning these two parameters is obtained through the use of mineral indicators. One such commonly used geothermometer/oxybarometer is that involving ilmenite/titano-magnetite. Anomalously low temperatures have been reported in cases in which the geothermometer/oxybarometer was employed. The studies suggest that low temperatures result from slow cooling rates which allows the Fe-Ti oxides to re-equilibrate. The current investigation is mainly concerned with the kinetics of the reduction of ilmenite-hematite solid solution, since this is the slower and, consequently, rate-controlling step in the re-equilibration process. The reaction rates determined for the reduction of ilmenites in the investigation are geologically rapid and must be considered when applying the considered geothermometer/oxybarometer.

Hammond, P. A.↗
NASA NTRS1987

An analysis of the Mariner 10 color ratio map of Mercury

Errors that emerged in the Hapke et al. (1980) geological analysis reproduction of the Mariner 10 orange/UV color ratio map of Mercury are presently noted, and it is judged that the relationships that emerge between the color and the terrain are nonlunar in that they lack Mercurian analogs of high Fe-Ti lunar maria basalts. The crust is found to be low in Fe(2+) and Ti(4+) in view of three major considerations: (1) rays and ejecta blankets are exceptionally blue; (2) the Fe(2+) band of the reflectance spectrum of Mercury is weak; and (3) Mercury albedo contrasts are less pronounced than the lunar ones. The extrusive origin of the smooth plains is supported by these observations.

Rava, Barry↗
NASA NTRS2003

Moessbauer Spectroscopy of Mineral Separates from SNC Meteorites

Numerous workers have recently focused attention on the issue of the oxygen fugacity (f(sub O2)) of martian samples. Estimates of fO2 based on Fe-Ti oxides and D(sub Eu)/D(sub Gd) and D(sub Eu)/D(sub Sm) ratios suggest a range of fO2 values for SNC meteorites from IW+2.5 - IW+3.5 for Shergotty to IW- 2.0 - IW+0.2 for QUE94201. Fe(3+)/Fe(2+) is also a function of f(sub O2), and synchrotron micro-XANES values for olivine, pyroxene, and feldspar Fe(3+) have been reported. However, the relationship between the reported Fe(3+) values and the other methods for estimating f(sub O2) is not clear, and further measurements of Fe(3+)/Fe(2+) by a more conventional technique have been needed. Accordingly, in this project, new Mossbauer spectroscopy data on mineral separates handpicked from 10 SNC meteorites are reported.

Dyar, M. D.↗
NASA NTRS2004

Evidence for a Wet, Reduced Martian Interior

Knowledge of the oxygen fugacity and hydrogen content of the source regions of martian meteorites is of paramount importance in constraining phase equilibria, crystallization sequences, and geodynamic processes of the martian interior, as well as models of the planet's evolution. To date, these interpretations have been hindered by the paucity in SNC meteorites of Fe-Ti oxides used in conventional oxybarometry, and by the presence of secondary alteration products that make it impossible to quantify primary hydrogen abundances in SNC minerals and melts based on whole rock samples. We present here the first transmission FTIR spectra of individual mineral grains from SNC meteorites, and interpret those results along with Mossbauer data on mineral separates from the same meteorites. Our goal is to quantify the amount of water and the oxygen fugacity present in the source regions for the rocks comprising the meteorites.

Dyar, M. D.↗
NASA NTRS2004

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.↗
NASA NTRS2004

Oxygen Fugacity of the Martian Mantle from Pigeonite/Melt Partitioning of Samarium, Europium and Gadolinium

This study is part of an ongoing effort to calibrate the pyroxene/melt Eu oxybarometer for conditions relevant to the martian meteorites. There is fairly good agreement between a determinations using equilibria between Fe-Ti oxides and the estimates from Eu anomalies in shergottite augites in tenns of which meteorites are more or less oxidized. The Eu calibration was for angrite composition pyroxenes which are rather extreme. However, application of a calibration for martian composition augites 113 does not significantly reduce the discrepancy between the two methods. One possible reason for this discrepancy is that augites are non-liquidus. The use of pigeonite rather than augite as the oxy-barometer phase is considered. We have conducted experiments on martian composition pigeonite/melt REE partitioning as a function of fO2.

Musselwhite, S.↗
NASA NTRS2009

Northwest Africa 5298: A Basaltic Shergottite

NWA 5298 is a single 445 g meteorite found near Bir Gandouz, Morocco in March 2008 [1]. This rock has a brown exterior weathered surface instead of a fusion crust and the interior is composed of green mineral grains with interstitial dark patches containing small vesicles and shock melts [1]. This meteorite is classified as a basaltic shergottite [2]. A petrologic study of this Martian meteorite is being carried out with electron microprobe analysis and soon trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Oxygen fugacity is calculated from Fe-Ti oxides pairs in the sample. The data from this study constrains the petrogenesis of basaltic shergottites.

Hui, Hejiu↗
NASA NTRS2008

Analysis of Lunar Highland Regolith Samples from Apollo 16 Drive Core 64001/2 and Lunar Regolith Simulants - An Expanding Comparative Database

We present modal data from QEMSCAN(registered TradeMark) beam analysis of Apollo 16 samples from drive core 64001/2. The analyzed lunar samples are thin sections 64002,6019 (5.0-8.0 cm depth) and 64001,6031 (50.0-53.1 cm depth) and sieved grain mounts 64002,262 and 64001,374 from depths corresponding to the thin sections, respectively. We also analyzed lunar highland regolith simulants NU-LHT-1M, -2M, and OB-1, low-Ti mare simulants JSC-1, -lA, -1AF, and FJS-1, and high-Ti mare simulant MLS-1. The preliminary results comprise the beginning of an internally consistent database of lunar regolith and regolith simulant mineral and glass information. This database, combined with previous and concurrent studies on phase chemistry, bulk chemistry, and with data on particle shape and size distribution, will serve to guide lunar scientists and engineers in choosing simulants for their applications. These results are modal% by phase rather than by particle type, so they are not directly comparable to most previously published lunar data that report lithic fragments, monomineralic particles, agglutinates, etc. Of the highland simulants, 08-1 has an integrated modal composition closer than NU-LHT-1M to that of the 64001/2 samples, However, this and other studies show that NU-LHT-1M and -2M have minor and trace mineral (e.g., Fe-Ti oxides and phosphates) populations and mineral and glass chemistry closer to these lunar samples. The finest fractions (0-20 microns) in the sieved lunar samples are enriched in glass relative to the integrated compositions by approx.30% for 64002,262 and approx.15% for 64001,374. Plagioclase, pyroxene, and olivine are depleted in these finest fractions. This could be important to lunar dust mitigation efforts and astronaut health - none of the analyzed simulants show this trend. Contrary to previously reported modal analyses of monomineralic grains in lunar regolith, these area% modal analyses do not show a systematic increase in plagiociase/pyroxene as size fraction decreases.

Schrader, Christian M.↗
NASA NTRS2010

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Sutton, S. R.↗
NASA NTRS2004

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Ming, Douglas W.↗
NASA NTRS2014

Looking for a Source of Water in Martian Basltic Breccia NWA 7034

The recently described martian meteorite NWA 7034 has high water content compared to other SNC meteorites. Deuterium to hydrogen isotope ratio measurements indicates that there are two distinct delta-D components in NWA 7034, a low temperature (150-500degC) light component around -100per mille and a high temperature (300-1000degC) heavy component around +300per mille. NWA 7034 contains iron-rich phases that are likely secondary aqueous alteration products. They are commonly found as spheroidal objects of various sizes that are often rich in Fe-Ti oxides and possibly iron hydroxides. Iron oxides and oxyhydroxides are very common in weathered rocks and soils on Earth and Mars and they are important components of terrestrial and Martian dust. In NWA 7034 iron-rich phases are found throughout the fine-grained basaltic groundmass of the meteorite. The total amount of martian H2O in NWA 7034 is reported to be 6000 ppm, and in this study we attempt to determine the phase distribution of this H2O by texturally describing and characterizing hydrous phases in NWA 7034, using Fourier transform infrared spectrometry (FTIR) and transmission electron microscopy (TEM).

Muttik, N.↗
NASA NTRS2016

The Cr Redox Record of fO2 Variation in Angrites. Evidence for Redox Conditions of Angrite Petrogenesis and Parent Body

Angrites represent some of the earliest stages of planetesimal differentiation. Not surprisingly, there is no simple petrogenetic model for their origin. Petrogenesis has been linked to both magmatic and impact processes. Studies demonstrated that melting of chondritic material (e.g. CM, CV) at redox conditions where pure iron metal is unstable (e.g., IW+1 to IW+2) produced angrite-like melts. Alternatively, angrites were produced at more reducing conditions (<IW) with their exotic melt compositions resulting from carbonates in the source or from nebular condensation. Clearly, understanding what role fO2 plays in producing angrite magmas is critical for deciphering their petrogenesis and extending our understanding of primordial melting of asteroids. Calculations for the fO2 conditions of angrite crystallization are limited, and only preliminary attempts been made to understand the changes in fO2 that occurred during petrogenesis. Many of the angrites have phase assemblages which provide conflicting signals about redox conditions during crystallization (e.g., Fe metal and a Fe-Ti oxide with potential Fe3+. There have been several estimates of fO2 for angrites. Most notably, experiments examined the variation of DEu/DGd with fO2, between plagioclase and fassaitic pyroxene in equilibrium with an angrite melt composition. They used their observations to estimate the fO2 of crystallization to be approximately IW+0.6 for angrite LEW 86010. This estimate is only a "snapshot" of fO2 conditions during co-crystallization of plagioclase and pyroxene. Preliminary XANES analyses of V redox state in pyroxenes from D'Orbigny reported changes in fO2 from IW-0.7 during early pyroxene crystallization to IW+0.5 during latter episodes of pyroxene crystallization [15]. As this was a preliminary report, it presented limited information concerning the effects of pyroxene orientation and composition on the V valence measurements, and the effect of melt composition on valence and partitioning behavior of V. A closer examination of fO2 as recorded by Cr valence state in olivine will allow us to test models for primordial melting of chondritic material to produce the angrite parent melts. Here, we report the our initial stages of examining the origin and conditions of primordial melting on the angrite parent body and test some of the above models by integrating an experimental study of Cr and V valence partitioning between olivine [OL] and an angrite melt, with micro-scale determinations of Cr and V oxidation state in OL in selected "volcanic" angrites.

Shearer, Charles K.↗
NASA NTRS2017

Feldspar Variability in Northwest Africa 7034

The martian meteorite Northwest Africa 7034 (and pairings) is a breccia that provides important information about the rocks and processes of the martian crust (e.g., 1-3). Additional information can be gleaned from the components of the breccia. These components, specifically those designated as clasts, record the history of their parent rock (i.e., the rock that has been physically broken down to produce the clasts). In order to study these parent rocks, we must first determine which clasts within the breccia are de-rived from the same parent. Previous studies have be-gun this process (e.g., 4), but the search for genetic linkages between clasts has not integrated clasts with different grain sizes. We begin to take this approach here, incorporating igneous-textured clasts with both fine and coarse mineral grains. In NWA 7034, almost all materials (clasts and breccia matrix) are composed of the same mineral assemblages (feldspar, pyroxene, Fe-Ti oxides, apatite) with largely the same mineral compositions [1, 4-6]. Bulk breccia Sm-Nd systematics define a single isochron [7]. These observations are consistent with a majority of the components within NWA 7034 originating from the same geochemical source and crystallizing at roughly the same time.

Santos, A. R.↗
DOE OSTI2020

Materials Data on TiFe by Materials Project

FeTi is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Ti is bonded in a body-centered cubic geometry to eight equivalent Fe atoms. All Ti–Fe bond lengths are 2.56 Å. Fe is bonded in a body-centered cubic geometry to eight equivalent Ti atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ti2Fe by Materials Project

Ti2Fe crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. there are two inequivalent Ti sites. In the first Ti site, Ti is bonded in a 12-coordinate geometry to six equivalent Ti and six equivalent Fe atoms. All Ti–Ti bond lengths are 2.87 Å. All Ti–Fe bond lengths are 2.46 Å. In the second Ti site, Ti is bonded in a 2-coordinate geometry to ten Ti and four equivalent Fe atoms. There are four shorter (2.96 Å) and four longer (3.01 Å) Ti–Ti bond lengths. There are two shorter (2.59 Å) and two longer (2.86 Å) Ti–Fe bond lengths. Fe is bonded in a 12-coordinate geometry to nine Ti atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ti4Fe by Materials Project

FeTi4 crystallizes in the orthorhombic Fmmm space group. The structure is three-dimensional. there are two inequivalent Ti sites. In the first Ti site, Ti is bonded in a distorted L-shaped geometry to two equivalent Ti and two equivalent Fe atoms. Both Ti–Ti bond lengths are 2.90 Å. Both Ti–Fe bond lengths are 2.40 Å. In the second Ti site, Ti is bonded in a distorted body-centered cubic geometry to eight Ti atoms. There are two shorter (2.78 Å) and four longer (2.82 Å) Ti–Ti bond lengths. Fe is bonded in a distorted square co-planar geometry to four equivalent Ti atoms.

36 MATERIALS SCIENCE↗