ALBERT

Description: Visible and near-IR refectivity, Moessbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to approximately 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration Fe(3+)/Fe(sub tot) and ranged from approximately 1000 nm (high-Ca pyroxene) to approximately 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the approximately 850 and approximately 1000nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relativly high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from the analyses of soil at the two Viking landing sites.

Description: The paper characterizes the mineralogy and spectral properties of three slightly palagonitized basaltic tephra samples collected near the summit of Mauna Kea in order to contribute to the basis for inferring mineralogy and processes for Martian surface materials. The mineralogy of size fractions of these samples is examined by diffuse reflectance and FIR spectroscopy, optical microscopy, X-ray diffraction, Moessbauer spectroscopy, magnetic analysis, EMPA, TEM, and SEM. For the 20-1000 micron size fraction, sample HWMK11 (red) is essentially completely oxidized and has a hematite (Ti-hematite) pigment dispersed throughout the silicate matrix. Sample HWMK12 (black) has the lowest proportion of ferric-bearing phases and is thus least weathered. For HWMK11, the amount of hematite is essentially constant, and mica is present only in the coarse clay-sized fraction; smectites are low in structural Fe.

Description: A novel method of producing mixtures of glass or minerals with iron metal is presented. A portion of the Fe(2+) in basaltic glass and minerals can be reduced to metal in a few hours at 1100 C and an oxygen fugacity well below the iron-wustite buffer. Part of the iron metals forms rounded submicrometer blebs on the surfaces and in some cases within the grains. A concentration of such blebs equivalent to 20-30 percent of a grain's surface area can totally dominate the reflectance spectra of basaltic glass, pyroxene, and olivine. The production of optically opaque iron metal blebs, combined with the decline in Fe(2+), affects the glass and mineral reflectance spectra in three ways: by lowering the overall reflectivity, reducing the spectral contrast of absorption features, and producing a continuum with a general rise in reflectivity toward longer wavelengths.

Description: We have examined a Hawaiian palagonitic tephra sample (PN-9) that has spectroscopic similarities to Martian bright regions using a number of analytical techniques, including Mossbauer and reflectance spectroscopy, X-ray diffraction, instrumental neutron activation analysis, electron probe microanalysis, transmission electron microscopy, and dithionite-citrate-bicarbonate extraction. Chemically, PN-9 has a Hawaiitic composition with alkali (and presumably silica) loss resulting from leaching by meteoric water during palagonitization; no Ce anomaly is present in the REE pattern. Mineralogically, our results show that nanophase ferric oxide (np-Ox) particles (either nanophase hematite (np-Hm) or a mixture of ferrihydrite and np-Hm) are responsible for the distinctive ferric doublet and visible-wavelength ferric absorption edge observed in Mossbauer and reflectivity spectra, respectively, for this and other spectrally similar palagonitic samples. The np-Ox particles appear to be imbedded in a hydrated aluminosilicate matrix material; no evidence was found for phyllosilicates. Other iron-bearing phases observed are titanomagnetite, which accounts for the magnetic nature of the sample; olivine; pyroxene; and glass. By analogy, np-Ox is likely the primary pigmenting agent of the bright soils and dust of Mars.

Description: Goethite-bearing samples with values of Mn(s) (Mn/(Mn+Fe) mole fraction) up to 0.206 were synthesized by precipitation from alkaline solution. Samples with Mn(s) less than or equal 0.061 were single-phase Mn-goethites: samples with higher Mn(s) values contained another Mn-bearing phase (probably jacobsite). Mn-hematites were prepared by dehydroxylation of corresponding Mn-goethites at 500 C. Orthorhombic a and b unit cell dimensions of Mn-goethites changed in a linear manner with Mn(s), but not at rates predicted by the Vegrad law. Hexagonal unit cell dimensions of Mn-hematites did not vary with Mn(s). Moessbauer parameters isomer shift (IS), quadrupole splitting (QS), and hyperfine field (B(sub hf)) were measured at 293 and 15 K. For all single-phase Mn-goethites and Mn-hematites (Mn(s) less than or equal 0.061), magnetic splitting was observed at both temperatures. At 293 K, small but systematic decreases in B(sub hf) were observed with increasing Mn substitution; IS and QS were not dependent on Mn(s). Mn substitution strongly lowered the Morin transition temperature of hematite. At 15 K, the Morin transition was not present for Mn(s) greater than 0.020(4). The saturation magnetization of Mn-goethites and Mn-hematites (Mn(s) less than or equal 0.061) was the expected zero (within error) for antiferromagnetic goethite and for hematites obtained from dehydroxylation of goethites. Mn-geothites with Mn(s) greater than 0.061 were magnetic because of the presence of strongly magnetic jacobsite. For reflectivity spectra, bands resulting from MN(3+) were centered near 454 and 596 nm for Mn-goethites and near 545 and 700 nm for Mn-hematites. There is evidence for a approximately 700 nm band in spectral data for Martian bright regions, but association of it with Mn(3+) is not a unique interpretation. Comparison of laboratory and Martian spectral data implies that Mn(s) less than 0.032 for the Mn(3+) content of Martian hematites.

Description: Experimental studies were made on the compositional dependence of the redox equilibrium of Eu in synthetic silicate liquids, together with an empirical model describing the observed compositional dependence. Electron paramagnetic resonance (EPR) was used to measure the concentration ratio of Eu(2+) to Eu(3+) in various glasses formed by rapidly quenching silicate liquids. The compositional field studied comprised mixtures of SiO2, TiO2, Al2O3, CaO, MgO, and Na2O. The proposed model describes the Eu(2+)/Eu(3+) ratio over the entire compositional field in terms of parameters easily related to each glass composition. The general applicability and utility of the model is further demonstrated by its application to the Fe(2+)-Fe(3+), Ce(3+)-Ce(4+), and Cr(3+)-Cr(6+) redox reactions in binary alkali oxide silicate glasses of Li, Na, and K.

Description: The spectral properties (0.35-2.20 microns) of submicron powders of hematite, maghemite, magnetite, goethite, and lepidocrocite are determined. Other physicochemical data are obtained for the powders in order to determine if deviations from stoichiometry occur due to their small particle size, to determine their state of chemical and phase purity, and to determine the physical characteristics of the individual powders. The physicochemical data obtained include mean particle diameter, discrete particle shape, chemical composition, crystallographic phase, magnetic parameters, and Moessbauer parameters. The positions of the spectral features for the hematite, maghemite, and magnetite powders are independent of temperature over the interval between about +20 and -110 C. For the goethite and lepidocrocite powders, a small shift of about 0.02 micron to shorter wavelengths is observed for some of the features after cooling to about -110 C. The spectral properties of the iron oxides and oxyhydroxides are important not only for understanding the basic physics and chemistry of the compounds but also for applications such as the remote sensing of the earth and Mars.

Description: Meteoritic impacts under oxidizing surface conditions occur on both earth and Mars. Oxidative alteration of impact melt sheets is reported at several terrestrial impact structures including Manicouagan, West Clearwater Lake, and the Ries Basin. A number of studies have advocated that a significant fraction of Martian soil may consist of erosional products of oxidatively altered impact melt sheets. If so, the signature of the Fe-bearing mineralogies formed by the process may be present in visible and near infrared reflectivity data for the Martian surface. Of concern is what mineral assemblages form in impact melt sheets produced under oxidizing conditions and what their spectral signatures are. Spectral and Moessbauer data for 19 powder samples of impact melt rock from Manicouagan Crater are reported. Results show for naturally occurring materials that composite hematite-pyroxene bands have minima in the 910-nm region. Thus many of the anomalous Phobos-2 spectra, characterized by a shallow band minimum in the near-IR whose position varies between approximately 850 and 1000 nm, can be explained by assemblages whose endmembers (hematite and pyroxene) are accepted to be present on Mars. Furthermore, results show that a mineralogically diverse suite of rocks can be generated at essentially constant composition, which implies that variations in Martian surface mineralogy do not necessarily imply variations in chemical composition.

Description: The kinetics of magnetite oxidation in O2-bearing atmospheres in the presence of electromagnetic radiation was studied. No perceptible oxidation of magnetite by ultraviolet (UV) photostimulation occurred. These results do not corroborate previous conclusions by Huguenin (1973, 1974) as to the occurrence of this process. Therefore, although the possibility that the process actually occurs cannot be ruled out, it is concluded that there is not yet a basis in laboratory experiments for inferring that UV photostimulated oxidation of magnetite occurs naturally on the surface of Mars.

Description: The geochemistry of the FeOOH polymorphs is an important consideration when evaluating the likelihood of an occurrence of detectable amounts of these minerals on Mars. An investigation is conducted regarding the stability of the FeOOH polymorphs geothite and lepidocrocite to dehydration in the presence of UV radiation. A thorough characterization of the FeOOH powders used in the laboratory experiments is presented, and the irradiational facility and experimental procedures are described. The results obtained in the conducted experiments are discussed. It is found that there is as yet no basis in laboratory experiments for inferring that perceptible UV photodehydration of FeOOH polymorphs will occur naturally on the surface of Mars on a time scale of at least 10-100 years.