Chemical and mineral composition of rocks from the Philippine Sea

The book is devoted to geology of the Philippine Sea floor. This region is studied most extensively among other marginal seas of the Pacific Ocean. Rocks of the sedimentary and basalt layers within this sea have been studied during five legs of D/S Glomar Challenger. International geological expedition on board R/V Dmitry Mendeleev carried out according to the Project ''Ophiolites of Continents and Comparable Rocks of the Ocean Floor''obtained unique collection of rocks from the second and third layers of the ocean crust in the Philippine Sea. The book provides detailed petrographic and geochemical description of igneous and sedimentary formations from the Philippine Sea and compares them with rocks of the continental ophiolite association. An analysis of structure and history of the ocean crust formation in the region is based on all known geological information. The main periods of tectonic movement activation and nature of their manifestations within the sea are shown.

Electron beam induced electronic transport in alkyl amine-intercalated VOx nanotubes

The electron beam induced electronic transport in primary alkyl amine-intercalated V2O5 nanotubes is investigated where the organic amine molecules are employed as molecular conductive wires to an aminosilanized substrate surface and contacted to Au interdigitated electrode contacts. The results demonstrate that the high conductivity of the nanotubes is related to the non-resonant tunnelling through the amine molecules and a reduced polaron hopping conduction through the vanadium oxide itself. Both nanotube networks and individual nanotubes exhibit similarly high conductivities where the minority carrier transport is bias dependent and nanotube diameter invariant.

The structural conversion from α-AgVO3 to β-AgVO3: Ag nanoparticle decorated nanowires with application as cathode materials for Li-ion batteries

The majority of electrode materials in batteries and related electrochemical energy storage devices are fashioned into slurries via the addition of a conductive additive and a binder. However, aggregation of smaller diameter nanoparticles in current generation electrode compositions can result in non-homogeneous active materials. Inconsistent slurry formulation may lead to inconsistent electrical conductivity throughout the material, local variations in electrochemical response, and the overall cell performance. Here we demonstrate the hydrothermal preparation of Ag nanoparticle (NP) decorated α-AgVO3 nanowires (NWs) and their conversion to tunnel structured β-AgVO3 NWs by annealing to form a uniform blend of intercalation materials that are well connected electrically. The synthesis of nanostructures with chemically bound conductive nanoparticles is an elegant means to overcome the intrinsic issues associated with electrode slurry production, as wire-to-wire conductive pathways are formed within the overall electrode active mass of NWs. The conversion from α-AgVO3 to β-AgVO3 is explained in detail through a comprehensive structural characterization. Meticulous EELS analysis of β-AgVO3 NWs offers insight into the true β-AgVO3 structure and how the annealing process facilitates a higher surface coverage of Ag NPs directly from ionic Ag content within the α-AgVO3 NWs. Variations in vanadium oxidation state across the surface of the nanowires indicate that the β-AgVO3 NWs have a core–shell oxidation state structure, and that the vanadium oxidation state under the Ag NP confirms a chemically bound NP from reduction of diffused ionic silver from the α-AgVO3 NWs core material. Electrochemical comparison of α-AgVO3 and β-AgVO3 NWs confirms that β-AgVO3 offers improved electrochemical performance. An ex situ structural characterization of β-AgVO3 NWs after the first galvanostatic discharge and charge offers new insight into the Li+ reaction mechanism for β-AgVO3. Ag+ between the van der Waals layers of the vanadium oxide is reduced during discharge and deposited as metallic Ag, the vacant sites are then occupied by Li+.

The geochemistry, mineralogy, and petrology of basalts at DSDP Leg 59 Holes

Legs 59 and 60 of the International Phase of Oceanic Drilling (IPOD) were designed to study the nature and history of volcanism of the active Mariana arc, its currently spreading inter-arc basin (the Mariana Trough), and the series of inactive basins and intervening ridges that lie to the west. The older basins and ridges were drilled during Leg 59 as the first part of a transect of single-bit holes drilled in each major basin and ridge. The eastern part of the transect - the technically active region - was drilled during Leg 60. The evolution of island-arc volcanos and magma genesis associated with lithospheric subduction remain some of the most complex petrologic problems confronting us. Many types of source material (mantle, oceanic crust, continental crust) and an unusually wide range of possible physical conditions at the time of magma genesis must be identified even before the roles of partial melting and subsequent magma fractionation, mixing, and contamination can be assessed.

Geochemistry in the mid Atlantic Ocean ridge basalts

The main objective of Leg 82 of the Glomar Challenger was to document mantle heterogeneity in the vicinity of, and away from, a so-called hot spot: the Azores Triple Junction. One of the geochemical tools that permits, at least in part, the recognition of mantle heterogeneities uses hygromagmaphile elements, those elements that have an affinity for the liquid. This tool is presented in terms of an extended Coryell-Masuda plot, which incorporates within the rare earth elements the hygromagmaphile transition elements Th, Ta, Zr, Hf, Ti, Y, and V. The extended Coryell-Masuda plot is used to summarize our knowledge of mantle heterogeneity along the ridge axis at zero-age. It is also used by choosing those hygromagmaphile elements that can be analyzed on board by X-ray fluorescence spectrometry to give preliminary information on the enriched or depleted character of recovered samples. Shore-based results, which include analyses of most of the hygromagmaphile elements measured either by X-ray spectrometry or neutron activation analysis, confirm the shipboard data. From the point of view of comparative geochemistry, the variety of basalts recovered during Leg 82 provides a good opportunity to test and verify the classification of the hygromagmaphile elements. Analyses from Leg 82 provide new data about the relationship between extended rare earth patterns (enriched or depleted) that can be estimated either by La/Sm ratio or Nb/Zr (or Ta/Hf) ratios: samples from Hole 556 are depleted (low Nb/Zr ratio) but have a high 206Pb/ 204Pb (19.5) ratio; in Hole 558 a moderately enriched basalt unit with a La/Sm (= Nb/Zr) ratio (chondrite normalized) of 2 has a high 206Pb/204Pb (20) ratio. One of the most interesting results of Leg 82 lies in the crossing patterns of extended Coryell-Masuda plots for basalts from the same hole. This result enhances the notion of local mantle heterogeneity versus regional mantle heterogeneity and is confirmed by isotope data; it also favors a model of short-lived, discrete magma chambers. The data tend to confirm the Hayes Fracture Zone as a southern limit for the influence of Azores-type mantle. Nevertheless, north of the Hayes Fracture Zone, the influence of a plumelike mantle source is not simple and probably requires an explanation more complex than a contribution from a single fixed hot spot.

Geochemistry of ODP Leg 135 igneous rock samples

Ocean Drilling Program Leg 135 provided igneous rock cores from six sites drilled on a transect across the Lau Basin between the Lau Ridge remnant arc and the modem spreading ridges of the Central and Eastern Lau Spreading Centers. The drill cores sampled crust from the earliest stage of backarc extension (latest Miocene time, about 6 Ma), and younger crust (late Pliocene, about 3.8-2 Ma, and middle Pleistocene, about 0.64-0.8 Ma). Nearly all of the igneous samples are from tholeiitic basalt flows; many of them are interbedded with arc-composition volcaniclastic sediments. Rock compositions range from olivine-plagioclase-clinopyroxene basalt, with up to 8% MgO, to oceanic andesites with less than 3.2% MgO and silica contents as high as 56%. The oldest rocks recovered are close in composition to rocks formed at the modern Central and Eastern Lau Spreading Centers and have MORB-like characteristics. Generation of the oldest units was coeval with arc-tholeiitic volcanism on the Lau Ridge less than 100 km to the west. The arc and backarc melts came from different mantle sources. At three sites near the center of the basin, the crust is arc-tholeiitic basalt, two-pyroxene basaltic-andesite, and two-pyroxene andesite. These rocks have many similarities to modem Tofua Arc lavas yet they were drilled within 70 km of the MORB-like Eastern Lau Spreading Center. Estimates of the minimum age for these arc-like rocks indicate that they are late Pliocene (about 2 Ma). These ages overlap the age of the nearby Eastern Lau Spreading Center. The heterogeneous crust of the Lau Basin carries many of the signatures of supra-subduction zone (SSZ) melts but also has a distinct MORB-like component. Mixing between SSZ and MORB mantle sources may explain the variations and the spatial distribution of magma types.

(Table 3, page 264), Composition of a manganese micronodule found in a fossil red clay bed from Western Timor

Chemical analyses are presented for two Cretaceous clays from Noil Tobee, Timor. Mineralogical examination has shown that they consist principally of quartz, feldspar, illite and chlorite, together with minor amounts of montmorillonite. Both chemically and mineralogically the clays are very similar to the recent argillaceous deep-sea sediments of the Pacific and Indian Oceans, which confirms Molengraaff's theory (1921) that they are of deep-sea origin. Further confirmation of this theory is provided by comparison of the composition of micromanganese nodules, separated from one of these clays, with that of manganese nodules from the Pacific Ocean.

Chemical composition of rocks and minerals from DSDP holes

The book summarizes materials obtained by Soviet scientists during participation in legs of D/S Glomar Challenger and in post-cruise studies. Results on stratigraphy and lithology of the sedimentary cover, petrography and geochemistry of magmatic rocks of the oceanic crust are discussed in the book. A modern analysis of the geophysical structure of the oceanic crust and of the tectonic structure of the ocean floor is given.

Detection of H2O and Evidence for TiO/VO in an Ultra-hot Exoplanet Atmosphere

We present a primary transit observation for the ultra-hot (T eq ~ 2400 K) gas giant expolanet WASP-121b, made using the Hubble Space Telescope Wide Field Camera 3 in spectroscopic mode across the 1.12–1.64 μm wavelength range. The 1.4 μm water absorption band is detected at high confidence (5.4σ) in the planetary atmosphere. We also reanalyze ground-based photometric light curves taken in the B, r', and z' filters. Significantly deeper transits are measured in these optical bandpasses relative to the near-infrared wavelengths. We conclude that scattering by high-altitude haze alone is unlikely to account for this difference and instead interpret it as evidence for titanium oxide and vanadium oxide absorption. Enhanced opacity is also inferred across the 1.12–1.3 μm wavelength range, possibly due to iron hydride absorption. If confirmed, WASP-121b will be the first exoplanet with titanium oxide, vanadium oxide, and iron hydride detected in transmission. The latter are important species in M/L dwarfs and their presence is likely to have a significant effect on the overall physics and chemistry of the atmosphere, including the production of a strong thermal inversion.

Enhanced oxidation activity from modified ceria: MnOx-ceria, CrOx-ceria and Mg doped VOx-ceria

Ceria is an important component of catalysts for oxidation reactions that proceed through the Mars-van Krevelen mechanism, promoting activity. A paradigm example of this is the VOx–CeO2 system for oxidative dehydrogenation reactions, where vanadium oxide species are supported on ceria and a special synergy between them is behind the enhanced activity: reduction of the catalyst is promoted by ceria undergoing reduction. This leads to favourable oxygen vacancy formation and hydrogen adsorption energies—useful descriptors for the oxidation activity of VOx–CeO2 catalysts. In this paper, we examine if this promoting effect on ceria-based catalysts holds for other metal oxide modifiers and we investigate MnOn– and CrOn–CeO2(111) (n = 0 − 4) as examples. We show, combining density functional theory calculations and statistical thermodynamics that similarly to the vanadia modifier, the stable species in each case is MnO2– and CrO2–CeO2. Both show favourable energetics for oxygen vacancy formation and hydrogen adsorption, indicating that VO2–CeO2 is not the only system of this type that can have an enhanced activity for oxidation reactions. However, the mechanism involved in each case is different: CrO2–CeO2 shows similar properties to VO2–CeO2 with ceria reduction upon oxygen removal stabilising the 5+ oxidation state of Cr. In contrast, with MnO2–CeO2, Mn is preferentially reduced. Finally, a model system of VO2–Mg:CeO2 is explored that shows a synergy between VO2 modification and Mg doping. These results shed light on the factors involved in active oxidation catalysts based on supported metal oxides on ceria that should be taken into consideration in a rational design of such catalysts.

Alloy/Oxide Equilibria in Iron--Vanadium--Oxygen and Iron--Niobium--Oxygen Systems

An experimental characterization of three-phase equilibria in Fe--V--O and Fe--Nb--O systems at 1823, 1873 and 1923K has been carried out using a solid state cell and by analysis of quenched samples. The oxygen potentials corresponding to these three-phase equilibria were monitored by a solid state cell incorporating Y sub 2 O sub 3 doped ThO sub 2 with Cr + Cr sub 2 O sub 3 as reference electrode. Similar measurements were carried out for Fe--Nb--O alloys in equilibrium with a mixture of FeNb sub 2 O sub 6 and NbO sub 2 . These measurements permit evaluation of interaction parameters (e exp V sub O = --6590/T + 2.892 and e exp Nb sub O = --4066/T + 1.502) and activity coefficients of vanadiun and niobium in dilute solution (ln gamma exp O sub V = --35 320/T + 12.68 and ln gamma sub Nb exp O = --12 386/T + 4.34) in liquid iron. The results obtained in this study resolve a number of discrepancies in thermodynamic data reported in the literature, especially regarding the activity coefficients of V and Nb and the stability ranges for V sub 2 O sub 3 and VO sub 1+x . 18 ref.--AA