Tantalum-bearing titanite: synthesis and crystal structure data

Synthetic titanite, CaTiOSiO₄, and the series of (Ca_1−x Na _x )(Ti_1−x Ta _x )OSiO₄ and Ca(Ti_1−2x Ta _x Al _x )OSiO₄ solid solutions have been prepared by ceramic methods, and their crystal structure determined by the Rietveld analysis. At ambient conditions, titanite can contain up to 20 mol% NaTaOSiO₄ or 60 mol% Ca(Al_0.5Ta_0.5)OSiO₄. These limits might differ in natural samples due to combination with substitutions involving fluorine and/or hydroxyl replacing oxygen together with vacancies at cationic sites. All cations located at the ^vii X- and ^vi Y-sites in the structures of tantalian titanite are disordered. Expansion of the <Si–O> bond from 1.618 to 1.621 Å in CaTi_0.8Ta_0.1Al_0.1OSiO₄ and CaTi_0.6Ta_0.2Al_0.2OSiO₄ to 1.644 Å in the CaTi_0.4Ta_0.3Al_0.3OSiO₄ titanite suggests the possible presence of some Al³⁺ in the tetrahedral site replacing Si⁴⁺ in the latter. All tantalian titanites crystallize in the space group A2/a. This implies that both single-site and complex double-site substitutional schemes induce P2₁/a → A2/a phase transition(s). The (Ca_1−x Na _x )(Ti_1−x Ta _x )OSiO₄ substitution scheme incorporates larger cations at both the ^vii X and ^vi Y sites, whereas the Ca(Ti_1−2x Ta _x Al _x )OSiO₄ scheme involves only ^vi Y-site (Al³⁺,Ta⁵⁺) cations with a slightly smaller “average” radius. Unit cell dimensions change insignificantly or increase incrementally with increase of average cationic radii in the (Ca_1−x Na _x )(Ti_1−x Ta _x )OSiO₄ series, and with an insignificant decrease in the ^viR _Y average cationic radii in the Ca(Ti_1−2x Ta _x Al _x )OSiO₄ series. Both Ta-doped titanite and CaTiOSiO₄ consist of distorted polyhedra with the XO₇, YO₆ coordination polyhedra and the SiO₄ tetrahedron in tantalian titanite being less distorted compared to those of the pure CaTiOSiO₄.     

Subsolidus deuteric/hydrothermal alteration of eudialyte in lujavrite from the Pilansberg alkaline complex, South Africa

The most evolved rocks of the Pilansberg alkaline complex are aegirine lujavrites in which three varieties of eudialyte are recognized on the basis of textural relationships and composition. Manganoan eudialyte-I is a relict orthomagmatic phase occurring as poikilitic plates or as relict grains in pseudomorphed euhedral phenocrysts. Late eudialyte-II ranges in composition from manganoan eudialyte through kentbrooksite to taseqite-like varieties and is considered to be formed by cation exchange with eudialyte-I and alkaline fluids. Eudialyte-III is a hydrothermal phase replacing eudialyte-II, and has either taseqite-like (5–7.3 wt.% SrO, < 2.0 wt.% REE₂O₃) or kentbrooksite (< 1.5 wt.% SrO,  8.5 wt.% REE₂O₃) compositions. Three styles of replacement of eudialyte-I and -II are recognizable. Type 1 involves replacement by complex aggregates of zircon, fergusonite-(Ce), allanite-(Ce), britholite-(Ce), titanite, pyrochlore, albite and potassium feldspar, i.e. a “miaskitic” paragenesis. Type 2 alteration consists of complex aggregates dominated by deuteric Na–Zr-silicates (?catapleiite), stronalsite, strontium-apatite and lamprophyllite replacing eudialyte-I and -II and relicts of the “miaskitic paragenesis”, i.e. a highly sodic “agpaitic-to-hyperagpaitic” paragenesis. Type 3 replacement involves mantling of any residual eudialyte-II and zircon, and replacement of deuteric Na–Zr-silicates by eudialyte-III together with barytolamprophyllite as late hydrothermal phases. Further alteration and replacement resulted in the superposition of natrolite, britholite, pyrochlore, allanite and diverse Ba- and Mn-based minerals onto the types 2 and 3 assemblages, and ultimately to the deposition of allanite-(La), La-dominant REE carbonates and rarely a silica phase. All of the alteration styles are considered to have occurred in situ under subsolidus conditions (< 450 °C) by interaction of pre-existing eudialyte and other minerals with deuteric, sodium- and chlorine-bearing aqueous fluids. The evolution of the replacement products is from a miaskitic through an agpaitic to a hyperagpaitic paragenesis and ultimately back to a low agpaitic-to-miaskitic assemblage, reflecting changes in the a(Na⁺)/a(Cl⁻) ratio and alkalinity of the deuteric/hydrothermal fluids.     

In situ oxygen,magnesium, and silicon isotopic compositions of the FUN inclusion Vigarano 1623-5

Oxygen, magnesium, and silicon isotopic abundances in Vigarano 1623-5 were studied using secondary ion mass spectrometry to investigate correlations between isotopic and petrologic properties of this unique forsterite-bearing FUN inclusion. Vigarano 1623-5 displays large, correlated mass-dependent fractionation effects, tightly linked to mineralogy within distinct petrologic units of the inclusion. The pyroxene-rich and melilite-rich interior parts of the inclusion display highly mass-fractionated isotopic compositions of oxygen, magnesium, and silicon, consistent with Rayleigh distillation during evaporation of a melt with initial oxygen composition close to a solar composition. However, the chemical composition, enriched in magnesium and silicon, suggests a precursor already fractionated by prior melt evaporation. A discontinuous igneous rim was produced by a flash-melting event followed by isotopic exchange in the rim melilite with planetary-like oxygen, mechanical fragmentation, and reassembly with an accretionary rim of heterogeneous materials. Al-rich minerals in 1623-5 show evidence for having crystallized with live ²⁶Al but at less than the “canonical” level of most CV calcium-aluminum-rich inclusions. However, well-defined ²⁶Al-²⁶Mg isochrons are not found and temporal implications are ambiguous.     

Is μCT irradiation nondestructive? A noble gas study on matrix samples from the CV3 chondrite Allende

Micro-computed tomography (μCT) is a fast and powerful technology for studying textural, physical, and chemical properties of solid objects in three dimensions. While regularly used for sample documentation and curation, it is often assumed that μCT techniques are essentially nondestructive or at least very little destructive. However, there are very few studies proving or rejecting the assumption of nondestructiveness. Here we study whether X-ray tomographic imaging affects the noble gas budget of matrix samples from the CV3 carbonaceous chondrite Allende. We irradiated powdered and homogenized matrix samples in the Bruker SkyScan 1272 μCT instrument at three different X-ray tube acceleration voltages of 30, 70, and 100 keV. By comparing the noble gas concentrations and especially the elemental and isotopic ratios of the irradiated samples with data for two non-irradiated aliquots, we found no significant differences. Our study therefore demonstrates that X-ray tomographic imaging has no measurable effect on the noble gas budget and can therefore safely be used for sample characterization prior to noble gas studies.