Temperature-dependence of Fe-Ti spectra in the visible region - Implications to mapping Ti concentrations of hot planetary surfaces
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Engineering topics
Publications and source records attributed to Burns, R. G..
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Techniques for obtaining information on the crystal chemistry of transition-metal ions from measurement of the electronic absorption spectra of lunar minerals are reviewed along with the theory of spectral interpretation. Typical polarized absorption spectra are examined for lunar pyroxenes, pyroxferroite, olivine, and plagioclase feldspars. Oxidation states of Fe, Ti, and Cr in lunar minerals are discussed, and conditions under which they crystallized are considered. It is shown how information on the gross mineralogy and petrology of different regions of the moon's surface may be extracted from remote reflectivity measurements of that surface.
Results are reported of Fe(++) crystal field spectral measurements for olivines and pyroxenes up to 400 C. The results are correlated with crystal structure data at elevated temperatures, and the validity of remote-sensed identifications of minerals on hot surfaces of the moon and Mercury is assessed. Two techniques were used to obtain spectra of minerals at elevated temperatures using a spectrophotometer. One employed a diamond cell assembly or a specially designed sample holder to measure polarized absorption spectra of heated single crystals. For the other technique, a sample holder was designed to attach to a diffuse reflectance accessory to produce reflectance spectra of heated powdered samples. Polarized absorption spectra of forsterite at 20-400 C are shown in a graph. Other graphs show the temperature dependence of Fe(++) crystal field bands in olivines, the diffuse reflectance spectra of olivine at 40-400 C, the polarization absorption spectra of orthopyroxene at 30-400 C, the diffuse reflectance spectra of pigeonite at 40-400 C, and unpolarized absorption spectra of lunar pyroxene from Apollo 15 rock 15058.
The following transitions are observed in the electronic absorption spectra of lunar titanaugites: Fe(2+) spin-allowed and spin-forbidden crystal field; Ti(3+) spin allowed and Jahn-Teller split crystal field; Ti(3+)-Ti(4+) CT; Fe(2+)-Ti(4+) CT; and O(2-)-Fe(2+), Ti(3+), Ti(4+) CT. Of these, the transitions involving Ti(3+) are unique to lunar or nonferric-bearing titanaugites. All titanaugites have the Fe(2+) crystal field and Fe(2+)-Ti(4+) CT transitions in common. These features in the diffuse reflectance spectra of lunar materials give rise to the '1.0 band' and to the observed absorption around 0.5-0.6 micron, respectively. Since regolith contains a variety of phases with coexisting Fe(2+), Ti(3+), and Ti(4+) ions, several metal-metal charge transfer processes are possible.
The minerals of chromium are tabulated together with sources of data on their crystal structures and on new or recent occurrences. Cr(3+) ions in octahedral coordination with oxygen and tetrahedral doubly negatively charged Cr(VI)O4 ions predominate in minerals on earth, whereas lunar minerals contain Cr(2+) and Cr(3+) ions. Meteorites also contain additional rare sulfide and nitride minerals of chromium.
Prominent bands in the spectral profiles of Fe-Ti phases in lunar samples have been attributed to charge-transfer transitions between Fe and Ti cations, and a model is presented for calculating charge transfer energies from energy levels computed by the SCF-X(alpha) scattered wave molecular orbital method for isolated MO6 octahedral coordination clusters containing Fe(2+), Fe(3+), Ti(3+), and Ti(4+) cations. The calculated charge transfer energy for the Fe(2+) to Ti(4+) transition correlates well with a measured spectral feature around 0.6 micron in ilmenite, and, since ilmenite is a major constituent of mare basalts and dark-mantling material, the observed darkness and blueness of the regolith in lunar black spots is attributed primarily to this transition. The Ti(3+) to Ti(4+) transition is thought to contribute to some phases.
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Analysis of the Moessbauer spectra of two Apollo 16 rocks showed that 60315,51 is much richer in iron metal and troilite, but poorer in olivine, than 62295,27. The values of magnetic parameters, derived from hysteresis loops at 175 and 300 K, indicate the high metal contents and the predominance of coarse multidomain grains in both rocks. These coexist with a superparamagnetic grain fraction in 60315 and with a small single-domain grain fraction in 62295. The high Fe(0)/Fe(2+) ratios, the nonlinear acquisition of laboratory thermoremanence, and the drastic changes in magnetic parameters upon heating support the proposed formation of both rocks from the lunar regolith, with incorporation of shocked meteoritic metal grains during high-temperature impact events and simultaneous acquisition of magnetic remanence. Values estimated for ancient lunar magnetic fields by comparing the natural remanence with laboratory thermoremanence acquired in fields of 0.05 and 0.5 Oe, range from 0.01 to more than 1 Oe.
Measurements have been made of the polarized absorption spectra (360-2200 nm) of compositionally zoned pyroxene minerals in rocks 10045, 10047 and 10058 and olivines in rocks 10020 and 10022. The Apollo 11 pyroxenes with relatively high Ti/Fe ratios were chosen initially to investigate the presence of crystal field spectra of Fe(2+) and Ti(3+) ions in the minerals. Broad intense bands at about 1000 and 2100 nm arise from spin-allowed, polarization-dependent transitions in Fe(2+) ions in pyroxenes. Several weak sharp peaks occur in the visible region. Peaks at 402, 425, 505, 550, and 585 nm represent spin-forbidden transitions in Fe(2+) ions, while broader bands at 460-470 nm and 650-660 nm are attributed to Ti(3+) ions. Charge transfer bands, which in terrestrial pyroxenes often extend into the visible region, are displaced to shorter wavelengths in lunar pyroxenes. This feature correlates with the absence of Ti(3+) ions in these minerals.
Criticism of a statistical approach used by Dasgupta (1972) in analyzing Snyder's (1959) chemical data for minerals from the Duluth Complex in Minnesota. Apart from obvious mathematical objections to citing correlation coefficients to four significant figures from Snyder's relatively inaccurate analytical data, several more fundamental criticisms are leveled at the statistical approach of Dasgupta. These relate to compositional zoning and disequilibrium in the minerals, inhomogeneities of the samples caused by inclusions and exsolved phases, measured site population data for the major cations in olivines and pyroxenes, and the importance of coupled substitutions in the crystal structures. It is concluded that the crystal field predictions of relative enrichments of Ni(2+) and Co(2+) ions in olivine and pyroxene structures have not been disproved by Dasgupta's statistical approach.
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Urease activity in soil is persistent for long periods under low water, low temperature, and sterile regimes, and it was suggested that some form of enzyme-protective mechanism exists in soil. Dublin soil was extracted by sonication in water followed by adding a mixture of salts. Urease activity is associated with the organo-mineral complex thus obtained and is resistant to the activities of proteolytic enzymes. Clay free soil organic matter prepared subsequently by filtration also exhibits urease activity which is resistant to proteolysis. Models consisting of enzymes with bentonite and lignin were found to mimic this resistance to proteolysis. A model system is presented which suggests both the origin and location of soil ureases and a reason for their persistence in nature.
Description of an extraction from a Dublin clay loam soil of a colloidal organic matter complex that is urease active and, by X-ray analysis, free of clays. Urease activity in the clay-free precipitates, as in the soil, was not destroyed by the activity of an added proteolytic enzyme, pronase. This is attributed to the circumstance that native soil urease resides in organic colloidal particles with pores large enough for water, urea, ammonia, and carbon dioxide to pass freely, but nevertheless small enough to exclude pronase.
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Absorption spectra in the visible and near infrared regions have been obtained for pyroxene single crystals in rocks from the Apollo 11, 12, 14, and 15 missions. The polarized spectra are compared with those obtained from terrestrial calcic clinopyroxenes, subcalcic augites, pigeonites, and orthopyroxenes. The lunar pyroxenes contain several broad, intense absorption bands in the near infrared, the positions of which are related to bulk composition, Fe(2+) site occupancy and structure type of the pyroxene. The visible spectra contain several sharp, weak peaks mainly due to spin-forbidden transitions in Fe(2+). Additional weak bands in this region in Apollo 11 pyroxenes are attributed to Ti(3+) ions. Spectral features from Fe(3+), Mn(2+), Cr(3+), and Cr(2+) were not observed.
Abundance, persistence, and localization of enzyme activity in terrestrial soil and exploration of soils suitable for planetary life