LREE distribution in perovskite,apatite and titanite from South West Ugandan xenoliths and kamafugite lavas

Summary In-situ microprobe LREE analyses of perovskite and titanite (La, Ce, Nd), and apatite (La, Ce), from SW Ugandan clinopyroxenite xenoliths and kamafugite lavas indicate that LREE distribution in these minerals is determined by a number of factors related to their different parageneses: In particular LREE content is affected by whether the LREE-bearing minerals have crystallised from metasomatic carbonate or from silicate (i.e. metasomatic or magmatic) melts in the mantle. In this situation LREE partition favours carbonate over silicate melts. Distribution of LREE in perovskite and apatite crystallised from magmatic mantle melts or mantle-derived lavas is chiefly determined by preference of LREE for perovskite > apatite > titanite. LREE zoning in perovskite is influenced by changes in melt structure: increasing melt polymerisation enhancing mineral_LREE/melt_LREE partition into perovskite rims in magmatic xenoliths; decreasing melt polymerisation depleting LREE in lava perovskite rims. This zoning is reinforced by perovskite competition with apatite for LREE: perovskite (cores/rims) co-crystallising with apatite is reduced in LREE. There are 37 instances of perovskitewith Ce below detection while La and Nd levels are normal. These occur in both xenoliths and lavas; in grain zones or whole grains. Likewise Ce alone of the LREE is below detection in six out of ten titanite analyses. These observations are interpreted as evidence for increased f_{O 2}, Ce⁴ + being excluded from these mineral structures. Recognition of these various processes can elucidate the interpretation of bulk rock and bulk mineral LREE signatures in kamafugite volcanism.

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LREE Verteilung in Perovskit, Apatit und Titanit aus Xenolithen und kamafugitischen Laven Südwest-Ugandas

Zusammenfassung In-situ LREE Analysen von Perovskit und Titanit (La, Ce, Nd) und Apatit (La, Ce) aus Klinopyroxenit-Xenolithen und kamafugitischen Laven Südwest-Ugandas zeigen, daß die LREE Verteilung in diesen Mineralen durch eine Vielzahl von Faktoren, die mit Unterschieden in den Paragenesen zusammenhängen, bestimmt wird: Der LREE-Gehalt wird im besonderen davon bestimmt, ob die LREE-führenden Minerale aus metasomatischen Karbonat- oder aus (metasomatischen oder magmatischen) Silikatschmelzen im Mantel auskristallisierten. Dabei erfolgt die LREE Fraktionierung zu Gunsten der Karbonatschmelzen. Die LREE-Verteilung von Perovskit und Apatit, die aus magmatischen Mantelschmelzen oder -laven kristallisierten, wird vorrangig durch den bevorzugten Einbau der LREE in Perovskit > Apatit > Titanit kontrolliert. Der LREE Zonarbau von Perovskit wird durch die Änderungen der Schmelzstruktur beinflußt: Verstärkte Schmelzpolymerisation führt zu verstärkter Mineral_LFEE/Schmelze_LREE Fraktionierung in den Perovskiträndern magmatischer Xenolithe, eine Abnahme der Schmelzpolymerisation hingegen resultiert in einer Abreicherung der LREE in den Perovskiträndern. Diese Art der Zonierung wird durch den Wettbewerb von Perovskit mit Apatit um die LREE verstärkt. Perovskit (Kerne/Ränder), der mit Apatit gemeinsam auskristallisierte, ist ärmer an LREE. 37 Fälle, in denenCe nicht nachweisbar war, La und Nd aber in normaler Konzentration auftreten, wurden sowohl in den Xenolithen als auch in den Laven gefunden; und zwar entweder in Kornbereichen oder in ganzen Körnern. Vergleichsweise liegt Ce nur in sechs von zehn Titanitproben unterhalb der Nachweisgrenze. Diese Beobachtungen werden als Hinweise auf erhöhte SauerstoffFugazitäten, bei denen Ce^4– aus der Mineralstruktur ausgeschlossen wird, angesehen.Ein Verständnis dieser verschiedenen Prozesse kann zur besseren Interpretation von LREE Gesamtgesteins- und Gesamtmineral-Signaturen in Kamafugiten beitragen.

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With 3 Figures     

Origin of spongy textures in clinopyroxene and spinel from mantle xenoliths, Hessian Depression, Germany

Summary Spongy textures are observed in anhydrous Group 1 mantle xenoliths (harzburgite, lherzolite and wehrlite) hosted in Tertiary alkali basaltic lavas from the Hessian Depression, Germany. These textures are developed only on clinopyroxene and spinel, and occur as rims or cross-cutting veinlets and patches showing optical continuity with the host grain. They are often associated with pools of amorphous glassy material. There is no preferential development of spongy domains against the xenolith-lava contact suggesting that the host magma did not play any significant role in their formation. Spongy clinopyroxene and spinel occur in all rock types, but, are more pervasive in wehrlite. Chemically, spongy domains of clinopyroxene and spinel are more refractory than unaffected areas, which is consistent with their formation through a partial melting event. The associated glassy material shows chemical characteristics which suggest that the melt pools are genetically related to the development of the spongy textures. The partial melting event was probably triggered by the infiltration of a low-density fluid. The fluid may have evolved from a silicate melt responsible for the metasomatic Fe-enrichment recorded in wehrlite. In this context, the more pervasive development of spongy clinopyroxene in wehrlite may be explained by a higher concentration of the evolved fluid phase at proximity to its silicate melt source. Received March 15, 2000; revised version accepted September 6, 2001     

Lower crustal melting and the role of open-system processes in the genesis of syn-orogenic quartz diorite–granite–leucogranite associations: constraints from Sr–Nd–O isotopes from the Bandombaai Complex, Namibia

The Bandombaai Complex (southern Kaoko Belt, Namibia) consists of three main intrusive rock types including metaluminous hornblende- and sphene-bearing quartz diorites, allanite-bearing granodiorites and granites, and peraluminous garnet- and muscovite-bearing leucogranites. Intrusion of the quartz diorites is constrained by a U–Pb zircon age of 540±3 Ma.

Quartz diorites, granodiorites and granites display heterogeneous initial Nd- and O isotope compositions (_{Nd (540 Ma)}=−6.3 to −19.8; δ¹⁸O=9.0–11.6‰) but rather low and uniform initial Sr isotope compositions (⁸⁷Sr/⁸⁶Sr_initial=0.70794–0.70982). Two leucogranites and one aplite have higher initial ⁸⁷Sr/⁸⁶Sr ratios (0.70828–0.71559), but similar initial _Nd (−11.9 to −15.8) and oxygen isotope values (10.5–12.9‰). The geochemical and isotopic characteristics of the Bandombaai Complex are distinct from other granitoids of the Kaoko Belt and the Central Zone of the Damara orogen. Our study suggests that the quartz diorites of the Bandombaai Complex are generated by melting of heterogeneous mafic lower crust. Based on a comparison with results from amphibolite-dehydration melting experiments, a lower crustal garnet- and amphibole-bearing metabasalt, probably enriched in K₂O, is a likely source rock for the quartz diorites. The granodiorites/granites show low Rb/Sr (<0.6) ratios and are probably generated by partial melting of meta-igneous (intermediate) lower crustal sources by amphibole-dehydration melting. Most of the leucogranites display higher Rb/Sr ratios (>1) and are most likely generated by biotite-dehydration melting of heterogeneous felsic lower crust. All segments of the lower crust underwent partial melting during the Pan-African orogeny at a time (540 Ma) when the middle crust of the central Damara orogen also underwent high T, medium P regional metamorphism and melting. Geochemical and isotope data from the Bandombaai Complex suggest that the Pan-African orogeny in this part of the orogen was not a major crust-forming episode. Instead, even the most primitive rock types of the region, the quartz diorites, represent recycled lower crustal material.     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

The accuracy of standard enthalpies and entropies for phases of petrological interest derived from density-functional calculations

The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO₃–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al₂SiO₅ polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.     

Book review of ENCYCLOPEDIA OF NONLINEAR SCIENCE,edited by Alwyn Scott,Routledge, Taylor and Francis Group, 2005, VII +1053 pp., 135, $225 hardback (ISBN 1-57958-385-7).

We present three-dimensional (3D) solutions of the magnetohydrostatic equations in the co-rotating frame of reference outside a magnetized rigidly rotating cylinder. We make no symmetry assumption for the magnetic field, but to be able to make analytical progress we neglect outflows and specify a particular form for the current density. The magnetohydrostatic equations can then be reduced to a single linear partial differential equation for a pseudo-potential U, from which the magnetic field can be calculated by differentiation. The equation for U can be solved by standard methods. The solutions can also be used to determine the plasma pressure, density and temperature as functions of all three spatial coordinates. Despite the obvious limitations of this approach, it can, for example, be used as a simple tool to create 3D models for the closed field line regions of rotating magnetospheres without rotational symmetry.     

Origin of glass in upper mantle xenoliths from the quaternary volcanics of Gees,West Eifel,Germany

Glasses have been analysed from six mantle-derived xenoliths (5 orthopyroxene and/or olivine-rich, 1 clinopyroxene-rich) from the Quaternary volcanics S.E. of Gees, West Eifel, Germany. The glasses in these xenoliths occur as pools surrounding and embaying spinels, as inclusions in spinels, as veins and stringers within phlogopiterich veins, and as jackets partially surrounding some of the xenoliths. Glasses analysed are felsic and characterised by low to intermediate SiO₂ (40–62 wt.%), variable CaO (1–11 wt.%) and MgO (1–4 wt.%), high Al₂O₃ (14–21 wt.%), and up to 11 wt.% Na₂O + K₂O. The jacket glasses have the lowest SiO₂, highest CaO and MgO. Variations in all of the glass compositions are similar and imply a unifying factor or process in their formation. Glass as pools and stringers within veins of phlogopite forms part of the same trends shown by all the glasses when plotted on bivariate (oxide vs SiO₂) diagrams but can be distinguished from glass surrounding and enclosed by spinels. Glasses occurring as jackets are similar in composition to those in pools and veinlets associated with phlogopite but are of quite different composition to the glasses found within the xenoliths that they partially enclose. The occurrence and chemistry of the glasses do not support such glasses as representing original or differentiated magma trapped during formation of the xenolithic assemblages. The chemistry of the glasses also makes it unlikely that they were produced by dissociation of phlogopite during ascent of the xenoliths. The most likely origin for the glasses is that they represent volatile-rich melts which migrated through upper mantle material. These melts are likely to be responsible for the heterogeneous nature of the mantle underlying this part of the West Eifel region.     

A theory for the scalar roughness and the scalar transfer coefficients over snow and sea ice

Although the bulk aerodynamic transfer coefficients for sensible (C _H ) and latent (C _E ) heat over snow and sea ice surfaces are necessary for accurately modeling the surface energy budget, they have been measured rarely. This paper, therefore, presents a theoretical model that predicts neutral-stability values of C _H and C _E as functions of the wind speed and a surface roughness parameter. The crux of the model is establishing the interfacial sublayer profiles of the scalars, temperature and water vapor, over aerodynamically smooth and rough surfaces on the basis of a surface-renewal model in which turbulent eddies continually scour the surface, transferring scalar contaminants across the interface by molecular diffusion. Matching these interfacial sublayer profiles with the semi-logarithmic inertial sublayer profiles yields the roughness lengths for temperature and water vapor. When coupled with a model for the drag coefficient over snow and sea ice based on actual measurements, these roughness lengths lead to the transfer coefficients. C _E is always a few percent larger than CH. Both decrease monotonically with increasing wind speed for speeds above 1 m s^–1, and both increase at all wind speeds as the surface gets rougher. Both, nevertheless, are almost always between 1.0 × 10^–3 and 1.5 × 10^–3.