Gianmario Molin

Intracrystalline Cation Distribution in Natural Clinopyroxenes of Tholeiitic, Transitional, and Alkaline Basaltic Rocks

Thermodynamic studies of Mueller (1962) and Thompson (1969) and the crystallographic work of Ghose (1965) gave new impetus to a rapidly developing branch of mineralogy. Orthopyroxenes were studied by Virgo and Hafner (1969) and Saxena and Ghose (1971) using Mossbauer technique. Site-occupancy data have been used in many mineralogical and petrological problems, e.g., to estimate the thermodynamic solution properties of pyroxenes and to understand the cooling history of rocks. A parallel development in the mineralogy of clinopyroxene did not take place, particularly because the Mossbauer technique proved unsatisfactory for calcic pyroxenes. Recognizing this, we undertook a detailed X-ray crystallographic study of the clinopyroxenes and succeeded to determine crystal-structural parameters for Fe-Mg site occupancies of the nonequivalent Ml and M2 sites. Until now there are no published site-occupancy data on a series of clinopyroxene of intermediate composition. This paper attempts to fill this important gap in the data on clinopyroxenes. Besides our concern for the crystal-chemical and thermodynamic aspects of such a study, we were also motivated by the possible use of pyroxene crystallographic parameters in the classification and characterization of magmatic rocks. With the advent of automation in X-ray crystallography, it is possible to study a number of crystals from one or more rock samples in a relatively short time and provide petrologically useful information.

Residual electron density at theM2 site inC2/c clinopyroxenes: Relationships with bulk chemistry and sub-solidus evolution

The systematic study of both natural and synthetic clinopyroxenes often indicates the presence in the difference Fourier map of a maximum of residual density of up to 0.8 electrons, here labelledM2′, close to theM2 site along the diad axis, defining a square pyramid co-ordination polyhedron. To investigate the nature and the crystalchemical implications of this feature, a limited but representative set of clinopyroxenes of volcanic, metamorphic and synthetic origin has been investigated by X-ray structure refinement (at 0.7 and 0.4 Å resolution), by microprobe analysis and by transmission electron microscopy. The most important results are: a) at increasing resolution, the height of theM2′ peak increases while its co-ordinates move towardM2; b) as (Ca + Na) content approaches 1.0 atom per formula unit,M2′ vanishes; c)M2′ has been found in clinopyroxenes which show differing incipient exsolution microstructures, from spinodal decomposition to non-periodic fluctuations, as well as in homogeneous specimens. The presence ofM2′ is interpreted in terms of the simultaneous coexistence in the crystals of two different structural models, approximately diopside and clinoenstatite. An accurate evaluation of the totalM2 + M2′ site occupancy is strongly suggested in XREF work, particularly when thermodynamic and kinetic considerations have to be obtained with accurate determinations of site occupancy factors as a starting point.

Crystal chemistry and evolution of the clinopyroxene in a suite of high pressure ultramafic nodules from the Newer Volcanics of Victoria, Australia

A clinopyroxene suite from lherzolite inclusions associated with the Victorian (Australia) “Newer Volcanics” has been investigated with the aim of understanding the clinopyroxene crystal-chemical response to increasing temperature (e.g. a melting model and/or crystallization processes prevailing at high pressure).The M1 clinopyroxene polyhedron dominates the intracrystalline physical-chemical variations, essentially given by the triple substitution AlVIFeM12Ti4+⇌Cr3+ Fe3+MgM12+corresponding to an increase in the volume of M1 with increasing Mg/Mg+Fe2+ (mg) for the clinopyroxene. A relative Ca2+ increase in M2 ensures the necessary charge balance. However, Na+ occupancy of M2 persists to the highest mg values, i.e. maximum thermal stability, where the volume of M2 is the largest due to FeM22+depletion. The variations of M1 and M2 volumes are greater than, and opposite to, the variations in the volume of T (tetrahedron) by factors of ca. 3 and 1.5, respectively. Inclusions with relatively low clinopyroxene content (Mt. Porndon specimens) show distinct intracrystalline variations, essentially reflecting lower AlVI, i.e. higher volume of M1, and implying a lower pressure regime compared to clinopyroxene-rich analogues (Mt. Leura specimens). The intracrystalline relationships of the Mt. Porndon clinopyroxene suggest that the host peridotite inclusions survived larger degree of mantle melting at shallower depths relative to the Leura analogues.

Primary trapped melt inclusions in olivine in the olivine-augite-orthopyroxene ureilite Hughes 009

We describe the first known occurrence of primary melt inclusions in a ureilite. The ureilite is Hughes 009, one of a small number of ureilites whose primary mineralogy is olivine-augite-orthopyroxene, rather than olivine-pigeonite. Hughes 009 has a coarse-grained, equilibrated texture typical of ureilites, and homogeneous primary mineral compositions: olivine — mg 87.3; augite — mg 89.2, Wo 37.0, Al2O3 = 1.6 wt.%; orthopyroxene — mg 88.3, Wo 4.9. It shows only limited secondary reduction effects and no petrographically recognizable carbon phases, which indicates that its original carbon content was lower than in most ureilites. The melt inclusions occur in olivine crystals. They are concentrated in the central regions of their hosts, showing elongate (mostly 20–60 μm in maximum dimension), negative olivine crystal shapes and parallel alignment. These and other features indicate that they were trapped during initial growth of their hosts from a liquid, and are likely to be representative samples of that liquid. They consist of glass and single, subhedral crystals of high-Ca pyroxene, with minor Cr-rich spinel and metal-phosphide-sulfide spherules. They are surrounded by halos of olivine with rounded outlines defined by tiny bits of metal and thin arcs of glass. Pyroxenes within each inclusion show zonation patterns indicating that they nucleated at the olivine/ liquid interface with compositions close to that of the primary augite, and then grew inward with dramatically increasing Al2O3 (to 10.8 wt.%), Wo (to ≈50), TiO2 and Cr2O3 contents. Glasses within each inclusion are relatively homogeneous. Glasses from all inclusions show well-defined trends of CaO, TiO2, Cr2O3, Na2O and SiO2 vs. Al2O3, (16–23 wt.%) that can be modelled as resulting principally from crystallization of various amounts of the pyroxene. The halos, which represent olivine that grew from the trapped melts, are zoned in Cr and Ca with concentrations decreasing inward, reflecting cocrystallization of pyroxene; they have homogeneous Fe/Mg identical to that of the primary olivine, indicating reequilibration with the host. We develop a petrologic model for the postentrapment history (crystallization, reaction and reequilibration) of the inclusions, based on which we reconstruct the composition of the primary trapped liquid (PTL). The PTL was saturated only with olivine. This result implies that Hughes 009 is a cumulate (consistent with the high Mn/Mg ratio of its olivine and a low abundance of graphite) and that the composition of the PTL is close to that of its parent magma. The low-pressure equilibrium crystallization sequence predicted by MAGPOX calculations for the PTL (olivine → augite → plagioclase → pigeonite) is not, however, consistent with the primary mineralogy of Hughes 009. If the conditions of these calculations are, indeed, appropriate, then complex processes such as magma mixing must have been involved in the petrogenesis of this ureilite. This conclusion is consistent with other evidence that the olivine-augite-orthopyroxene ureilites record a more complex magmatic evolution than is evident in the olivine-pigeonite ureilites. TEM investigations of microtextural features in all phases and XRD determination of Fe2+-Mg site distribution in orthopyroxene have elucidated the cooling and shock history of this ureilite. Hughes 009 experienced an extremely high cooling rate (7 ± 5°C/h at the closure T of 630°C) late in its evolution, and two distinguishable shock events—the first at peak pressures of 5 to 10 GPa, resulting in mechanical polysynthetic twinning in augite and orthopyroxene and mild undulatory extinction in olivine; and the second at lower pressures, resulting only in brecciation and redistribution of metal. Its late history is similar to that of most ureilites, and probably reflects impact excavation.

Iron-magnesium order-disorder in an orthopyroxene crystal from the Johnstown meteorite

Abstract Equilibrium reversals of Fe 2+ Mg distribution between the M1 and M2 sites of an orthopyroxene from the Johnstown meteorite were achieved at several temperatures between 700 and 1000°C. One single crystal was used for the whole thermal treatment and for collecting all the X-ray data after quenching. The intracrystalline ion exchange for the bulk chemical composition: (Mg 1.453 Fe 0.441 Cr 0.024 Ca 0.054 Mn 0.015 Fe 0.005 Ti 0.003 Al 0.005 )(Si 1.960 Al 0.040 )O 6 is given by: ln K D = −3027(±39)/ T (K) + 0.872(±0.013)> where K D is the distribution coefficient for the reaction: Fe M2 2+ + Mg M1 = Mg M2 + Fe M1 2+ . A transmission electron microscopy (TEM) study of part of the crystal showed the presence of very thin augite lamellae and Guinier-Preston zones indicating a relatively rapid cooling of the host rock at temperatures close to 1000°C. The new temperature scale yields a relatively high quenching temperature of 379 (±8)°C for the pyroxene which appears consistent with a rapid cooling (estimated few degrees per hundred years) of a magmatic cumulate excavated by an impact on its parental body.

Single-crystal thermometric calibration of Fe-Mg order-disorder in pigeonites

Abstract The single-crystal X-ray technique was used to calibrate a new intracrystalline geothermometer based on equilibrium Mg-Fe* fractionation (Fe* = Fe2+ + Mn2+) between M1 and M2 sites of natural P21/c pigeonite. Suitable crystals free of exsolution textures and sharp diffraction maxima were selected by careful TEM and XRD investigations from a large number of samples. Two single crystals, PCA82506-3 (Wo6En76Fs18) from the Pecora Escarpment 82506 Antarctic ureilite, and BTS308- 2 (Wo10En47Fs43) from the BTS308 Paranà rhyodacite, were annealed at temperatures ranging from 600 to 1000 °C. The TEM investigation, carried out on fragments of selected single crystals both before and after thermal treatment, shows heating-induced texture modifications preliminary to spinodal decomposition in both crystals and a size increase in antiphase domains in BTS308-2. The two geothermometric equations calculated by linear regression of ln KD* vs. 1/T are: ln KD* = -3291(± 269)/T(K) + 0.971(±0.253); (r2 = 0.974) ln KD* = -2816(± 83)/T(K) + 0.542(±0.083); (r2 = 0.995) respectively for PCA82506-3 (XFe* = 0.20) and BTS308-2 (XFe* = 0.49) [XFe* = Fe*/(Fe* + Mg)]. These results imply negligible compositional effects on Mg-Fe* site partitioning within the range of compositions encompassed by the samples. Comparison of the intracrystalline fractionation data of pigeonites with those of Pbca orthopyroxenes shows a similar degree of ordering for both at a given temperature. This result suggests only a small effect of Ca on Fe*-Mg ordering in pyroxene with Ca content up to Wo10-.

X-ray diffraction study of Fe2+-Mg order-disorder in orthopyroxene. Some kinetic results

AbstractKinetic rates of Fe2+-Mg disordering in three orthopyroxenes (mean value of XFe = Fe2+/(Fe2++Mg) = 0.175,0.482,0.770 respectively) have been determined employing heating experiments and single crystal X-ray structural refinements. Disordering rate constants

Antarctic FRO90011 lodranite: Cooling history from pyroxene crystal chemistry and microstructure

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