Geochemistry of interstitial waters of Lau Backarc Basin sediment samples

Interstitial water samples from Sites 834 through 839, drilled during Ocean Drilling Program Leg 135 in the backarc Lau basin (Southwestern Pacific), have been analyzed for major elements, manganese, copper, strontium, barium, vanadium, and 87Sr/86Sr isotopic composition values. The concentration-depth profiles of the major chemical components show almost straight concentration gradients at all sites, and seem to reflect slight alteration of volcanic material. However, in the lower part of the sedimentary cover, where volcanogenic material is abundant and where diagenetic minerals occur, systematic decreases in calcium, strontium, manganese, copper, and vanadium concentrations are observed. A downwelling flow of bottom seawater, which affected the diagenetic chemical signature of the interstitial water, is probably responsible for the recorded chemical features. This hypothesis is supported by strontium isotope data obtained from interstitial water samples at Site 835. It is also in accordance with data from heat flow and physical properties.

Magnetic properties and incompatible element geochemistry of some igneous rocks at DSDP Leg 64 Holes

I received five unoriented samples of igneous rocks from four Sites of Leg 64 of the Deep Sea Drilling Project (DSDP). I have measured several magnetic properties, alkalis (K, Rb, and Cs), alkaline-earth (Ba and Sr) element concentrations, and 87Sr/86Sr ratios of these samples. This study reports the results.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.

Lanthanide series rare earths : an annotated list of unclassified references.

AEC Report No. TID-3029.

Theory of strongly correlated electron systems. I. Intersite coulomb interaction and the approximation of renormalized fermions in total energy calculations

The diagrammatic strong-coupling perturbation theory (SCPT) for correlated electron systems is developed for intersite Coulomb interaction and for a nonorthogonal basis set. The construction is based on iterations of exact closed equations for many - electron Green functions (GFs) for Hubbard operators in terms of functional derivatives with respect to external sources. The graphs, which do not contain the contributions from the fluctuations of the local population numbers of the ion states, play a special role: a one-to-one correspondence is found between the subset of such graphs for the many - electron GFs and the complete set of Feynman graphs of weak-coupling perturbation theory (WCPT) for single-electron GFs. This fact is used for formulation of the approximation of renormalized Fermions (ARF) in which the many-electron quasi-particles behave analogously to normal Fermions. Then, by analyzing: (a) Sham's equation, which connects the self-energy and the exchange- correlation potential in density functional theory (DFT); and (b) the Galitskii and Migdal expressions for the total energy, written within WCPT and within ARF SCPT, a way we suggest a method to improve the description of the systems with correlated electrons within the local density approximation (LDA) to DFT. The formulation, in terms of renormalized Fermions LIDA (RF LDA), is obtained by introducing the spectral weights of the many electron GFs into the definitions of the charge density, the overlap matrices, effective mixing and hopping matrix elements, into existing electronic structure codes, whereas the weights themselves have to be found from an additional set of equations. Compared with LDA+U and self-interaction correction (SIC) methods, RF LDA has the advantage of taking into account the transfer of spectral weights, and, when formulated in terms of GFs, also allows for consideration of excitations and nonzero temperature. Going beyond the ARF SCPT, as well as RF LIDA, and taking into account the fluctuations of ion population numbers would require writing completely new codes for ab initio calculations. The application of RF LDA for ab initio band structure calculations for rare earth metals is presented in part 11 of this study (this issue). (c) 2005 Wiley Periodicals, Inc.

Transport phenomena in hydrogel membranes

In this thesis the factors surrounding the permeation of alkali and alkaline earth metal salts through hydrogel membranes are investigated. Although of relevance to aqueous separations in general, it was with their potential application in sensors that this work was particularly concerned. In order to study the effect that the nature of the solute has on the transport process, a single polymer matrix, poly (2-hydroxyethyl methacrylate), was initially studied. The influence of cation variation in the presence of a fixed anion was looked at, followed by the effect of the anion in the presence of a fixed cation. The anion was found to possess the dominant influence and tended to subsume any influence by the cation. This is explained in terms of the structure-making and structure-breaking characteristics of the ions in their solute-water interactions. Analogies in the transport behaviour of the salts are made with the Hofmeister series. The effect of the chemical composition of the polymer backbone on the water structuring in the hydrogel and, consequently, transport through the membrane, was investigated by preparing a series of poly (2-hydroxyethyl methacrylate) copolymer membranes and determining the permeability coefficient of salts with a fixed anion. The results were discussed in terms of the `free-volume' model of permeation and the water structuring of the polymer backbone. The ability of ionophores to selectively modulate the permeation of salts through hydrogel membranes was also examined. The results indicated that a dualsorption model was in operation. Finally, hydrogels were used as membrane overlays on coated wire ion-selective electrodes that employed conventional plasticised-PVC-valinomycin based sensing membranes. The hydrogel overlays were found to affect the access of the analyte but not the underlying electrochemistry.

Hierarchical porous catalysts tailored for biodiesel production

There is a pressing need for sustainable transportation fuels to combat both climate change and dwindling fossil fuel reserves. Biodiesel, synthesised from non-food plant (e.g., Jatropha curcas) or algal crops is one possible solution, but its energy efficient production requires design of new solid catalysts optimized for the bulky triglyceride and fatty acid feedstocks. Here we report on the synthesis of hierarchical macroporous-mesoporous silica and alumina architectures, and their subsequent functionalization by propylsulfonic acid groups or alkaline earth oxides to generate novel solid acid and base catalysts. These materials possess high surface areas and well-defined, interconnected macro-mesopore networks with respective narrow pore size distributions tuneable around 300 nm and 5 nm. Their high conductivity and improved mass transport characteristics enhance activity towards transesterification of bulky tricaprylin and palmitic acid esterification, over mesoporous analogues. This opens the way to the wider application of hierarchical catalysts in biofuel synthesis and biomass conversion.

Structure, energetics and reactions of metal cation complexes of dipeptides in the gas phase

Structure, energetics and reactions of ions in the gas phase can be revealed by mass spectrometry techniques coupled to ions activation methods. Ions can gain enough energy for dissociation by absorbing IR light photons introduced by an IR laser to the mass spectrometer. Also collisions with a neutral molecule can increase the internal energy of ions and provide the dissociation threshold energy. Infrared multiple photon dissociation (IRMPD) or sustained off-resonance irradiation collision-induced dissociation (SORI-CID) methods are combined with Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometers where ions can be held at low pressures for a long time. The outcome of ion activation techniques especially when it is compared to the computational methods results is of great importance since it provides useful information about the structure, thermochemistry and reactivity of ions of interest. In this work structure, energetics and reactivity of metal cation complexes with dipeptides are investigated. Effect of metal cation size and charge as well as microsolvation on the structure of these complexes has been studied. Structures of bare and hydrated Na and Ca complexes with isomeric dipeptides AlaGly and GlyAla are characterized by means of IRMPD spectroscopy and computational methods. At the second step unimolecular dissociation reactions of singly charged and doubly charged multimetallic complexes of alkaline earth metal cations with GlyGly are examined by CID method. Also structural features of these complexes are revealed by comparing their IRMPD spectra with calculated IR spectra of possible structures. At last the unimolecular dissociation reactions of Mn complexes are studied. IRMPD spectroscopy along with computational methods is also employed for structural elucidation of Mn complexes. In addition the ion-molecule reactions of Mn complexes with CO and water are explored in the low pressures obtained in the ICR cell.

Electrolytes for ceramic oxide fuel cells

The main objective of this dissertation is the development and processing of novel ionic conducting ceramic materials for use as electrolytes in proton or oxide-ion conducting solid oxide fuel cells. The research aims to develop new processing routes and/or materials offering superior electrochemical behavior, based on nanometric ceramic oxide powders prepared by mechanochemical processes. Protonic ceramic fuel cells (PCFCs) require electrolyte materials with high proton conductivity at intermediate temperatures, 500-700ºC, such as reported for perovskite zirconate oxides containing alkaline earth metal cations. In the current work, BaZrO3 containing 15 mol% of Y (BZY) was chosen as the base material for further study. Despite offering high bulk proton conductivity the widespread application of this material is limited by its poor sinterability and grain growth. Thus, minor additions of oxides of zinc, phosphorous and boron were studied as possible sintering additives. The introduction of ZnO can produce substantially enhanced densification, compared to the un-doped material, lowering the sintering temperature from 1600ºC to 1300ºC. Thus, the current work discusses the best solid solution mechanism to accommodate this sintering additive. Maximum proton conductivity was shown to be obtained in materials where the Zn additive is intentionally adopted into the base perovskite composition. P2O5 additions were shown to be less effective as a sintering additive. The presence of P2O5 was shown to impair grain growth, despite improving densification of BZY for intermediate concentrations in the range 4 – 8 mol%. Interreaction of BZY with P was also shown to have a highly detrimental effect on its electrical transport properties, decreasing both bulk and grain boundary conductivities. The densification behavior of H3BO3 added BaZrO3 (BZO) shows boron to be a very effective sintering aid. Nonetheless, in the yttrium containing analogue, BaZr0.85Y0.15O3- (BZY) the densification behavior with boron additives was shown to be less successful, yielding impaired levels of densification compared to the plain BZY. This phenomenon was shown to be related to the undesirable formation of barium borate compositions of high melting temperatures. In the last section of the work, the emerging oxide-ion conducting materials, (Ba,Sr)GeO3 doped with K, were studied. Work assessed if these materials could be formed by mechanochemical process and the role of the ionic radius of the alkaline earth metal cation on the crystallographic structure, compositional homogeneity and ionic transport. An abrupt jump in oxide-ion conductivity was shown on increasing operation temperature in both the Sr and Ba analogues.

Testing the universality of free fall with rubidium and ytterbium in a very large baseline atom interferometer

We propose a very long baseline atom interferometer test of Einstein's equivalence principle (EEP) with ytterbium and rubidium extending over 10m of free fall. In view of existing parametrizations of EEP violations, this choice of test masses significantly broadens the scope of atom interferometric EEP tests with respect to other performed or proposed tests by comparing two elements with high atomic numbfers. In the first step, our experimental scheme will allow us to reach an accuracy in the Eotvos ratio of 7 . 10(-13). This achievement will constrain violation scenarios beyond our present knowledge and will represent an important milestone for exploring a variety of schemes for further improvements of the tests as outlined in the paper. We will discuss the technical realisation in the new infrastructure of the Hanover Institute of Technology (HITec) and give a short overview of the requirements needed to reach this accuracy. The experiment will demonstrate a variety of techniques, which will be employed in future tests of EEP, high-accuracy gravimetry and gravity gradiometry. It includes operation of a force-sensitive atom interferometer with an alkaline earth-like element in free fall, beam splitting over macroscopic distances and novel source concepts.

África Austral: Los minerales como recurso estratégico para los intereses de Estados Unidos y China, período 2000-2010

La región de África Austral emerge como un nuevo escenario geopolítico complejo, en el que la lucha por la adquisición de los derechos de exploración, extracción y distribución de minerales estratégicos ha intensificado la presencia del número de actores estratégicos en esta zona. En este sentido, es interesante analizar el juego de poder que se desarrolla entre Estados Unidos y China con el fin de neutralizar la debilidad estratégica que representa la carencia de estos recursos naturales, esenciales para el desarrollo de sus industrias, así como también la oportunidad que representan como mecanismo para ampliar las esferas de influencia extra continental. Así pues, la presente investigación analiza a partir de la explotación de los minerales como recursos estratégicos, los efectos de la geoestrategia reciente de estos dos jugadores activos del sistema internacional contemporáneo en la relación con los Estados que conforman la región meridional del continente africano, durante el periodo 2000-2010.

Synthesis, characterization and spectroscopic investigation of new tetrakis(acetylacetonato)thulate(III) complexes containing alkaline metals as countercations

In this work a series of tetrakis complexes C[Tm(acac)(4)] where C(+) = Li(+) Na(+) and K(+) countercations and acac = acetylacetonate ligand were synthesized and characterized for photoluminescence investigation The relevant aspect is that these complexes are water-free in the first coordination sphere The emission spectra of the tetrakis Tm(3+)-complexes present narrow bands characteristic of the (1)G(4)->(3)H(6) (479 nm) (1)G(4)->(3)F(4) (650 nm) and (1)G(4) ->(3)H(5) (779 nm) transitions of the Tm(3+) ion with the blue emission color at 479 nm as the most prominent one The lifetime values (tau) of the emitting (1)G(4) level of the C[Tm(acac)(4)] complexes were 344 360 and 400 ns for the Li(+) Na(+) and K(+) countercations respectively showing an increasing linear behavior versus the ionic radius of the alkaline ion An efficient intramolecular energy transfer process from the triplet state (T) of the ligands to the emitting (1)G(4) state of the Tm(3+) ion is observed This fact together with the absence of water molecules in first coordination sphere allows these tetrakis Tm(3+)-complexes to act as efficient blue light conversion molecular devices (c) 2010 Elsevier B V All rights reserved