Lead isotopic disequilibrium between sulfide and plagioclase in the bushveld complex and the chemical evolution of large layered intrusions

The Pb isotopic compositions of coexisting plagioclase and sulfide from the Bushveld Complex were determined by laser ablation multi-collector ICPMS (LA MC-ICPMS). The samples are of the upper Critical Zone in the northeast corner of the Complex and were collected from drill core and underground mine exposures. All the rocks are fresh and exhibit no evidence for alteration, weathering, or disruption of the Pb isotope systematics subsequent to the initial cooling of the intrusion. Furthermore, individual plagioclase and sulfide crystals do not contain enough U to warrant correction for radiogenic in-growth. For these reasons, the measured Pb isotope ratios approximate the initial ones. For plagioclase, ²⁰⁷Pb/²⁰⁶Pb ranges from 0.98 to 1.02 and ²⁰⁸Pb/²⁰⁶Pb from 2.26 to 2.35. Low ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios characterize grain boundaries and partially annealed microcracks, some of which contain minute fragments of sulfide and other phases, and this accounts for most, if not all, the heterogeneity exhibited by individual samples. Real compositional differences exist, however, in plagioclase from different lithologic layers. For example, plagioclase ²⁰⁷Pb/²⁰⁶Pb values vary from 1.004 in norite beneath the Merensky pyroxenite to 1.009 in the mineralized pyroxenite, and 0.997 in overlying norite. In most samples in which sulfide and plagioclase coexist, the sulfide ²⁰⁷Pb/²⁰⁶Pb ratio is lower and ²⁰⁸Pb/²⁰⁶Pb ratio higher than the corresponding ones in plagioclase. For example, in a mineralized Merensky reef sample, average sulfide ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios are 0.993 and 2.313, respectively, while those in plagioclase are 1.000 and 2.292. In one sample, the sulfide is extremely heterogeneous, with ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios as low as 0.84 and 2.12. In this particular sample, the compositions must represent an isolated occurrence of addition of a young Pb component.The array of sulfide and plagioclase compositions requires multiple sources of Pb at the time of crystallization or soon thereafter. The disequilibrium between plagioclase and sulfide implies that some of the Pb originated from the isotopically distinct country rocks and was introduced at temperatures at which the composition of sulfide but not plagioclase could be modified. Thus, Bushveld sulfide, and to some extent plagioclase, do not reliably record the initial Pb isotopic composition(s) of the parent magma(s).     

Petrogenesis and chronology of lunar meteorite Northwest Africa 4472: A KREEPy regolith breccia from the Moon

Northwest Africa (NWA) 4472 is a polymict lunar regolith meteorite. The sample is KREEP-rich (high concentrations of potassium, rare earth elements and phosphorus) and comprises a heterogeneous array of lithic and mineral fragments. These clasts and mineral fragments were sourced from a range of lunar rock types including the lunar High Magnesian Suite, the High Alkali Suite, KREEP basalts, mare basalts and a variety of impact crater environments. The KREEP-rich nature of NWA 4472 indicates that the sample was ejected from regolith on the nearside of the Moon in the Procellarum KREEP Terrane and we have used Lunar Prospector gamma-ray remote sensing data to show that the meteorite is most similar to (and most likely sourced from) regoliths adjacent to the Imbrium impact basin.U-Pb and Pb-Pb age dates of NWA 4472 phosphate phases reveal that the breccia has sampled Pre-Nectarian (4.35 Ga) rocks related to early episodes of KREEP driven magmatism. Some younger phosphate U-Pb and Pb-Pb age dates are likely indicative of impact resetting events at 3.9-4 Ga, consistent with the suggested timing of basin formation on the Moon. Our study also shows that NWA 4472 has sampled impact melts and glass with an alkali-depleted, incompatible trace element-rich (high Sc, low Rb/Th ratios, low K) compositional signature not related to typical Apollo high-K KREEP, or that sampled by KREEPy lunar meteorite Sayh al Uhaymir (SaU) 169. This provides evidence that there are numerous sources of KREEP-rich protoliths on the Moon.     

Petrology of andesites from the Yamato central rise,Sea of Japan

The composition of andesites from the Yamato central submarine rise and adjacent structures (Sea of Japan) points to the presence of a Late Cretaceous shortened and Oligocene-Miocene extended calc-alkaline series. With the general similarity of mineral assemblages of andesites, they are distinct in composition of minerals, which testifies to different formation conditions. The andesites of the extended type are the products of crystallization differentiation, whereas those of the shortened type are characterized by nonequilibrium composition of minerals, which reflects the heterogeneous primary melt, the composition of which discretely varied (probably repeatedly) during crystallization.     

Platinum group minerals in podiform chromitites of the Bou Azzer ophiolite, Anti Atlas, Central Morocco

Summary The Neoproterozoic Bou Azzer ophiolite complex hosts numerous, small lenticular bodies of massive and disseminated chromite. Metallurgical-grade high-Mg and high-Cr spinels (cores with 48–62 wt% Cr₂O₃) reveal complex alteration patterns of successive Cr and Mn enrichment and loss of Al towards the rims, while the Mg# ratios [(Mg/(Mg + Fe²⁺)] remain almost constant. Concentration patterns of platinum-group elements are typical for ophiolitic chromitite poor in sulfides, with predominance of the IPGE, variable Rh, and low Pt and Pd. The most abundant platinum-group mineral is Rh-bearing laurite that occurs either included in spinel or in silicate matrix, whereas Os-Ir-Ru alloy is always included in spinel. Laurite inclusions reveal complex intergrowth textures with Rh-Ru-Pt rich alloy, and with Rh-rich sulfide. Most laurites display trends to sulfur-poor compositions leading to local formation of very fine-grained Ru-Os-Ir alloy phases. Ni-Co-Fe sulfides, arsenides and sulfarsenides devoid of PGE are associated with the alteration of chromite. Textural position and chemical composition of the base metal inclusions, as well as comparison of alteration features between chromite and accessory chromian spinel in the Co-Ni-As ores of the Bou Azzer ophiolite indicate a close connection. It is suggested that hydrothermal fluids percolated through the marginal zones of the ophiolite belt during greenschist facies metamorphism and deposited Ni-Co-Fe arsenides, sulfarsenides and minor sulfides as accessories within altered chromitites, and also in structurally favourable zones as Ni-Co-As ores. Author’s address: Dr. Frank Melcher, Federal Institute for Geosciences and Natural Resources, Stilleweg 2, 30655 Hannover, Germany     

Facile synthesis of hexamine–silicotungstic acid hybrid and its photocatalytic activity toward degradation of dyes

A new organic hybrid of silicotungstic acid was prepared by means of an easily available, very cheap, and non-toxic amine via a facile precipitation method. Characterization of hybrid was carried out by elemental analyses, Fourier transform infrared spectroscopy, powder X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. Dye adsorption and photocatalytic properties of the prepared water-insoluble hybrid were examined by studying the decolorization of model dyes such as methylene blue and methyl, orange and their mixture solutions under ultraviolet, visible, and sunlight irradiation. The effect of different factors containing the initial concentration, pH, catalyst dosage, H₂O₂ dosage, and salt adding was investigated on the decolorization of dyes. The results showed that the hybrid is a good heterogeneous photocatalyst in the degradation of methylene blue, methyl orange and their mixture and can be recovered and reused. The methylene blue is removed via combination of adsorption and photocatalytic degradation under ultraviolet, visible, and sunlight through direct oxidation by hybrid. The methyl orange is removed via ultraviolet and solar photocatalytic degradation through indirect oxidation by ^·OH radicals. While the visible light is not able to degrade methyl orange solution alone in the presence of hybrid, it degrades the methyl orange mixed with methylene blue solution.     

The effect of anatase, rutile and sodium titanate on the dissolution of boehmite and gibbsite at 90 °C

Industrial plants that refine bauxite to alumina using the high temperature process have always held the belief that anatase was detrimental to the extraction of boehmite while rutile was not. This study shows that this effect is real and that it is observable at temperatures as low as 90 °C. The extraction of gibbsite is shown to be unaffected which leads us to believe that the kinetics of both the Ti-bearing mineral and the Al-bearing mineral is important in this phenomenon. In addition, it is shown that not only is the presence of anatase an issue in boehmite extraction but so too is the presence of sodium titanate. Rutile was found to have the least impact of the three mineral phases.     

Sources and evolution of the Cenozoic suprasubduction magmatism of the Olyutorsky tectonic block,southern Koryak highland

This paper reports the results of an investigation of the geochemical and isotopic compositions of rocks formed during the Eocene suprasubduction magmatism in the Olyutorsky tectonic block. The contribution of various suprasubduction components to the formation of magmatic melts was estimated; the characteristics of the Eocene and Miocene-Quaternary suprasubduction magmatism of the Olyutorsky tectonic block were compared; and relations of the Cenozoic magmatism to the tectonic development of the block were evaluated. The Eocene-early Oligocene suprasubduction magmas were derived from geochemically and isotopically heterogeneous garnet lherzolites in a mantle wedge. The initially depleted lherzolites of the mantle wedge were probably locally and variably enriched by OIB-type mantle melts before the generation of island-arc magmas and then again depleted below the MORB level by the extraction of magmatic materials from them. In the Eocene, a considerable amount of quartz-feldspar sediments enriched in radiogenic Nd was consumed in the subduction zone, which resulted in a strong contamination of magmas derived from the garnet lherzolites of the mantle wedge. The later stages of subduction were accompanied by active generation of adakite magmas with depleted Nd isotope signatures and HFSE-rich melts showing no evidence for their contamination by sialic sediments. It was supposed that the Late Cenozoic subduction zone plunged northward beneath the Olyutorsky tectonic block. It was shown that the established characteristics of the suprasubduction magmatism of the Olyutorsky tectonic block could be related to Cenozoic spreading processes in the proto-Komandorsky basin of the Bering Sea.     

Ionic conductivity in gem-quality single-crystal alkali feldspar from the Eifel: temperature,orientation and composition dependence

We measured the ion conductivity of single-crystal alkali feldspar originating from two different locations in the Eifel/Germany, named Volkesfeld and Rockeskyller sanidine and having potassium site fractions \(C_\mathrm{K}\) of 0.83 and 0.71, respectively. The dc conductivities resulting from electrochemical impedance spectroscopy over the temperature range of 300–900 \(^{\circ }\hbox {C}\) show a weak composition dependence but pronounced differences between the b-direction [\(\perp (010)\)] and \(c^{*}\)-direction [\(\perp (001)\)] of the monoclinic feldspar structure. Conductivity activation energies obtained from the observed linear Arrhenius plots are close to 1.2 eV in all cases, which is closely similar to the activation energies of the \(^{22}\mathrm{Na}\) tracer diffusivity in the same crystals. Taking into account literature data on K tracer diffusion and diffusion correlation effects, the present results point to a predominance of the interstitialcy mechanism over the vacancy mechanism in mass and charge transport on the alkali sublattice in potassium-rich alkali feldspar.     

Rigid Unit Modes in disordered nepheline: a study of a displacive incommensurate phase transition

 Calculations of the Rigid Unit Modes (RUMs) allowed in the nepheline structure are used to explain the diffuse scattering previously seen in electron diffraction experiments. The RUM calculations also show that the modulation wavelength for incommensurate nephelines is essentially determined by the framework topology. X-ray diffraction is used to measure the intensity of the diffuse scattering as a function of temperature. The diffuse intensity increases sharply at 308 K. This effect is interpreted as being due to the softening of a phonon mode, indicating a phase transition. Measurements of this phase transition below the transition temperature are made using hard mode infrared spectroscopy. Received: 17 February 1999 / Revised, accepted. 15 October 1999