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Experimental evidence shows that compositional effects on Fe-Mg exchange between olivine and liquid cannot be overlooked. High contents of alkalis and/or titanium decrease K(sub D), in contrast to the weak positive pressure dependence.
A finite one-dimensional kinetic model was developed to estimate the cooling rates of lunar rocks. The model takes into consideration the compositional zonation of olivine and applies Buening and Buseck (1973) data on ion diffusion in olivine. Since the 'as-solidified' profile of a given olivine is not known, a step-function, with infinite gradient, is assumed; the position of this step is based on mass balance considerations of the measured compositional profile. A minimum cooling rate would be associated with the preservation of a given gradient. The linear cooling rates of lunar rocks 12002 and 15555 were estimated by use of the olivine cooling-rate indicator to be 10 C/day and 5 C/day, respectively. These values are lower than those obtained by dynamic crystallization studies (10-20 C/day).
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Experiments demonstrated that oxidation of ferromagnesian silicates and magnetite occurs when these minerals are heated at 800 C in 1 atmosphere of CO2, under which conditions hematite is thermodynamically stable. The 30 ppm oxygen impurity in CO2 presumably facilitates the oxidation of some of the ferrous iron initially present in the crystal structures of the minerals. Mossbauer spectral measurements reveal, however, that only CO2 degraded olivine and pigeonite is hematite formed as a magnetically ordered phase at ambient temperatures. In orthopyroxene, some of the ferric iron produced by oxidation is present as nanophase hematite which, because it remains superparamagnetic until 4.2 K, must exist as particles less than or equal to 4 nm in diameter. In the calcic pyroxenes much of the oxidized ferrous iron may still remain as structural Fe3(+) in the host silicates. Some ferric iron may also be present as unit cell sized Fe2O3 inclusions in the pyroxenes, or be segregated along cleavage planes, or be coating mineral grains. In these states of aggregation, the Fe2O3 is unidentifiable by x ray diffraction and in low temperature Mossbauer spectra. Applications of this research to the surface of Venus are discussed.
Orthopyroxene crystals in a number of meteorites exhibit compositional zoning of Fe and Mg, which provide important constraint on their cooling rates. However, attempts to model cooling rate of these crystals from Fe-Mg zoning profiles suffer from the lack of any measured or theoretically well constrained Fe-Mg interdiffusion data in OP(x) It has been assumed that Fe-Mg interdiffusion in OP(x) only slightly slower than that in olivine. The purpose of this paper is to (1) calculate the Fe-Mg fractionation, and (2) provide analytical formulation relating cooling rate to the length of the diffusion zone across the interface of the overgrowth of a mineral on itself with application to Mg diffusion profile across OP(x) growth on OP(x) in certain mesosiderites.
Primitive mid-ocean ridge basalts (MORBs) exhibit Fe isotopic compositions heavier than the upper mantle by +0.074 ± 0.028 ‰ for δ 56 Fe. The processes responsible for this isotopic difference remain unclear. Modeling of Fe isotope fractionation during mantle partial melting requires reliable equilibrium Fe isotope fractionation factors between minerals and melts, for which consistent data are still lacking. Here, in this study, we used Nuclear Resonant Inelastic X-ray Scattering (NRIXS) technique to measure Fe force constants for a MORB glass (ALV 519-4-1) and natural mantle minerals (olivine, orthopyroxene, clinopyroxene, and spinel) to determine the equilibrium Fe isotope fractionation factors between them. The force constants determined in this study, in increasing order, are 167 ± 26 N/m for spinel, 175 ± 17 N/m for olivine, 176 ± 20 N/m for MORB glass, 205 ± 26 N/m for clinopyroxene, and 219 ± 36 N/m for orthopyroxene. We evaluated the previously proposed mechanisms for the heavy Fe isotopic composition of MORBs, including (i) mantle partial melting, (ii) mantle lithological heterogeneity, with pyroxenite in the source, (iii) mantle metasomatism by low-degree melts, and (iv) fractional crystallization of olivine from melts. For (i), we used the pMELTS program to simulate adiabatic decompression melting of mantle peridotites, and calculated Fe isotope fractionation based on Fe 3+ –Fe 2+ equilibrium-controlled fractionation, where Fe 3+ forms stronger bonds and is more incompatible than Fe 2+ . At 10 wt% peridotite melting, corresponding to MORB generation, only +0.03 ‰ Fe isotope fractionation between the melt and the original bulk composition (Δ 56 Fe = δ 56 Fe melt - δ 56 Fe 0 ) was produced, insufficient to account for the observed MORB-upper mantle difference. For (ii), melting of pyroxenites yields smaller Fe isotope fractionation than melting of peridotites, making it unlikely the cause for the MORB-upper mantle isotopic difference. For (iii), both the Fe 3+ /ΣFe ratio and the δ 56 Fe of melts increase with the degree of partial melting, indicating that low-degree melts are not isotopically heavy enough to significantly alter the isotopic composition of lithospheric mantle through metasomatism. For (iv), equilibrium isotope fractionation between olivine and melt is near zero. These results suggest that equilibrium Fe isotope fractionation alone cannot explain the MORB isotopic signature, highlighting the potential role of kinetic isotope fractionation. Using a diffusion model, we calculated kinetic Fe and Mg isotope fractionations associated with (iv) olivine crystallization from a melt, and found that the predicted Fe and Mg isotope fractionations were inconsistent with observations in MORBs. Qualitatively, two processes could have induced kinetic Fe isotope fractionation during MORB generation: (a) Fe-Mg interdiffusion between melt and solid during melt migration and (b) reactive melt-rock interactions during melt focusing. However, a quantitative understanding of their role in modifying the melt isotopic composition remains limited and requires further investigation.
Mid-infrared (MIR) spectroscopy has been used with great success to quantitatively determine the mineralogy of geologic samples. It has been employed in a variety of contexts from determining bulk composition of powdered samples to spectroscopic imaging of rock thin sections via micro-Fourier transform infrared (micro-FTIR) imaging spectroscopy. Recent advances allow for IR measurements at the nanoscale. Near field nanoscale infrared imaging and spectroscopy with a broadband source (nano-FTIR) enable understanding of the spatial relationships between compositionally distinct materials within a sample. This will be of particular use when analyzing returned samples from Bennu and Ryugu, which are thought to be compositionally like CI or CM1/2 carbonaceous chondrites. Returned samples will likely contain olivine/pyroxene chondrules that have been transformed into hydrous phyllosilicates, sulfides, carbonates, and other alteration phases. The use of near-field infrared techniques to probe the boundaries between once pristine chondrules and alteration phases at the nanoscale is a novel approach to furthering our understanding of the compositional evolution of carbonaceous asteroids and the processes that drive their evolution. Here we report the results of nano-FTIR spectroscopy and imaging measurements performed on the carbonaceous chondrite Allan Hills (ALH) 83100 (CM1/2). We show with nanoscale resolution that spatially resolved Fe-Mg variations exist within the phyllosilicates around a chondrule rim. We also present effects of crystal orientation on the nano-FTIR spectra to account for the spectral differences between the meteorite and mineral spectra.
Askival is a light-toned, coarsely crystalline float rock, which was identified near the base of Vera Rubin Ridge in Gale crater. We have studied Askival, principally with the ChemCam instrument but also using APXS compositional data and MAHLI images. Askival and an earlier identified sample, Bindi, represent two rare examples of feldspathic cumulate float rocks in Gale crater with >65% relict plagioclase. Bindi appears unaltered whereas Askival shows textural and compositional signatures of silicification, along with alkali remobilization and hydration. Askival likely experienced multiple stages of alteration, occurring first through acidic hydrolysis of metal cations, followed by deposition of silica and possible phyllosilicates at low T and neutral-alkaline pH. Through laser-induced breakdown spectroscopy compositional analyses and normative calculations, we suggest that an assemblage of Fe-Mg silicates including amphibole and pyroxene, Fe phases, and possibly Mg-rich phyllosilicate are present. Thermodynamic modeling of the more pristine Bindi composition predicts that amphibole and feldspar are stable within an upper crustal setting. This is consistent with the presence of amphibole in the parent igneous rocks of Askival and suggests that the paucity of amphiboles in other known Martian samples reflects the lack of representative samples of the Martian crust rather than their absence on Mars.
Principal components analysis is used to study the chemical compositions of pyroxenes of five Apollo 12 specimens. Important correlations are recognized in the variation of oxide weight per cent. These correlations indicating substitutional relationships can be interpreted as representative of stable and metastable trends of crystallization by using crystal-chemical and thermodynamic information. The per cent variance of pyroxene groups with characteristic trends in each specimen can be evaluated and interpreted in terms of history of crystallization. Distribution of Fe and Mg in certain pairs of olivine and pyroxene, which are found in contact in the rock and which may have crystallized simultaneously, is useful in recognizing the tendency towards chemical equilibrium in Fe-Mg distribution during a limited interval in the liquidus or subsolidus stages.
The paper presents microprobe data on controlled cooling experiments on the eucrite meteorite Stannern, with emphasis on pyroxene zoning and chemistry, development of immiscible liquids in the mesostasis, and compositional boundary layer development adjacent to crystals. Controlled cooling rate experiments on melted samples of the meteorite yield a variety of petrographic textures that can be related to the cooling rate. Textures of clasts in Stannern suggest natural cooling rates of .1 to 100 C/hr for various clasts in the meteorite. Residual liquids are found to unmix at temperatures below about 990 C at moderate cooling rates. Results indicate that Stannern's pyroxenes have evidently undergone subsolidus internal cation exchange, thereby removing Fe-Mg variation in pyroxenes, lowering Al contents, and promoting exosolution.
Thermodynamic and phase equilibrium data are used to generate an internally consistent set of enthalpies and entropies for important components of the CaO-MgO-Al2O3-SiO2 (CMAS) system in silica-undersaturated compositions. The addition of Na and Fe(2+) to the CMAS system produces shifts in the plagioclase, spinel and garnet stability fields. While the Morgan and Anders (1979) model Martian composition has stability fields of plagioclase and garnet lherzolite, and a small spinel lherzolite field at temperatures below 900 C, the Martian mantle composition of McGetchin and Smyth (1978) would not contain orthopyroxene, and a low pressure assemblage of plagioclase-spinel wehrlite would be replaced by garnet-spinel wehrlite at higher pressure. In both cases, the Fe-Mg ratio would be substantially greater than that found in primitive terrestrial basalts.
Cordierite-bearing metapelites of the Eastern Ghat granulite terrain occur in close association of Khondalites, quartzites, calc-silicate rocks and charnockites. Rocks occurring between Bobbili in the north and Guntur in the south of Andhra Pradesh are studied. The association of the mineral and textural relationships suggest the following metamorphic reactions: Garnet + sillimanite + quartz = cordierite, hypersthene + sillimanite + quartz = cordierite, sillimanite + spinel = cordierite + corundum, and biotite + quartz + sillimanite = cordierite + K=feldspar. Generally the minerals are not chemically zoned except garnet-biotite showing zoning when they come in close contact with one another. The potential thermometers are provided by the Fe-Mg distribution of coexisting biotite-garnet and cordierite-garnet. Conflicting interpretation of the P/T dependence of these reactions involving cordierite are due to H2O in the cordierite. The presence of alkali feldspar-quartz assemblage which is common in these gneisses will be constrained from melting only if H2O activity is less than 0.5. The piezometric array inferred is convex towards the temperature array, indicating a rapid and isothermal crustal uplift probably aided by thrust tectonics.
Small fragments of rock found among soil particles in sample 67513 from Station 11 on the southern rim of North Ray Crater at Apollo 16 yield information regarding the mafic, ferroan rocks from which they drive. We have identified a set of particles that have distinctive trace element geochemistry and whose bulk and mineral compositions indicate a genetic relationship to one another. These include polymict as well as monomict lithologies. Igneous members range from fragments with abundant anorthite to some with abundant exsolved pigeonite and augite. Consideration of this set of rock fragments, combined with mafic ferroan clasts from large breccias and from lunar-highlands meteorites suggests that there may be separate differentiation trends within the ferroan suite which are subparallel and which are less steem in Fe-Mg vs. An fractionation that the vertical trend obtained when the entire ferroan suite is taken together. This may result from a complex magma system with isolated reservoirs or separate, independently evolving magmas. Mineral compositional and textural variations are consistent with a model set forth by Longhi and Boudreau wherein the anorthite-rich samples reflect adcumulus growth with mafic crystals forming only from trapped liquid, and the more mafic samples by anorthite and pyroxene orthocumulate development.
The petrologic sequence observed in the CO3 chondrite group has been suggested to be the result of thermal metamorphism on a parent body. A model developed to examine the possibility that chondrule and matrix olivines equilibrated in situ, during parent body metamorphism is presented. The model considers Fe-Mg interdiffusion between chondrule and matrix olivines. Zoning profiles comparable to those observed in chondrule olivines from partially equilibrated members of the series are reproduced successfully. Metamorphism of CO3 chondrites on a parent body is therefore a viable model for the observed equilibration. Results indicate that peak metamorphic temperatures experienced by the CO3 chondrites were around 500 C, and that the range of peak temperatures between unequilibrated and equilibrated subtypes was relatively narrow, around 100 C.
Experimentally produced analogues of porphyritic olivine (PO) chondrules in ordinary chondrites provide an important insight into chondrule formation processes. We have studied experimental samples with PO textures grown at three different cooling rates (2, 5 and 100 C/h), and samples that have been annealed at high temperatures (1000-1200 C) subsequent to cooling. These are compared with natural chondrules of similar composition and texture from the ordinary chondrites Semarkona (LL3.0) and ALH 81251 (LL3.3). Zoning properties of olivine grains indicate that the Semarkona chondrules cooled at comparable rates to the experiments. Zoning in olivine from chondrules in ALH 81251 is not consistent with cooling alone but indicates that the chondrules underwent an annealing process. Chromium loss from olivine is very rapid during annealing and calculated diffusion coefficients for Cr in olivine are very similar to those of Fe-Mg interdiffusion coefficients under the same conditions. Annealed experimental samples contain an aluminous, low-Ca pyroxene which forms by reaction of olivine and liquid. No similar reaction texture is observed in ALH 81251 chondrules, and this may be evidence that annealing of the natural samples took place at considerably lower temperatures than the experimental analogues. The study supports the model of chondrule formation in a cool nebula and metamorphism of partly equilibrated chondrites during reheating episodes on the chondrite parent bodies.
We report microprobe, instrumental neutron activation analysis, and radiochemical neutron activation analysis data for three large igneous inclusions in the Yamato (Y-)75097, Y-793241, and Y-794046 ordinary chondrites. The inclusions in the first two chondrites are troctolitic cumulates that have undergone appreciable reactions with their hosts either during emplacement and/or cooling. Olivine-spinel Fe-Mg exchange pairs in these two inclusions record equilibration temperatures of about 710 C, and these temperatures are similar to those exhibited by mineral pairs in the Y-75097 and Y-793241 hosts. The inclusion in Y-794046 is texturally unique, consisting of fine-grained, randomly distributed olivines, coarse (approximately 2 mm) fascicular pyroxene laths, and angular pockets of maskelynite/plagioclase feldspar. The phase compositions are readily interpreted as having resulted from extremely rapid, essentially isochemical cooling to temperatures less than 1000 C of a melt with an initial temperature greater than 1670 C. We suggest that this igneous inclusion formed in-situ by shock.
Reconstruction of stratigraphic relationships in the ancient lunar crust has proved to be a formidable task. The intense bombardment during the first 700 m.y. of lunar history has severely perturbed the original stratigraphy and destroyed the primary textures of all but a few nonmare rocks. However, a knowledge of the crustal stratigraphy as it existed prior to the cataclysmic bombardment about 3.9 Ga is essential to test the major models proposed for crustal origin, i.e., crystal fractionation in a global magmasphere or serial magmatism in a large number of smaller bodies. Despite the large difference in scale implicit in these two models, both require an efficient separation of plagioclase and mafic minerals to form the anorthositic crust and the mafic mantle. Despite the havoc wreaked by the large body impactors, these same impact processes have brought to the lunar surface crystalline samples derived from at least the upper half of the lunar crust, thereby providing an opportunity to reconstruct the stratigraphy in areas sampled by the Apollo missions. As noted, ejecta from the large multiring basins are dominantly, or even exclusively, of crustal origin. Given the most recent determinations of crustal thicknesses, this implies an upper limit to the depth of excavation of about 60 km. Of all the lunar samples studied, a small set has been recognized as "pristine", and within this pristine group, a small fraction have retained some vestiges of primary features formed during the earliest stages of crystallization or recrystallization prior to 4.0 Ga. We have examined a number of these samples that have retained some record of primary crystallization to deduce thermal histories from an analysis of structural, textural, and compositional features in minerals from these samples. Specifically, by quantitative modeling of (1) the growth rate and development of compositional profiles of exsolution lamellae in pyroxenes and (2) the rate of Fe-Mg ordering in orthopyroxenes, we can constrain the cooling rates of appropriate lunar samples. These cooling rates are used to compute depths of burial at the time of crystallization, which enable us to reconstruct parts of the crustal stratigraphy as it existed during the earliest stages of lunar history.
Fe-Mg site occupancy determinations of orthopyroxene from troctolite 76535 yield closure temperatures of ordering of 500-550 C and cooling rates of 1-10 C per year corresponding to shallow burial. 76535 was excavated from deep lunar crust before it had cooled to approx. 550 C. Additional information is contained in the original extended abstract.