Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

Estrategias de monitorización de CO2 y otros gases en los estudios de análogos naturales

La Universidad Politécnica de Madrid (UPM) y la Università degli Studi di Firenze (UniFi), bajo la coordinación técnica de AMPHOS21, participan desde 2009 en el proyecto de investigación “Estrategias de Monitorización de CO2 y otros gases en el estudio de Análogos Naturales”, financiado por la Fundación Ciudad de la Energía (CIUDEN) en el marco del Proyecto Compostilla OXYCFB300 (http://www.compostillaproject.eu), del Programa “European Energy Program for Recovery - EEPR”. El objetivo principal del proyecto fue el desarrollo y puesta a punto de metodologías de monitorización superficiales para su aplicación en el seguimiento y control de los emplazamientos donde se realice el almacenamiento geológico de CO2, analizando técnicas que permitan detectar y cuantificar las posibles fugas de CO2 a la atmósfera. Los trabajos se realizaron tanto en análogos naturales (españoles e italianos) como en la Planta de Desarrollo Tecnológico de Almacenamiento de CO2 de Hontomín. Las técnicas analizadas se centran en la medición de gases y aguas superficiales (de escorrentía y manantiales). En cuanto a la medición de gases se analizó el flujo de CO2 que emana desde el suelo a la atmósfera y la aplicabilidad de trazadores naturales (como el radón) para la detección e identificación de las fugas de CO2. En cuanto al análisis químico de las aguas se analizaron los datos geoquímicos e isotópicos y los gases disueltos en las aguas de los alrededores de la PDT de Hontomín, con objeto de determinar qué parámetros son los más apropiados para la detección de una posible migración del CO2 inyectado, o de la salmuera, a los ambientes superficiales. Las medidas de flujo de CO2 se realizaron con la técnica de la cámara de acúmulo. A pesar de ser una técnica desarrollada y aplicada en diferentes ámbitos científicos se estimó necesario adaptar un protocolo de medida y de análisis de datos a las características específicas de los proyectos de captura y almacenamiento de CO2 (CAC). Donde los flujos de CO2 esperados son bajos y en caso de producirse una fuga habrá que detectar pequeñas variaciones en los valores flujo con un “ruido” en la señal alto, debido a actividad biológica en el suelo. La medida de flujo de CO2 mediante la técnica de la cámara de acúmulo se puede realizar sin limpiar la superficie donde se coloca la cámara o limpiando y esperando al reequilibrio del flujo después de la distorsión al sistema. Sin embargo, los resultados obtenidos después de limpiar y esperar muestran menor dispersión, lo que nos indica que este procedimiento es el mejor para la monitorización de los complejos de almacenamiento geológico de CO2. El protocolo de medida resultante, utilizado para la obtención de la línea base de flujo de CO2 en Hontomín, sigue los siguiente pasos: a) con una espátula se prepara el punto de medición limpiando y retirando el recubrimiento vegetal o la primera capa compacta de suelo, b) se espera un tiempo para la realización de la medida de flujo, facilitando el reequilibrio del flujo del gas tras la alteración provocada en el suelo y c) se realiza la medida de flujo de CO2. Una vez realizada la medición de flujo de CO2, y detectada si existen zonas de anomalías, se debe estimar la cantidad de CO2 que se está escapando a la atmósfera (emanación total), con el objetivo de cuantificar la posible fuga. Existen un amplio rango de metodologías para realizar dicha estimación, siendo necesario entender cuáles son las más apropiadas para obtener el valor más representativo del sistema. En esta tesis se comparan seis técnicas estadísticas: media aritmética, estimador insegado de la media (aplicando la función de Sichel), remuestreo con reemplazamiento (bootstrap), separación en diferentes poblaciones mediante métodos gráficos y métodos basados en criterios de máxima verosimilitud, y la simulación Gaussiana secuencial. Para este análisis se realizaron ocho campañas de muestreo, tanto en la Planta de Desarrollo Tecnológico de Hontomón como en análogos naturales (italianos y españoles). Los resultados muestran que la simulación Gaussiana secuencial suele ser el método más preciso para realizar el cálculo, sin embargo, existen ocasiones donde otros métodos son más apropiados. Como consecuencia, se desarrolla un procedimiento de actuación para seleccionar el método que proporcione el mejor estimador. Este procedimiento consiste, en primer lugar, en realizar un análisis variográfico. Si existe una autocorrelación entre los datos, modelizada mediante el variograma, la mejor técnica para calcular la emanación total y su intervalo de confianza es la simulación Gaussiana secuencial (sGs). Si los datos son independientes se debe comprobar la distribución muestral, aplicando la media aritmética o el estimador insesgado de la media (Sichel) para datos normales o lognormales respectivamente. Cuando los datos no son normales o corresponden a una mezcla de poblaciones la mejor técnica de estimación es la de remuestreo con reemplazamiento (bootstrap). Siguiendo este procedimiento el máximo valor del intervalo de confianza estuvo en el orden del ±20/25%, con la mayoría de valores comprendidos entre ±3,5% y ±8%. La identificación de las diferentes poblaciones muestrales en los datos de flujo de CO2 puede ayudar a interpretar los resultados obtenidos, toda vez que esta distribución se ve afectada por la presencia de varios procesos geoquímicos como, por ejemplo, una fuente geológica o biológica del CO2. Así pues, este análisis puede ser una herramienta útil en el programa de monitorización, donde el principal objetivo es demostrar que no hay fugas desde el reservorio a la atmósfera y, si ocurren, detectarlas y cuantificarlas. Los resultados obtenidos muestran que el mejor proceso para realizar la separación de poblaciones está basado en criterios de máxima verosimilitud. Los procedimientos gráficos, aunque existen pautas para realizarlos, tienen un cierto grado de subjetividad en la interpretación de manera que los resultados son menos reproducibles. Durante el desarrollo de la tesis se analizó, en análogos naturales, la relación existente entre el CO2 y los isótopos del radón (222Rn y 220Rn), detectándose en todas las zonas de emisión de CO2 una relación positiva entre los valores de concentración de 222Rn en aire del suelo y el flujo de CO2. Comparando la concentración de 220Rn con el flujo de CO2 la relación no es tan clara, mientras que en algunos casos aumenta en otros se detecta una disminución, hecho que parece estar relacionado con la profundidad de origen del radón. Estos resultados confirmarían la posible aplicación de los isótopos del radón como trazadores del origen de los gases y su aplicación en la detección de fugas. Con respecto a la determinación de la línea base de flujo CO2 en la PDT de Hontomín, se realizaron mediciones con la cámara de acúmulo en las proximidades de los sondeos petrolíferos, perforados en los ochenta y denominados H-1, H-2, H-3 y H-4, en la zona donde se instalarán el sondeo de inyección (H-I) y el de monitorización (H-A) y en las proximidades de la falla sur. Desde noviembre de 2009 a abril de 2011 se realizaron siete campañas de muestreo, adquiriéndose más de 4.000 registros de flujo de CO2 con los que se determinó la línea base y su variación estacional. Los valores obtenidos fueron bajos (valores medios entre 5 y 13 g•m-2•d-1), detectándose pocos valores anómalos, principalmente en las proximidades del sondeo H-2. Sin embargo, estos valores no se pudieron asociar a una fuente profunda del CO2 y seguramente estuvieran más relacionados con procesos biológicos, como la respiración del suelo. No se detectaron valores anómalos cerca del sistema de fracturación (falla Ubierna), toda vez que en esta zona los valores de flujo son tan bajos como en el resto de puntos de muestreo. En este sentido, los valores de flujo de CO2 aparentemente están controlados por la actividad biológica, corroborado al obtenerse los menores valores durante los meses de otoño-invierno e ir aumentando en los periodos cálidos. Se calcularon dos grupos de valores de referencia, el primer grupo (UCL50) es 5 g•m-2•d-1 en las zonas no aradas en los meses de otoño-invierno y 3,5 y 12 g•m-2•d-1 en primavera-verano para zonas aradas y no aradas, respectivamente. El segundo grupo (UCL99) corresponde a 26 g•m-2•d- 1 durante los meses de otoño-invierno en las zonas no aradas y 34 y 42 g•m-2•d-1 para los meses de primavera-verano en zonas aradas y no aradas, respectivamente. Flujos mayores a estos valores de referencia podrían ser indicativos de una posible fuga durante la inyección y posterior a la misma. Los primeros datos geoquímicos e isotópicos de las aguas superficiales (de escorrentía y de manantiales) en el área de Hontomín–Huermeces fueron analizados. Los datos sugieren que las aguas estudiadas están relacionadas con aguas meteóricas con un circuito hidrogeológico superficial, caracterizadas por valores de TDS relativamente bajos (menor a 800 mg/L) y una fácie hidrogeoquímica de Ca2+(Mg2+)-HCO3 −. Algunas aguas de manantiales se caracterizan por concentraciones elevadas de NO3 − (concentraciones de hasta 123 mg/l), lo que sugiere una contaminación antropogénica. Se obtuvieron concentraciones anómalas de of Cl−, SO4 2−, As, B y Ba en dos manantiales cercanos a los sondeos petrolíferos y en el rio Ubierna, estos componentes son probablemente indicadores de una posible mezcla entre los acuíferos profundos y superficiales. El estudio de los gases disueltos en las aguas también evidencia el circuito superficial de las aguas. Estando, por lo general, dominado por la componente atmosférica (N2, O2 y Ar). Sin embargo, en algunos casos el gas predominante fue el CO2 (con concentraciones que llegan al 63% v/v), aunque los valores isotópicos del carbono (<-17,7 ‰) muestran que lo más probable es que esté relacionado con un origen biológico. Los datos geoquímicos e isotópicos de las aguas superficiales obtenidos en la zona de Hontomín se pueden considerar como el valor de fondo con el que comparar durante la fase operacional, la clausura y posterior a la clausura. En este sentido, la composición de los elementos mayoritarios y traza, la composición isotópica del carbono del CO2 disuelto y del TDIC (Carbono inorgánico disuelto) y algunos elementos traza se pueden considerar como parámetros adecuados para detectar la migración del CO2 a los ambientes superficiales. ABSTRACT Since 2009, a group made up of Universidad Politécnica de Madrid (UPM; Spain) and Università degli Studi Firenze (UniFi; Italy) has been taking part in a joint project called “Strategies for Monitoring CO2 and other Gases in Natural analogues”. The group was coordinated by AMPHOS XXI, a private company established in Barcelona. The Project was financially supported by Fundación Ciudad de la Energía (CIUDEN; Spain) as a part of the EC-funded OXYCFB300 project (European Energy Program for Recovery -EEPR-; www.compostillaproject.eu). The main objectives of the project were aimed to develop and optimize analytical methodologies to be applied at the surface to Monitor and Verify the feasibility of geologically stored carbon dioxide. These techniques were oriented to detect and quantify possible CO2 leakages to the atmosphere. Several investigations were made in natural analogues from Spain and Italy and in the Tecnchnological Development Plant for CO2 injection al Hontomín (Burgos, Spain). The studying techniques were mainly focused on the measurements of diffuse soil gases and surface and shallow waters. The soil-gas measurements included the determination of CO2 flux and the application to natural trace gases (e.g. radon) that may help to detect any CO2 leakage. As far as the water chemistry is concerned, geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of the PDT of Hontomín were analyzed to determine the most suitable parameters to trace the migration of the injected CO2 into the near-surface environments. The accumulation chamber method was used to measure the diffuse emission of CO2 at the soil-atmosphere interface. Although this technique has widely been applied in different scientific areas, it was considered of the utmost importance to adapt the optimum methodology for measuring the CO2 soil flux and estimating the total CO2 output to the specific features of the site where CO2 is to be stored shortly. During the pre-injection phase CO2 fluxes are expected to be relatively low where in the intra- and post-injection phases, if leakages are to be occurring, small variation in CO2 flux might be detected when the CO2 “noise” is overcoming the biological activity of the soil (soil respiration). CO2 flux measurements by the accumulation chamber method could be performed without vegetation clearance or after vegetation clearance. However, the results obtained after clearance show less dispersion and this suggests that this procedure appears to be more suitable for monitoring CO2 Storage sites. The measurement protocol, applied for the determination of the CO2 flux baseline at Hontomín, has included the following steps: a) cleaning and removal of both the vegetal cover and top 2 cm of soil, b) waiting to reduce flux perturbation due to the soil removal and c) measuring the CO2 flux. Once completing the CO2 flux measurements and detected whether there were anomalies zones, the total CO2 output was estimated to quantify the amount of CO2 released to the atmosphere in each of the studied areas. There is a wide range of methodologies for the estimation of the CO2 output, which were applied to understand which one was the most representative. In this study six statistical methods are presented: arithmetic mean, minimum variances unbiased estimator, bootstrap resample, partitioning of data into different populations with a graphical and a maximum likelihood procedures, and sequential Gaussian simulation. Eight campaigns were carried out in the Hontomín CO2 Storage Technology Development Plant and in natural CO2 analogues. The results show that sequential Gaussian simulation is the most accurate method to estimate the total CO2 output and the confidential interval. Nevertheless, a variety of statistic methods were also used. As a consequence, an application procedure for selecting the most realistic method was developed. The first step to estimate the total emanation rate was the variogram analysis. If the relation among the data can be explained with the variogram, the best technique to calculate the total CO2 output and its confidence interval is the sequential Gaussian simulation method (sGs). If the data are independent, their distribution is to be analyzed. For normal and log-normal distribution the proper methods are the arithmetic mean and minimum variances unbiased estimator, respectively. If the data are not normal (log-normal) or are a mixture of different populations the best approach is the bootstrap resampling. According to these steps, the maximum confidence interval was about ±20/25%, with most of values between ±3.5% and ±8%. Partitioning of CO2 flux data into different populations may help to interpret the data as their distribution can be affected by different geochemical processes, e.g. geological or biological sources of CO2. Consequently, it may be an important tool in a monitoring CCS program, where the main goal is to demonstrate that there are not leakages from the reservoir to the atmosphere and, if occurring, to be able to detect and quantify it. Results show that the partitioning of populations is better performed by maximum likelihood criteria, since graphical procedures have a degree of subjectivity in the interpretation and results may not be reproducible. The relationship between CO2 flux and radon isotopes (222Rn and 220Rn) was studied in natural analogues. In all emissions zones, a positive relation between 222Rn and CO2 was observed. However, the relationship between activity of 220Rn and CO2 flux is not clear. In some cases the 220Rn activity indeed increased with the CO2 flux in other measurements a decrease was recognized. We can speculate that this effect was possibly related to the route (deep or shallow) of the radon source. These results may confirm the possible use of the radon isotopes as tracers for the gas origin and their application in the detection of leakages. With respect to the CO2 flux baseline at the TDP of Hontomín, soil flux measurements in the vicinity of oil boreholes, drilled in the eighties and named H-1 to H-4, and injection and monitoring wells were performed using an accumulation chamber. Seven surveys were carried out from November 2009 to summer 2011. More than 4,000 measurements were used to determine the baseline flux of CO2 and its seasonal variations. The measured values were relatively low (from 5 to 13 g•m-2•day-1) and few outliers were identified, mainly located close to the H-2 oil well. Nevertheless, these values cannot be associated to a deep source of CO2, being more likely related to biological processes, i.e. soil respiration. No anomalies were recognized close to the deep fault system (Ubierna Fault) detected by geophysical investigations. There, the CO2 flux is indeed as low as other measurement stations. CO2 fluxes appear to be controlled by the biological activity since the lowest values were recorded during autumn-winter seasons and they tend to increase in warm periods. Two reference CO2 flux values (UCL50 of 5 g•m-2•d-1 for non-ploughed areas in autumn-winter seasons and 3.5 and 12 g•m-2•d-1 for in ploughed and non-ploughed areas, respectively, in spring-summer time, and UCL99 of 26 g•m-2•d-1 for autumn-winter in not-ploughed areas and 34 and 42 g•m-2•d-1 for spring-summer in ploughed and not-ploughed areas, respectively, were calculated. Fluxes higher than these reference values could be indicative of possible leakage during the operational and post-closure stages of the storage project. The first geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of Hontomín–Huermeces (Burgos, Spain) are presented and discussed. The chemical and features of the spring waters suggest that they are related to a shallow hydrogeological system as the concentration of the Total Dissolved Solids approaches 800 mg/L with a Ca2+(Mg2+)-HCO3 − composition, similar to that of the surface waters. Some spring waters are characterized by relatively high concentrations of NO3 − (up to 123 mg/L), unequivocally suggesting an anthropogenic source. Anomalous concentrations of Cl−, SO4 2−, As, B and Ba were measured in two springs, discharging a few hundred meters from the oil wells, and in the Rio Ubierna. These contents are possibly indicative of mixing processes between deep and shallow aquifers. The chemistry of the dissolved gases also evidences the shallow circuits of the Hontomín– Huermeces, mainly characterized by an atmospheric source as highlighted by the contents of N2, O2, Ar and their relative ratios. Nevertheless, significant concentrations (up to 63% by vol.) of isotopically negative CO2 (<−17.7‰ V-PDB) were found in some water samples, likely related to a biogenic source. The geochemical and isotopic data of the surface and spring waters in the surroundings of Hontomín can be considered as background values when intra- and post-injection monitoring programs will be carried out. In this respect, main and minor solutes, the isotopic carbon of dissolved CO2 and TDIC (Total Dissolved Inorganic Carbon) and selected trace elements can be considered as useful parameters to trace the migration of the injected CO2 into near-surface environments.

Cu-NirK from Haloferax mediterranei as an example of metalloprotein maturation and exportation via Tat system

The green Cu-NirK from Haloferax mediterranei (Cu-NirK) has been expressed, refolded and retrieved as a trimeric enzyme using an expression method developed for halophilic Archaea. This method utilizes Haloferax volcanii as a halophilic host and an expression vector with a constitutive and strong promoter. The enzymatic activity of recombinant Cu-NirK was detected in both cellular fractions (cytoplasmic fraction and membranes) and in the culture media. The characterization of the enzyme isolated from the cytoplasmic fraction as well as the culture media revealed important differences in the primary structure of both forms indicating that Hfx. mediterranei could carry out a maturation and exportation process within the cell before the protein is exported to the S-layer. Several conserved signals found in Cu-NirK from Hfx. mediterranei sequence indicate that these processes are closely related to the Tat system. Furthermore, the N-terminal sequence of the two Cu-NirK subunits constituting different isoforms revealed that translation of this protein could begin at two different points, identifying two possible start codons. The hypothesis proposed in this work for halophilic Cu-NirK processing and exportation via the Tat system represents the first approximation of this mechanism in the Halobacteriaceae family and in Prokarya in general.

Exploring Multi-Component Superconducting Compounds by a High-Pressure Method and Ceramic Combinatorial Chemistry

In this short review, we provide some new insights into the material synthesis and characterization of modern multi-component superconducting oxides. Two different approaches such as the high-pressure, high-temperature method and ceramic combinatorial chemistry will be reported with application to several typical examples. First, we highlight the key role of the extreme conditions in the growth of Fe-based superconductors, where a careful control of the composition-structure relation is vital for understanding the microscopic physics. The availability of high-quality LnFeAsO (Ln = lanthanide) single crystals with substitution of O by F, Sm by Th, Fe by Co, and As by P allowed us to measure intrinsic and anisotropic superconducting properties such as Hc2, Jc. Furthermore, we demonstrate that combinatorial ceramic chemistry is an efficient way to search for new superconducting compounds. A single-sample synthesis concept based on multi-element ceramic mixtures can produce a variety of local products. Such a system needs local probe analyses and separation techniques to identify compounds of interest. We present the results obtained from random mixtures of Ca, Sr, Ba, La, Zr, Pb, Tl, Y, Bi, and Cu oxides reacted at different conditions. By adding Zr but removing Tl, Y, and Bi, the bulk state superconductivity got enhanced up to about 122 K.

Geochemistry of basalts at DSDP Site 89-462

At Site 462 in the Nauru Basin, western Pacific Ocean, 56 lithologic units have been recovered from an extensive flood basalt province. Fossil evidence suggests that the lavas were emplaced during the interval 100-115 Ma, some 30 m.y. after formation of the underlying Jurassic ocean crust. The lithologic units can be broadly divided into three chemical units, the lowermost two of which are chemically monotonous, suggesting rapid eruption of basalt from a compositionally homogeneous magma chamber. All the basalts are hypersthene- (hy-) rich tholeiites, with approximately chondritic La/Sm, La/Yb, Zr/Nb, La/Ta, and Th/Hf ratios. Chemically they resemble, in part, "transitional" mid-ocean ridge basalts (MORB) from areas such as the Reykjanes Ridge, although Rb, Ba, and K contents are very low and similar to those of "normal" MORB. Their 87Sr/86Sr ratios are higher than in N-type MORB (Fujii et al., 1981). The chemistry of the Nauru basalts differs from that of continental flood basalts, which tend to be strongly enriched in large-ion lithophile (LIL) elements, although the extent to which the differences result from sialic contamination or source variability is not clear.

Estudo de um compósito Nb-15%pCu obtidos por moagem de alta energia e sinterizados por fase líquida

There is great difficulty in forming a composite refractory metal niobium with copper. This is due to the fact that Nb-Cu system is almost mutually immiscible and may be neglected solubility between them. These properties hinder or prevent obtaining homogeneous and high-density structures, conventionally prepared. This study aims to analyze the use of high-energy milling process (MAE) to implement these natural difficulties, with regard to the densification of the sintered bodies. The MAE and the press were used in the preparation of powders, to obtain a fine and homogeneous distribution of the grain size. Four loads Nb and Cu powders containing 15% by weight of Cu were then milled for MAE in a planetary type ball mill under various milling times and speeds. The results obtained by MAE were analyzed by scanning electron microscopy (SEM), according to the parameters of time and grinding speed. The samples were compacted under pressure of 200 MPa, were then sintered in liquid phase in a vacuum furnace at temperatures of 1100 ° C / 60 min and 1200 ° C / 60 min. Then it was used to characterize diffraction of X-rays to identify the phases. The microstructures of the sintered samples were observed and evaluated using scanning electron microscopy (SEM). Vickers Microhardness tests were performed, obtaining higher values for the sintered bodies in the largest of the post milling times and the larger grinding speeds. It was found that the liquid phase sintering of the samples that were processed by MAE produced at the end of a homogeneous and densified structure in 77,4% relative to the value of the theoretical density of the composite

Geochemistry of basement basaltic rocks of ODP Hole 131-808C

Major- and trace-element analyses, mineral chemistry, and Sr-Nd isotopic determinations were obtained on representative igneous rocks drilled from the Nankai accretionary complex (Site 808) during Ocean Drilling Program Leg 131. For the first time, the oceanic basement of the subducting plate below an accretionary prism has been reached. The Nankai Trough basement was encountered at a depth of 1289.9 mbsf and a total of 37.1 m of igneous rocks, middle Miocene (15.6 Ma) in age, was penetrated. Two main lithological units have been distinguished from the top downward; sill-like rocks (Unit I: Cores 105, 106, 107) and pillow lavas (Unit II: Core 108). Basalts are predominantly nonvesicular, hypocrystalline, aphyric to slightly phyric with intersertal to intergranular textures. Alteration is generally slight to moderate. All the basaltic rocks are cut by ramifying veins of varying widths. Secondary mineral assemblages (including vein fillings) are typical of submarine alteration and zeolite to low greenschist facies metamorphism. The order of crystallization of primary minerals is: olivine, plagioclase, clinopyroxene. This, together with mineral chemistry, characterized by forsteritic olivine (Fo 84-85), highly anorthitic Plagioclase (up to An 90), and in particular the composition of clinopyroxene, are typical of normal mid-ocean ridge basalts (MORB). In terms of Zr/Y (2.9-3.8) and Zr/Nb (21-58), all the analyzed samples plot in the normal MORB field. The chondrite-normalized REE patterns confirm the close affinity with normal MORB type (LaN/SmN: 0.6-0.8). Note that such magmatism does not reveal any evidence of subduction-related geochemical components. The 87Sr/86Sr isotopic ratios range from 0.70339 in pillow lavas to 0.70317 in the least-altered basalts of sill units (ratios reduced to 0.70265-0.70271 by HC1 2.5 N hot leaching), whereas 143Nd/144Nd ratios are 0.51314-0.51326. These values conform with those of normal MORB. Stratigraphy, petrography, and geochemistry of the basaltic rocks recovered at Site 808 appear very similar to those from the Shikoku Basin basement (particularly Sites 442 and 443, DSDP Leg 58), analogously identified as normal MORB.

Structure and superconducting properties of Tl1?yPbyY1?xCaxSr2Cu2O7star, open: Dependence of Tc on hole concentration

Structure and superconducting properties of Tl1?yPbyY1?xCaxSr2Cu2O7 (y=0.0, 0.1, 0.25 and 0.5) , derived from the parent insulator TlYSr2Cu2O7, have been investigated for different values of x. XANES studies show Pb to be in the 4+ state while Tl is in the 3+ state, suggesting thereby that in this series, (x?y) approximately corresponds to the hole concentration. The in-plane Cu---O distance decreases with increase in x for all values of y. The apical Cu---O distance as well as the Tl(Pb)---O(2) distance show anomalies at x=0.5 in the series with y=0.25; at this composition, Tc also reaches a maximum. In general, the composition (value of x) at which the Tc of Tl1?yPbyY1?xCaxSr2Cu2O7 reaches a maximum depends on the Pb content and the maximum Tc itself increases with increase in y, reaching a value of 105 K at y=0.5. More interestingly, a maximum Tc occurs at an (x?y) value of not, vert, similar0.25, which is close to the hole concentration at maximum Tc in other cuprate superconductors containing two CuO2 layers.

Evaluación de hongos entomopatogenos sobre plagas claves en el cultivo del arroz (Julio a octubre del 2000)

Con el objetivo de evaluar el efecto de tres cepas de hongos entomopatógenos formuladas en polvo y aceite, sobre las poblaciones del chinche de la espiga del arroz Oebalus insularis (Stal), la novia del arroz Rupela albinella (Cramer) y el saltamonte Conocephalus sp se realizó un experimento en condiciones de campo y laboratorio durante Agosto a Diciembre del 2000. A nivel de laboratorio se evaluaron las cepas 38, 64, 114 y 121 de Beauveria bassiana (Bals), sobre la mortalidad del chinche, las cepas evaluadas a nivel de campo fueron 114 y 121 también de Beauveria bassiana(Bals) y la cepa Niña bonita de Metarhizium anisopliae (Metch); se evaluó además la mezcla de las cepas Ma-NB más Bb-121, comparadas con una parcela sin aplicación de hongos y uso de Metamidofos. Se utilizó el umbral de 0.6 chinches en 10 redadas para realizar las aplicaciones, los muestreos se realizaron cada se mana, iniciando antes de la floración hasta finalizar el período de protección de espiga. Se seleccionaron cinco sitios al azar en cada tratamiento y se registró el número de plagas capturadas. Se inició con una aplicación preventiva del hongo, cuando se observó entre el 5 y 10% de floración, posteriormente fueron aplicados cuando se alcanzó el umbral de daño. Los resultados obtenidos indican que los tratamientos tuvieron un comportamiento similar, se encontró diferencias significativas entre las poblaciones de plagas en las fechas de muestreo (P:0.0001); sin embargo, se pudo observar que las cepas Ma-N B y Bb-114 formuladas en polvo iniciaron con la mayor población y al final del ciclo la incidencia de la plagas en dichas parcelas fue un poco menor que en las demás. En cambio los tratamientos Ma-NB + Bb-121 y Bb-114 formuladas en aceite presentaron poblaciones de la plaga ligeramente mayores que los demás tratamientos. Las cepas Bb-114 y Ma-NB, así como la mezcla de ambas, formuladas en polvo, en concentraciones de 10 12 conidias/ml son promisorias para el manejo de las plagas objeto de estudio. A nivel de laboratorio las cepas que se comportaron mejor fueron la 64 y 114 de Beauveria bassiana.

利用多重示踪技术研究正常鼠和肿瘤鼠的微量元素代谢(英文)

利用25 MeV/u40Ar +Se中能重离子核反应,制备包含24种元素在内的多重示踪剂,通过对元素γ谱的分析,研究了正常鼠和肿瘤鼠体内微量元素的分布及代谢。Mg,Sr, Ga, As,Sc, V, Cr, Mo, Co,Fe, Y,Zr, Nb和Ru等元素在肿瘤鼠的粪便和尿液中的排泄时间与正常鼠不同。肿瘤鼠与正常鼠相比,Na, Mn,Fe和Co的排泄变化较大,肿瘤鼠的排泄率较正常鼠高;而Ca, Y,Zr和Mo的排泄率肿瘤鼠则较正常鼠低;在正常鼠脏器、组织和血液样品中测出了Na,Rb,Ga,Sc, As,Zn, V,Cr, Mn,Co,Fe、Y,Zr, Tc, Ru, Ag和In等17种元素,肿瘤鼠检测出了除Zn和As之外的其它15种元素。几乎所有的元素在正常鼠中的吸收均比肿瘤鼠高。大部分元素分布在肝、肾和毛皮以及实体瘤中,而Fe和Na在肿瘤组织则没有检测到。

YBa_2Cu_3O_7的化学键性质和穆斯堡尔谱的研究

利用电介质的平均能带模型计算了YBa2 Cu3O7的化学键参数 ,得到Cu(1)—O键的平均共价性为 0 40 6,Cu(2 )—O键的平均共价性为0 2 76。应用化学环境因子计算了Fe :Y 12 3的穆斯堡尔同质异能位移 ,确定了5 7Fe在Y 12 3中的价态和占位情况。由电声子强度参数与共价性的关系说明了超导相中Cu(2 )离子的重要性

冲绳海槽西南端中全新世以来的沉积特征及其物源与环境意义

作为大陆向大洋的过渡带，由于享有得天独厚的沉积环境，具有独特的构造特征以及与黑潮主流之间的密切关系，一直以来，冲绳海槽都是中外学者研究的重点靶区。2005年5月，由我国与法国联合主持的IMAGES 航次在台湾东北海域获取MD05-2908柱状岩芯（24º48.04′N,122 º29.35′E,水深为1275米），该柱状岩芯为一34.17米长高质量的连续沉积记录，岩性以深灰色粘土质粉砂为主，含水量较高，粘性、可塑性强，含有数层厚度不等的夹层。岩芯年龄模式依据17个AMS 14C定年数据建立，岩芯底部年代约6.8ka，为中全新世以来的沉积。在实验室对样品按照2cm的间隔进行分割后分别进行了粒度分析、粘土矿物提取与测试、碎屑矿物提取与鉴定、常微量元素和稀土元素分析等实验。 粒度分析结果显示，MD05-2908岩芯沉积物粒度垂向上总体比较均一，以细颗粒的粘土与粉砂质为主，但不同层位也稍有差别，表现为底部层位粒度较粗，含砂量较高，说明底部沉积环境比较复杂。粘土粒级（<2µm）矿物主要由四种粘土矿物和少量石英、长石碎屑组成。其中，粘土矿物相对含量变化中，伊利石（～68％）与绿泥石（～17%）构成主要成分，含有蒙皂石（～10％）和高岭石（～5％）。结合台湾东北外海表层沉积物的研究，利用粘土矿物伊利石/蒙皂石和绿泥石/高岭石比值得出岩芯粘土矿物主要为陆源碎屑粘土矿物，其源岩主要为台湾中央山脉的变质岩与台湾东部的沉积岩。重矿物分析共选取了41个层位，对63~250μm粒级的样品在实体镜和偏光显微镜下进行鉴定，结果显示，岩芯重矿物主要由绿泥石（29%）、普通角闪石（22%）、白云石（10%）、黑云母（8%）、绿帘石（7%）、白云母（7%）、褐铁矿（5%）等组成。稳定矿物少，矿物成熟度低。碎屑矿物风化程度低，磨蚀不明显，分选较差，表明沉积物来自于近源，后期改造作用不明显。常量元素分析结果表明，SiO2 、Al2O3和Fe2O3是岩芯沉积物中的最主要组分，这三种组分占沉积物总量的82%左右。 整个岩芯自下而上各常量组分变化不大，其平均值与东海陆架沉积物基本接近。微量元素变化比较明显， Ba、Cr、Cu、Zn元素的含量比东海陆架沉积物中的含量要高，而Sr的含量明显低于东海陆架。对常微量元素的R型因子分析表明，常量元素SiO2、Al2O3、Fe2O3、MgO和K2O，微量元素Cr、Cu、Ni、Zn、Pb、Rb和Mn可代表陆源物质；常量元素CaO和微量元素Sr、Ba可代表生物源物质。岩芯沉积物以陆源物质为主，生源物质的贡献起次要作用。岩芯沉积物中稀土元素总量平均为169.87×10-6，并且轻稀土含量均高于重稀土，LREE/HREE平均值为10.14，表明了轻稀土对稀土总量的贡献远高于重稀土，沉积物富集轻稀土，反映了沉积物的陆源特征。 岩芯MD05-2908中全新世以来平均5m/ka的高沉积速率主要源于丰富的物质供应和适宜的沉积环境。岩芯细粒级沉积物中，地球化学特征表明沉积物主要来源于陆源碎屑物质，粘土矿物特征与台湾东部陆源物质相同；粗粒级沉积物中，重矿物含量及矿物特征也表明岩芯沉积物粗颗粒组分主要来自于近源沉积。台湾宜兰境内的兰阳溪每年携带约一千万吨冲积物入海成为研究区重要的物质来源。由于受到黑潮的强烈影响，逆时针涡流及底层反向流的存在是岩芯高沉积速率重要控制因素。因此，利用动力分选的粉砂组分可以用来示踪古洋流强度，结果显示，6.8ka以来黑潮的强弱波动频繁，并表现出一定的旋回性变化，频谱分析表明，其具有的千年尺度周期（1500a）、百年尺度周期（604a、242a、192a、153a、133a）与十年尺度周期（22a）的周期性变化均与太阳辐射量变化有密切关系，因此，黑潮的强弱变化在大背景上是由太阳活动所控制的。 根据测年资料可以识别出岩芯存在5期快速堆积事件，这与区域性降水增加有关，降雨量增加导致陆源物质输入的增加。另外，岩芯位于大陆斜坡区，附近存在有三支海底峡谷，并且地震活动频繁，沉积在宜兰陆架及东海陆架处的浅海沉积物由于受到地震、风暴等活动的影响而受扰动崩塌、因重力作用而向低处输送，产生二次侵蚀并经由海底峡谷搬运到冲绳海槽南段堆积,使得沉积环境更为复杂，但同时也为冲绳海槽提供了丰富的物质供应。

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。

姚安和马厂箐富碱侵入岩体的地球化学特征

姚安岩体和马厂箐岩体属哀牢山-金沙江富碱侵入岩带的组成部分,位于NW-WNW向哀牢山-金沙江深大断裂东侧。姚安岩体主要为正长斑岩,马厂箐岩体主要为花岗斑岩两岩体化学成分上具有富碱、高钾的特点。岩石富轻稀土和Rb、Sr、Ba、Th、La等大离子亲石元素而亏损Nb、Ta和Ti等高场强元素。岩石的Rb/Sr、La/Nb和Ba/Nb以及LREE/HREE比值高,铕异常不明显,ISr值偏高,εNd值偏低。研究表明:(1)姚安岩体和马厂箐岩体形成于喜山期大陆弧伸展环境。两岩体的岩浆均起源于富集地幔(EMII),其壳幔混合特征,主要是俯冲带地幔楔内壳-幔物质源区混合的结果;(2)尽管姚安和马厂箐岩体在成岩构造背景、成岩时代、成岩方式和源区特征以及成分上高碱富钾等方面具相似性,但它们在岩性和组成上仍存在较大差异。这种差异可能是由源区物质部分熔融程度不同,以及岩浆结晶时温压和氧逸度等条件的不同所造成;(3)金矿化主要与相对高温、低压和高氧逸度的碱性系列岩浆活动有关,而铜矿化则主要与相对低温、高压和低氧逸度的碱性-亚碱性过度系列岩浆活动有关。

胶东北部碱性超基性脉岩地球化学特征及环境和成因探讨

胶东地区脉岩属碱性超基性岩系(Na2O+K2O=4．67％～5．43％；SiO2=36．70％-39．99％)，岩性为单一的橄榄辉石岩。从主量元素(包括CIPW标准矿物组成)和过渡元素组成来看，该岩系近似原始岩浆组成。电子探针结果显示：橄榄石为富镁质橄榄石(贵橄榄石)(Fo=71—90)，单斜辉石为透辉石(次透辉石为主)。岩石富集大离子亲石元素(K、Rb、Sr、Th和Ba)，但不具有高场强元素(Nb、Ta、Zr和Hf)的亏损，表明岩石形成于大陆板内环境。为地幔橄榄岩低度部分熔融(3．4％)的产物。同时，它具有大陆边缘弧的特性。暗示其为一种滞后型弧岩浆作用的产物。稀土元素特征显示，岩石强烈富集LREE，而相对亏损HREE，暗示了源区的富集特性。Eu／Eu^+=0．89—1．00，总体不表现明显的负Eu异常，暗示斜长石不是主要的分馏矿物相。结合板内碱性岩石的矿物结晶顺序认为，本区岩浆分馏以较弱的橄榄石分馏为主。