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.

Determinação do estado fundamental de compostos antiferromagnéticos da série Tb(1-x)Y(x)RhIn(5): aproximação teórico experimental

We present the results of electrical resistivity, magnetic susceptibility, specific heat and x-ray absorption spectroscopy measurements in Tb1−xYxRhIn5 (x = 0.00, 0.15, 0.4.0, 0.50 e 0.70) single crystals. Tb1−xYxRhIn5 is an antiferromagnetic AFM compound with ordering temperature TN ≈ 46 K, the higher TN within the RRhIn5 serie (R : rare earth). We evaluate the physical properties evolution and the supression of the AFM state considering doping and Crystalline Electric Field (CEF) effects on magnetic exchange interaction between Tb3+ magnetic ions. CEF acts like a perturbation potential, breaking the (2J + 1) multiplet s degeneracy. Also, we studied linear-polarization-dependent soft x-ray absorption at Tb M4 and M5 edges to validate X-ray Absorption Spectroscopy as a complementary technique in determining the rare earth CEF ground state. Samples were grown by the indium excess flux and the experimental data (magnetic susceptibility and specific heat) were adjusted with a mean field model that takes account magnetic exchange interaction between first neighbors and CEF effects. XAS experiments were carried on Total Electron Yield mode at Laborat´onio Nacional de Luz S´ıncrotron, Campinas. We measured X-ray absorption at Tb M4,5 edges with incident polarized X-ray beam parallel and perpendicular to c-axis (E || c e E ⊥ c). The mean field model simulates the mean behavior of the whole system and, due to many independent parameters, gives a non unique CEF scheme. XAS is site- and elemental- specific technique and gained the scientific community s attention as complementary technique in determining CEF ground state in rare earth based compounds. In this work we wil discuss the non conclusive results of XAS technique in TbRhIn5 compounds.

Voltammetric determination of L-dopa using an electrode modified with trinuclear ruthenium ammine complex (Ru-red) supported on Y-type zeolite

The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson's disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH3)(5)Ru-III-O-Ru-IV(NH3)(4)-O-Ru-III(NH3)(5)](6+) (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2 x 10(-4) and 1.0 x 10(-2) Mol l(-1) (r = 0.9988) with a detection limit of 8.5 x 10(-5) mol l(-1). The variation coefficient for a 1.0 x 10(-3) mol l(-1) L-dopa (n = 10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa. (C) 2004 Elsevier B.V. All rights reserved.

Origen y distribución de tierras raras (RREs) en el agua y sedimentos de la Laguna de El Hito (Cuenca, España Central).

Determination of Rare Earth Elements (REEs) in the waters and sediments of El Hito Lake and its drainage basin was carried out. Distribution maps for REEs concentrations show increasing values in the lake sediments from the center to the eastern edge reaching 166.5 mg/kg. In the drainage basin, higher values were observed with a maximum of 350.9 mg/kg in the southern part. Concentrations in the water were considerably lower with a maximum value of 1.3 µg/L. Ce, La and Nd were the most abundant elements. When normalized REE concentrations against NASC (North American Shale Composite), a positive anomaly of Eu in the water and of Nd in the sediments (lake and basin) was observed. The (La/Gd)NASC and (La/Yb)NASC ratios determined the predominance of light REE (LREE) over medium (MREE) and heavy REE (HREE). Key-words: Rare Earth Elements, lacustrine sediments and water, Eu anomaly, sulfates RESUMEN: Se llevó a cabo el estudio de Tierras Raras (REEs) del agua y los sedimentos de la Laguna de El Hito así como de su cuenca de recepción. Los mapas de distribución de las concentraciones de REE en los sedimentos de la laguna mostraron valores crecientes desde el centro hacia el margen este alcanzando 166.5 mg/kg. En la cuenca se midieron valores más elevados llegando hasta 350.9 mg/kg en la mitad sur. Los valores en el agua fueron notablemente inferiores, con un máximo de 1.3 µg/L. El elemento más abundante fue el Ce seguido del Nd. Se normalizaron las concentraciones de REEs frente a las del NASC (North American Shale Composite), observándose una anomalía positiva de Eu en el agua, así como de Nd en los sedimentos (laguna y cuenca). Mediante los índices (La/Gd)NASC y (La/Yb)NASC se determinó el predominio de las REEs ligeras (LREEs) frente a las medias (MREE) y pesadas (HREE).

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.

Limestone and speleothem trace element geochemistry as tools for palaeoclimatic reconstruction, Mount Etna region, central-coastal Queensland

This study investigated potential palaeoclimate proxies provided by rare earth element (REE) geochemistry in speleothems and in clay mineralogy of cave sediments. Speleothem and sediment samples were collected from a series of cave fill deposits that occurred with rich vertebrate fossil assemblages in and around Mount Etna National Park, Rockhampton (central coastal Queensland). The fossil deposits range from Plio- Pleistocene to Holocene in age (based on uranium/thorium dating) and appear to represent depositional environments ranging from enclosed rainforest to semi-arid grasslands. Therefore, the Mount Etna cave deposits offer the perfect opportunity to test new palaeoclimate tools as they include deposits that span a known significant climate shift on the basis of independent faunal data. The first section of this study investigates the REE distribution of the host limestone to provide baseline geochemistry for subsequent speleothem investigations. The Devonian Mount Etna Beds were found to be more complex than previous literature had documented. The studied limestone massif is overturned, highly recrystallised in parts and consists of numerous allochthonous blocks with different spatial orientations. Despite the complex geologic history of the Mount Etna Beds, Devonian seawater-like REE patterns were recovered in some parts of the limestone and baseline geochemistry was determined for the bulk limestone for comparison with speleothem REE patterns. The second part of the study focused on REE distribution in the karst system and the palaeoclimatic implications of such records. It was found that REEs have a high affinity for calcite surfaces and that REE distributions in speleothems vary between growth bands much more than along growth bands, thus providing a temporal record that may relate to environmental changes. The morphology of different speleothems (i.e., stalactites, stalagmites, and flowstones) has little bearing on REE distributions provided they are not contaminated with particulate fines. Thus, baseline knowledge developed in the study suggested that speleothems were basically comparable for assessing palaeoclimatically controlled variations in REE distributions. Speleothems from rainforest and semi-arid phases were compared and it was found that there are definable differences in REE distribution that can be attributed to climate. In particular during semiarid phases, total REE concentration decreased, LREE became more depleted, Y/Ho increased, La anomalies were more positive and Ce anomalies were more negative. This may reflect more soil development during rainforest phases and more organic particles and colloids, which are known to transport REEs, in karst waters. However, on a finer temporal scale (i.e. growth bands) within speleothems from the same climate regime, no difference was seen. It is suggested that this may be due to inadequate time for soil development changes on the time frames represented by differences in growth band density. The third part of the study was a reconnaissance investigation focused on mineralogy of clay cave sediments, illite/kaolinite ratios in particular, and the potential palaeoclimatic implications of such records. Although the sample distribution was not optimal, the preliminary results suggest that the illite/kaolinite ratio increased during cold and dry intervals, consistent with decreased chemical weathering during those times. The study provides a basic framework for future studies at differing latitudes to further constrain the parameters of the proxy. The identification of such a proxy recorded in cave sediment has broad implications as clay ratios could potentially provide a basic local climate proxy in the absence of fossil faunas and speleothem material. This study suggests that REEs distributed in speleothems may provide information about water throughput and soil formation, thus providing a potential palaeoclimate proxy. It highlights the importance of understanding the host limestone geochemistry and broadens the distribution and potential number of cave field sites as palaeoclimate information no longer relies solely on the presence of fossil faunas and or speleothems. However, additional research is required to better understand the temporal scales required for the proxies to be recognised.

Infrared and Raman spectroscopic characterization of the carbonate mineral weloganite – Sr3Na2Zr(CO3)6·3H2O and in comparison with selected carbonates

The mineral weloganite Na2Sr3Zr(CO3)6·3H2O has been studied by using vibrational spectroscopy and a comparison is made with the spectra of weloganite with other carbonate minerals. Weloganite is member of the mckelveyite group that includes donnayite-(Y) and mckelveyite-(Y). The Raman spectrum of weloganite is characterized by an intense band at 1082 cm−1 with shoulder bands at 1061 and 1073 cm−1, attributed to the View the MathML source symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of View the MathML source symmetric stretching vibration varies with mineral composition. The Raman bands at 1350, 1371, 1385, 1417, 1526, 1546, and 1563 cm−1 are assigned to the ν3 (CO3)2− antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for weloganite is significant in that it shows distortion of the carbonate anion in the mineral structure. The Raman band observed at 870 cm−1 is assigned to the (CO3)2− ν2 bending mode. Raman bands observed for weloganite at 679, 682, 696, 728, 736, 749, and 762 cm−1 are assigned to the (CO3)2− ν4 bending modes. A comparison of the vibrational spectra is made with that of the rare earth carbonates decrespignyite, bastnasite, hydroxybastnasite, parisite, and northupite.

Impact of recent coastal development and human activities on Nha Trang Bay, Vietnam : evidence from a Porites lutea geochemical record

Nha Trang Bay (NTB) is located on the Central Vietnam coast, western South China Sea. Recent coastal development of Nha Trang City has raised public concern over an increasing level of pollution within the bay and degradation of nearby coral reefs. In this study, multiple proxies (e.g., trace metals, rare earth elements (REEs), and Y/Ho) recorded in a massive Porites lutea coral colony were used to reconstruct changes in seawater conditions in the NTB from 1995 to 2009. A 14-year record of REEs and other trace metals revealed that the concentrations of terrestrial trace metals have increased dramatically in response to an increase in coastal development projects such as road, port, and resort constructions, port and river dredging, and dumping activities since 2000. The effects of such developmental processes are also evident in changes in REE patterns and Y/Ho ratios through time, suggesting that both parameters are critical proxies for marine pollution.

Controls on mid-Holocene fringing reef growth and termination in a high latitude, estuarine setting, Wellington Point, Southeast Queensland

Several fringing coral reefs in Moreton Bay, Southeast Queensland, some 300 km south of the Great Barrier Reef (GBR), are set in a relatively high latitude, estuarine environment that is considered marginal for coral growth. Previous work indicated that these marginal reefs, as with many fringing reefs of the inner GBR, ceased accreting in the mid-Holocene. This research presents for the first time data from the subsurface profile of the mid-Holocene fossil reef at Wellington Point comprising U/Th dates of in situ and framework corals, and trace element analysis from the age constrained carbonate fragments. Based on trace element proxies the palaeo-water quality during reef accretion was reconstructed. Results demonstrate that the reef initiated more than 7,000 yr BP during the post glacial transgression, and the initiation progressed to the west as sea level rose. In situ micro-atolls indicate that sea level was at least 1 m above present mean sea level by 6,680 years ago. The reef remained in "catch-up" mode, with a seaward sloping upper surface, until it stopped aggrading abruptly at ca 6,000 yr BP; no lateral progradation occurred. Changes in sediment composition encountered in the cores suggest that after the laterite substrate was covered by the reef, most of the sediment was produced by the carbonate factory with minimal terrigenous influence. Rare earth element, Y and Ba proxies indicate that water quality during reef accretion was similar to oceanic waters, considered suitable for coral growth. A slight decline in water quality on the basis of increased Ba in the later stages of growth may be related to increased riverine input and partial closing up of the bay due to either tidal delta progradation, climatic change and/or slight sea level fall. The age data suggest that termination of reef growth coincided with a slight lowering of sea level, activation of ENSO and consequent increase in seasonality, lowering of temperatures and the constrictions to oceanic flushing. At the cessation of reef accretion the environmental conditions in the western Moreton Bay were changing from open marine to estuarine. The living coral community appears to be similar to the fossil community, but without the branching Acropora spp. that were more common in the fossil reef. In this marginal setting coral growth periods do not always correspond to periods of reef accretion due to insufficient coral abundance. Due to several environmental constraints modern coral growth is insufficient for reef growth. Based on these findings Moreton Bay may be unsuitable as a long term coral refuge for most species currently living in the GBR.

Fuel additive

A fuel additive comprising one or more complex oxides having a nominal compn. as set out in formula (1): AxB1-yMyOn; wherein A is selected from one or more group III elements including the lanthanide elements or one or more divalent or monovalent cations; B is selected from one or more elements with at. no. 22 to 24, 40 to 42 and 72 to 75; M is selected from one or more elements with at. no. 25 to 30; x is defined as a no. where 0 < x ≤ l; y is defined as a no. where 0 ≤ y < 0.5. [on SciFinder(R)]

Void Geometry Driven Spin Crossover in Zeolite-Encapsulated Cobalt Tris(bipyridyl) Complex Ion

The cobalt(II) tris(bipyridyl) complex ion encapsulated in zeolite-Y supercages exhibits a thermally driven interconversion between a low-spin and a high-spin state-a phenomenon not observed for this ion either in solid state or in solution. From a comparative study of the magnetism and optical spectroscopy of the encapsulated and unencapsulated complex ion, supported by molecular modeling, such spin behavior is shown to be intramolecular in origin. In the unencapsulated or free state, the [Co(bipy)(3)](2+) ion exhibits a marked trigonal prismatic distortion, but on encapsulation, the topology of the supercage forces it to adopt a near-octahedral geometry. An analysis using the angular overlap ligand field model with spectroscopically derived parameters shows that the geometry does indeed give rise to a low-spin ground state, and suggests a possible scenario for the spin state interconversion.

Novel 1122 thallium cuprates showing high Tc superconductivity: TlCa1-xY,Ba2Cu2Oy,T,1-xPbxCaSr2Cu2Oy and TlCa0.5Ln0.5Sr2Cu2Oy

Substitution of Ca by Y in TlCaBa2Cu2Oy does not favour superconductivity, but substitution of Tl by Pb or of Ca by Ln (Ln = Y or rare earth) in TlCaSr2Cu2Oy results in high Tc superconductivity (Tc π 60-90 K). TlCa1-xLnxSr2Cu2Oy is a new series of high Tc superconductors, but the x = 0.0 composition does not exhibit bulk superconductivity.

Memory effect in Dy0.5Sr0.5MnO3 single crystals

We have performed a series of magnetic aging experiments on single crystals of Dy0.5Sr0.5MnO3. The results demonstrate striking memory and chaos-like effects in this insulating half-doped perovskite manganite and suggest the existence of strong magnetic relaxation mechanisms of a clustered magnetic state. The spin-glass-like state established below a temperature T-sg approximate to 34 K originates from quenched disorder arising due to the ionic-radii mismatch at the rare earth site. However, deviations from the typical behavior seen in canonical spin glass materials are observed which indicate that the glassy magnetic properties are due to cooperative and frustrated dynamics in a heterogeneous or clustered magnetic state. In particular, the microscopic spin flip time obtained from dynamical scaling near the spin glass freezing temperature is four orders of magnitude larger than microscopic times found in atomic spin glasses. The magnetic viscosity deduced from the time dependence of the zero-field-cooled magnetization exhibits a peak at a temperature T < T-sg and displays a marked dependence on waiting time in zero field.

Occurrence of maximum Tc at an optimal carrier concentration in superconducting bismuth and thallium cuprates

The superconducting transition temperatures in Bi2Ca1−xLnxSr2Cu2O8+δ, TlCa1−xLnxSr2Cu2O6+δ, and Tl0.8Ca1−xLnxBa2Cu23O6+δ (Ln=Y or rare earth) vary with composition and show a maximum at a specific value of x or δ. This observation suggests that an optimal carrier concentration is required to attain maximum Tc in such cuprates which seem to be two‐band systems

Reversible Insertion of a Trivalent Cation onto MnO2 Leading to Enhanced Capacitance

Supercapacitor properties of MnO2 are studied generally in aqueous alkali metal salt solutions, often in a Na salt solution. During electrochemical discharge-charge processes, Na+ ions from the electrolyte get reversibly inserted/deinserted on the surface of MnO2 particles, which leads to redox reaction between MnOONa and MnO2. In the present study, it has been shown that MnO2 exhibits enhanced capacitance behaviour in a rare earth metal salt solution, namely, La(NO3)(3) solution in comparison with NaNO3 and Mg(NO3)(2) aqueous solutions. The specific capacitance increases with an increase in charge on the solution cation (Na+, Mg2+ and La3+). It is proposed that the number of surface sites for adsorption of cations remains unaltered in all solutions. The surface insertion of cation facilitates the reduction of Mn4+ in MnO2 to Mn3+ equivalent to the charge present on the cation. As the specific capacitance is related to the quantity of charge that is exchanged between the solid MnO2 and the aqueous solution, the trivalent cation (La3+) provides greater specific capacitance than in Mg(NO3)(2) and NaNO3 electrolytes. Accordingly, the number of Mn(IV)/Mn(III) redox pairs involved in the neighbourhood of the adsorption site is one, two and three when Na+, Mg2+ and La3+ ions, respectively, are adsorbed. (C) 2011 The Electrochemical Society. DOI: 10.1149/1.3565177] All rights reserved.