ALBERT

Description: Using in-situ x-ray fluorescence, we determined the Cr/Fe, Mn/Fe and Ni/Fe of a particle captured in aerogel on MIR are approximately chondritic, indicating an extraterrestrial origin. Impurity of the aerogel precluded determining the Cu and Zn.

Description: 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.

Description: 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.

Description: We measured minor element contents of carbonate from ALH84001 and report trends in the Ca, V, Mn and Sr in carbonate and the associated magnetite bands. Additional information is contained in the original extended abstract.

Description: The Cl/Br ratios in fracture-filling materials in veins in Nakhla olivine was determined using x-ray microprobe (Br) and EDX (Cl) techniques. The Cl/Br ratio of 55 (standard deviation: 13) shows that the secondary altered material is pristine, extraterrestrial and akin to the Martian soil. Additional information is contained in the original extended abstract.

Description: Combined X-ray microprobe (XRM), energy dispersive x-ray fluorescence using a Transmission Electron Microscope (TEM), and electron microprobe measurements have determined that the average bulk chemical composition of the interplanetary dust particles (IDPs) collected from the Earth s stratosphere is enriched relative to the CI meteorite composition by a factor of 2 to 4 for carbon and for the moderately volatile elements Na, K, P, Mn, Cu, Zn, Ga, Ge, and Se, and enriched to approximately 30 times CI for Br. However, Jessberger et al., who have reported similar bulk enrichments using Proton Induced X-ray Emission (PIXE), attribute the enrichments to contamination by meteor-derived atmospheric aerosols during the several weeks these IDPs reside in the Earth s atmosphere prior to collection. Using scanning Auger spectroscopy, a very sensitive surface analysis technique, Mackinnon and Mogk have observed S contamination on the surface of IDPs, presumably due to the accretion of sulfate aerosols during stratospheric residence. But the S-rich layer they detected was so thin (approximately 100 angstroms thick) that the total amount of S on the surface was too small to significantly perturb the bulk S-content of a chondritic IDP. Stephan et al. provide support for the contamination hypothesis by reporting the enrichment of Br on the edges of the IDPs using Time-of-Flight Secondary-Ion Mass-Spectrometry (TOFSIMS), but TOF-SIMS is notorious for producing false edge-effects, particularly on irregularly-shaped samples like IDPs. Sutton et al. mapped the spatial distribution of Fe, Ni, Zn, Br, and Sr, at the approximately 2 m scale, in four IDPs using element-specific x-ray fluorescence (XRF) computed microtomography. They found the moderately volatile elements Zn and Br, although spatially inhomogeneous, were not concentrated on the surface of any of the IDPs they examined, suggesting that the Zn and the Br enrichments in the IDPs are not due to contamination during stratospheric residence.

Description: X-ray pleochroism is a predictable source of scatter in synchrotron microXANES analyses of elemental oxidation states. The magnitude of the effect is illustrated and a procedure to compensate for it has been implemented, reducing errors significantly. Additional information is contained in the original extended abstract.

Description: Microanalysis of Fe-3+/Total(Fe) in extraterrestrial samples is important due to sample size constraints of sample return missions. We compare Fe XANES spectra with Co optical spectra that predict valence electron levels based on 'Z1' model. Additional information is contained in the original extended abstract.

Description: Using elemental abundances determined by SPIRIT APX spectrometer on rocks and soils at Gusev Plains and Columbia Hills/ West Spur regions, the Athena Team discussed the aqueous geochemical implications at these sites on Mars. They suggested that these rocks were exposed to variable degrees of aqueous alteration (low to high) at Gusev crater. Earlier, we developed analytical procedures for studying aqueous geochemical behavior of fluids on rocks at Meridiani. In the present study, we apply these methods to rocks at Columbia Hills/West Spur in order to understand the significance of the Gusev rock results in reference to aqueous geochemical processes on Mars . The data analysis procedure is based on treating SO3 ("a") and Cl ("b") as two variables and tracking the relationship between "a" and "b" when the fluids undergo evaporation. This process of evaporation leads to concentration changes in these two elements finally producing salt assemblages on Martian rocks. In some cases on plotting "a"/ "b" versus "b" in salt assemblages, they yield a hyperbolic distribution. The relationship is transformed into a straight line when "a"/"b" is again plotted against 1/"b" in the system. Earlier, we used this procedure in the case of Merdiani rock abrasion tool (RAT) rocks and in this study, we discuss the application of this procedure to Gusev rocks. This study shows that the Gusev Plains rocks were exposed to low SO3/Cl solutions (sulfate-poor) for short period of time (weak interaction), whereas solutions with high SO3/Cl ratios (sulfate-rich) seem to have pervasively interacted with Columbia Hills/ West Spur rocks (strong interaction) at Gusev crater. Our conclusions seem to be consistent with the Mossbauer results given for these rocks

Description: Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Mossbauer studies on rocks at Meridian and Gusev, whereas MgSO4 is deduced from MgO - SO3 correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum and alunogen/ S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/ sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. To understand the implications of these observations for the formation of the Gas-rich Impact-melt (GRIM) glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques.