Chemical composition of altered volcanic rocks from ODP Sites 193-1188 and 193-1189

The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350°C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250°C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.

Pedology, geochronology, palynology and macrofossils of soil profiles in the Altdarss area, german Baltic Sea coast

A new site with Lateglacial palaeosols covered by 0.8 - 2.4 m thick aeolian sands is presented. The buried soils were subjected to multidisciplinary analyses (pedology, micromorphology, geochronology, dendrology, palynology, macrofossils). The buried soil cover comprises a catena from relatively dry ('Nano'-Podzol, Arenosol) via moist (Histic Gleysol, Gleysol) to wet conditions (Histosol). Dry soils are similar to the so-called Usselo soil, as described from sites in NW Europe and central Poland. The buried soil surface covers ca. 3.4 km**2. Pollen analyses date this surface into the late Aller0d. Due to a possible contamination by younger carbon, radiocarbon dates are too young. OSL dates indicate that the covering by aeolian sands most probably occurred during the Younger Dryas. Botanical analyses enables the reconstruction of a vegetation pattern typical for the late Allerod. Large wooden remains of pine and birch were recorded.

Mineralogy and geochemistry of latest Miocene deposits in the Tyrrhenian Sea

Late Miocene sediments from ODP Sites 652 and 654, drilled on the Sardinian margin in the Western Tyrrhenian Sea, are investigated through mineralogical, micromorphological, geochemical, and microgeochemical analyses. Clay associations appear to be little controlled by conditions of deposition, and largely depend on pre- and post-depositional conditions. The sedimentary series from Central Mediterranean gives very different geodynamic information, according to the sector considered. While relatively stable conditions, like those encountered in Caltanissetta Basin, Sicily, favor the mineralogical expression of warm-temperate and subarid Messinian climate, the Eastern Sardinia margin (Site 654) clay suites mainly reflect the transition from tectonically active to relaxed conditions. The series deposited at the foot of the same margin above a thinner crust (Site 652) experienced the effects of burial diagenesis, enhanced by strong geothermal gradient.

Chemical and boron isotopic compositions of volcanics from ODP Sites 135-834 to 135-840

The influence of fluid flux on petrogenesis in the Tonga-Kermadec Arc was investigated using ion microprobe measurements of B/Be and boron isotope ratios (11B/10B) to document the source and relative volumes of the fluids released from the subducting oceanic plate. We analyzed young lavas from eight different islands along the Tonga-Kermadec Arc, as well as glass shards in volcanic sediments from Ocean Drilling Program (ODP) Site 840, which record the variations in the chemistry of Tonga magmatism since 7 Ma. B/Be is variable (5.8-122), in young Tonga-Kermadec Arc lavas. In contrast, glass shards from around 3 to 4 Ma old volcanic sediments at Site 840 have the highest B/Be values yet reported for arc lavas (18-607). These values are too high to be related simply to a sediment influence on petrogenesis. Together with very high d11B values (-11.6 to +37.5) for the same shards and lavas these data indicate that most of the B is derived from fluid escaped from the subducting altered Pacific oceanic crust, rather than from sediment. High d11B values also reflect large degrees of isotopic fractionation in this cold fast subduction zone. Lower d11B values noted in the Kermadec Arc (17 to -4.4) are related to the influence of sediment eroded from New Zealand and slower convergence. High fluid flux (B/Be) is synchronous in Tonga and the Marianas at 3 to 4 Ma and may be related to acceleration of the Pacific Plate just prior to this time. The timing of maximum B/Be at 3 to 4 Ma correlates with maximum light rare earth (LREE) and high field strength element depletion. This suggests maximum degrees of partial melting at this time. Although thinning of the arc lithosphere during rifting to form the Lau Basin is expected to influence the arc geochemistry, variable aqueous fluid flux from the subducting plate alone appears capable of explaining boron and other trace element systematics in the Tonga-Kermadec Arc with no indication of slab melting.

Tephrostratigraphy and radiometric dating of authigenic carbonates

At convergent margins, fluids rise through the forearc in response to consolidation of the upper plate and dewatering of the subducting plate, and produce various cold-seep-related features on the seafloor (mud diapirs, mud mounds). At the Central American forearc, authigenic carbonates precipitated from rising fluids within such structures during active venting while typical mixed-mud sediments were ejected onto the surrounding seafloor where they became intercalated with normal pelagic background sediments, indicating that mud mounds evolved unsteadily through alternating active and inactive phases. Intercalated regional ash layers from Plinian eruptions at the Central American volcanic arc provide time marks that constrain the ages of mud ejection activity. U/Th dating of drill core samples of authigenic carbonate caps of mud mounds yields ages agreeing well with those constrained by ash layers and showing that carbonate caps grow inward rather than outward during active venting. Both dating approaches show that offshore Nicaragua and Costa Rica (1) active and inactive phases can occur simultaneously at neighboring mounds, (2) mounds along the forearc have individual histories of activity, but there are distinct time intervals when nearly all mounds have been active or inactive, (3) lifetimes of mounds reach several hundred thousand years, and (4) highly active periods last 10-50 k.y. with intervening periods of >10 k.y. of relative quiescence.

South Pacific dissolved Nd isotope compositions, rare earth element and nutrient concentrations from SONNE cruise SO213

Despite its enormous extent and importance for global climate, the South Pacific has been poorly investigated in comparison to other regions with respect to chemical oceanography. Here we present the first detailed analysis of dissolved radiogenic Nd isotopes (epsilon-Nd) and rare earth elements (REEs) in intermediate and deep waters of the mid-latitude (~40°S) South Pacific along a meridional transect between South America and New Zealand. The goal of our study is to gain better insight into the distribution and mixing of water masses in the South Pacific and to evaluate the validity of Nd isotopes as a water mass tracer in this remote region of the ocean. The results demonstrate that biogeochemical cycling (scavenging processes in the Eastern Equatorial Pacific) and release of LREEs from the sediment clearly influence the distribution of the dissolved REE concentrations at certain locations. Nevertheless, the Nd isotope signatures clearly trace water masses including AAIW (Antarctic Intermediate Water) (average epsilon-Nd = -8.2 ± 0.3), LCDW (Lower Circumpolar Deep Water) (average epsilon-Nd = -8.3 ± 0.3), NPDW (North Pacific Deep Water) (average epsilon-Nd = -5.9 ± 0.3), and the remnants of NADW (North Atlantic Deep Water) (average epsilon-Nd = -9.7 ± 0.3). Filtered water samples taken from the sediment-water interface under the deep western boundary current off New Zealand suggest that boundary exchange processes are limited at this location and highlight the spatial and temporal variability of this process. These data will serve as a basis for the paleoceanographic application of Nd isotopes in the South Pacific.

137Cs in waters and bottom sediments of the Sea of Japan in 2002 and 1994

During an expedition aboard R/V Pavel Gordienko (September, 2002) investigations in the Sea of Japan areas, where radioactive wastes were disposed by the former Soviet Union, were carried out in order to assess present level of radioactive contamination of marine environment. Concentration of I37Cs, radioecologically one of the most important radionuclides, in near-bottom sea water and bottom sediments were measured to be low, 2.8-17.2 Bq/m**3 and 3.2-27.2 Bq/kg dry weight, respectively, that did not differ significantly from levels elsewhere in the northwest Pacific Ocean arising from global fallout. Results of measurements were compared with results of the Joint Japanese- Korean -Russian expedition to the Sea of Japan in 1994.

Analysis of elements at DSDP Holes 70-506 and 70-509B

Sediments in the area of the Galapagos hydrothermal mounds are divided into two major categories. The first group, pelagic sediments, are nannofossil oozes with varying amounts of siliceous microfossils. The second group are hydrothermal sediments consisting of manganese-oxide crust fragments and green nontronitic clay granules. Hydrothermal sediments occur only in the upper half to two-thirds of the cores and are interbedded and mixed with pelagic sediments. Petrologic evidence indicates that hydrothermal nontronite forms as both a primary precipitate and as a replacement mineral of pre-existing pelagic sediment and hydrothermal manganese-oxide crust fragments. In addition, physical evidence supports chemical equations indicating that the pelagic sediments are being dissolved by hydrothermal solutions. The formation of hydrothermal nontronite is not merely confined to the surface of mounds, but also occurs at depth within their immediate area; hydrothermal nontronite is very likely forming today. Geologically speaking, the mounds and their hydrothermal sediments form almost instantaneously. The Galapagos mounds area is a unique one in the ocean basins, where pelagic sediments can be diagenetically transformed, dissolved, and replaced, possibly within a matter of years.

Age determination and Argon geochemistry of Hawaiian Emperor seamounts

The Hawaiian-Emperor bend has played a prominent yet controversial role in deciphering past Pacific plate motions and the tempo of plate motion change. New ages for volcanoes of the central and southern Emperor chain define large changes in volcanic migration rate with little associated change in the chain's trend, which suggests that the bend did not form by slowing of the Hawaiian hot spot. Initiation of the bend near Kimmei seamount about 50 million years ago (MA) was coincident with realignment of Pacific spreading centers and early magmatism in western Pacific arcs, consistent with formation of the bend by changed Pacific plate motion.

A new set of relativistic screening constants for the screened hydrogenic model

AnewRelativisticScreenedHydrogenicModel has been developed to calculate atomic data needed to compute the optical and thermodynamic properties of high energy density plasmas. The model is based on anewset of universal screeningconstants, including nlj-splitting that has been obtained by fitting to a large database of ionization potentials and excitation energies. This database was built with energies compiled from the National Institute of Standards and Technology (NIST) database of experimental atomic energy levels, and energies calculated with the Flexible Atomic Code (FAC). The screeningconstants have been computed up to the 5p3/2 subshell using a Genetic Algorithm technique with an objective function designed to minimize both the relative error and the maximum error. To select the best set of screeningconstants some additional physical criteria has been applied, which are based on the reproduction of the filling order of the shells and on obtaining the best ground state configuration. A statistical error analysis has been performed to test the model, which indicated that approximately 88% of the data lie within a ±10% error interval. We validate the model by comparing the results with ionization energies, transition energies, and wave functions computed using sophisticated self-consistent codes and experimental data.

Energy/power consumption model for an embedded processor board

This dissertation, whose research has been conducted at the Group of Electronic and Microelectronic Design (GDEM) within the framework of the project Power Consumption Control in Multimedia Terminals (PCCMUTE), focuses on the development of an energy estimation model for the battery-powered embedded processor board. The main objectives and contributions of the work are summarized as follows: A model is proposed to obtain the accurate energy estimation results based on the linear correlation between the performance monitoring counters (PMCs) and energy consumption. the uniqueness of the appropriate PMCs for each different system, the modeling methodology is improved to obtain stable accuracies with slight variations among multiple scenarios and to be repeatable in other systems. It includes two steps: the former, the PMC-filter, to identify the most proper set among the available PMCs of a system and the latter, the k-fold cross validation method, to avoid the bias during the model training stage. The methodology is implemented on a commercial embedded board running the 2.6.34 Linux kernel and the PAPI, a cross-platform interface to configure and access PMCs. The results show that the methodology is able to keep a good stability in different scenarios and provide robust estimation results with the average relative error being less than 5%. Este trabajo fin de máster, cuya investigación se ha desarrollado en el Grupo de Diseño Electrónico y Microelectrónico (GDEM) en el marco del proyecto PccMuTe, se centra en el desarrollo de un modelo de estimación de energía para un sistema empotrado alimentado por batería. Los objetivos principales y las contribuciones de esta tesis se resumen como sigue: Se propone un modelo para obtener estimaciones precisas del consumo de energía de un sistema empotrado. El modelo se basa en la correlación lineal entre los valores de los contadores de prestaciones y el consumo de energía. Considerando la particularidad de los contadores de prestaciones en cada sistema, la metodología de modelado se ha mejorado para obtener precisiones estables, con ligeras variaciones entre escenarios múltiples y para replicar los resultados en diferentes sistemas. La metodología incluye dos etapas: la primera, filtrado-PMC, que consiste en identificar el conjunto más apropiado de contadores de prestaciones de entre los disponibles en un sistema y la segunda, el método de validación cruzada de K iteraciones, cuyo fin es evitar los sesgos durante la fase de entrenamiento. La metodología se implementa en un sistema empotrado que ejecuta el kernel 2.6.34 de Linux y PAPI, un interfaz multiplataforma para configurar y acceder a los contadores. Los resultados muestran que esta metodología consigue una buena estabilidad en diferentes escenarios y proporciona unos resultados robustos de estimación con un error medio relativo inferior al 5%.

Tree height integrated into pantropical forest biomass estimates

Aboveground tropical tree biomass and carbon storage estimates commonly ignore tree height (H). We estimate the effect of incorporating H on tropics-wide forest biomass estimates in 327 plots across four continents using 42 656 H and diameter measurements and harvested trees from 20 sites to answer the following questions: 1. What is the best H-model form and geographic unit to include in biomass models to minimise site-level uncertainty in estimates of destructive biomass? 2. To what extent does including H estimates derived in (1) reduce uncertainty in biomass estimates across all 327 plots? 3. What effect does accounting for H have on plot- and continental-scale forest biomass estimates? The mean relative error in biomass estimates of destructively harvested trees when including H (mean 0.06), was half that when excluding H (mean 0.13). Power- andWeibull-H models provided the greatest reduction in uncertainty, with regional Weibull-H models preferred because they reduce uncertainty in smaller-diameter classes (?40 cm D) that store about one-third of biomass per hectare in most forests. Propagating the relationships from destructively harvested tree biomass to each of the 327 plots from across the tropics shows that including H reduces errors from 41.8Mgha?1 (range 6.6 to 112.4) to 8.0Mgha?1 (?2.5 to 23.0). For all plots, aboveground live biomass was ?52.2 Mgha?1 (?82.0 to ?20.3 bootstrapped 95%CI), or 13%, lower when including H estimates, with the greatest relative reductions in estimated biomass in forests of the Brazilian Shield, east Africa, and Australia, and relatively little change in the Guiana Shield, central Africa and southeast Asia. Appreciably different stand structure was observed among regions across the tropical continents, with some storing significantly more biomass in small diameter stems, which affects selection of the best height models to reduce uncertainty and biomass reductions due to H. After accounting for variation in H, total biomass per hectare is greatest in Australia, the Guiana Shield, Asia, central and east Africa, and lowest in eastcentral Amazonia, W. Africa, W. Amazonia, and the Brazilian Shield (descending order). Thus, if tropical forests span 1668 million km2 and store 285 Pg C (estimate including H), then applying our regional relationships implies that carbon storage is overestimated by 35 PgC (31?39 bootstrapped 95%CI) if H is ignored, assuming that the sampled plots are an unbiased statistical representation of all tropical forest in terms of biomass and height factors. Our results show that tree H is an important allometric factor that needs to be included in future forest biomass estimates to reduce error in estimates of tropical carbon stocks and emissions due to deforestation.

Estimate of the total ice volume of Svalbard glaciers and their potential contribution to sea-level rise = Estimación del volumen de hielo de Svalbard y su contribución potencial a la subida del nivel del mar

El objetivo final de las investigaciones recogidas en esta tesis doctoral es la estimación del volumen de hielo total de los ms de 1600 glaciares de Svalbard, en el Ártico, y, con ello, su contribución potencial a la subida del nivel medio del mar en un escenario de calentamiento global. Los cálculos más exactos del volumen de un glaciar se efectúan a partir de medidas del espesor de hielo obtenidas con georradar. Sin embargo, estas medidas no son viables para conjuntos grandes de glaciares, debido al coste, dificultades logísticas y tiempo requerido por ellas, especialmente en las regiones polares o de montaña. Frente a ello, la determinación de áreas de glaciares a partir de imágenes de satélite sí es viable a escalas global y regional, por lo que las relaciones de escala volumen-área constituyen el mecanismo más adecuado para las estimaciones de volúmenes globales y regionales, como las realizadas para Svalbard en esta tesis. Como parte del trabajo de tesis, hemos elaborado un inventario de los glaciares de Svalbard en los que se han efectuado radioecosondeos, y hemos realizado los cálculos del volumen de hielo de más de 80 cuencas glaciares de Svalbard a partir de datos de georradar. Estos volúmenes han sido utilizados para calibrar las relaciones volumen-área desarrolladas en la tesis. Los datos de georradar han sido obtenidos en diversas campañas llevadas a cabo por grupos de investigación internacionales, gran parte de ellas lideradas por el Grupo de Simulación Numérica en Ciencias e Ingeniería de la Universidad Politécnica de Madrid, del que forman parte la doctoranda y los directores de tesis. Además, se ha desarrollado una metodología para la estimación del error en el cálculo de volumen, que aporta una novedosa técnica de cálculo del error de interpolación para conjuntos de datos del tipo de los obtenidos con perfiles de georradar, que presentan distribuciones espaciales con unos patrones muy característicos pero con una densidad de datos muy irregular. Hemos obtenido en este trabajo de tesis relaciones de escala específicas para los glaciares de Svalbard, explorando la sensibilidad de los parámetros a diferentes morfologías glaciares, e incorporando nuevas variables. En particular, hemos efectuado experimentos orientados a verificar si las relaciones de escala obtenidas caracterizando los glaciares individuales por su tamaño, pendiente o forma implican diferencias significativas en el volumen total estimado para los glaciares de Svalbard, y si esta partición implica algún patrón significativo en los parámetros de las relaciones de escala. Nuestros resultados indican que, para un valor constante del factor multiplicativo de la relacin de escala, el exponente que afecta al área en la relación volumen-área decrece según aumentan la pendiente y el factor de forma, mientras que las clasificaciones basadas en tamaño no muestran un patrón significativo. Esto significa que los glaciares con mayores pendientes y de tipo circo son menos sensibles a los cambios de área. Además, los volúmenes de la población total de los glaciares de Svalbard calculados con fraccionamiento en grupos por tamaño y pendiente son un 1-4% menores que los obtenidas usando la totalidad de glaciares sin fraccionamiento en grupos, mientras que los volúmenes calculados fraccionando por forma son un 3-5% mayores. También realizamos experimentos multivariable para obtener estimaciones óptimas del volumen total mediante una combinación de distintos predictores. Nuestros resultados muestran que un modelo potencial simple volumen-área explica el 98.6% de la varianza. Sólo el predictor longitud del glaciar proporciona significación estadística cuando se usa además del área del glaciar, aunque el coeficiente de determinación disminuye en comparación con el modelo más simple V-A. El predictor intervalo de altitud no proporciona información adicional cuando se usa además del área del glaciar. Nuestras estimaciones del volumen de la totalidad de glaciares de Svalbard usando las diferentes relaciones de escala obtenidas en esta tesis oscilan entre 6890 y 8106 km3, con errores relativos del orden de 6.6-8.1%. El valor medio de nuestras estimaciones, que puede ser considerado como nuestra mejor estimación del volumen, es de 7.504 km3. En términos de equivalente en nivel del mar (SLE), nuestras estimaciones corresponden a una subida potencial del nivel del mar de 17-20 mm SLE, promediando 19_2 mm SLE, donde el error corresponde al error en volumen antes indicado. En comparación, las estimaciones usando las relaciones V-A de otros autores son de 13-26 mm SLE, promediando 20 _ 2 mm SLE, donde el error representa la desviación estándar de las distintas estimaciones. ABSTRACT The final aim of the research involved in this doctoral thesis is the estimation of the total ice volume of the more than 1600 glaciers of Svalbard, in the Arctic region, and thus their potential contribution to sea-level rise under a global warming scenario. The most accurate calculations of glacier volumes are those based on ice-thicknesses measured by groundpenetrating radar (GPR). However, such measurements are not viable for very large sets of glaciers, due to their cost, logistic difficulties and time requirements, especially in polar or mountain regions. On the contrary, the calculation of glacier areas from satellite images is perfectly viable at global and regional scales, so the volume-area scaling relationships are the most useful tool to determine glacier volumes at global and regional scales, as done for Svalbard in this PhD thesis. As part of the PhD work, we have compiled an inventory of the radio-echo sounded glaciers in Svalbard, and we have performed the volume calculations for more than 80 glacier basins in Svalbard from GPR data. These volumes have been used to calibrate the volume-area relationships derived in this dissertation. Such GPR data have been obtained during fieldwork campaigns carried out by international teams, often lead by the Group of Numerical Simulation in Science and Engineering of the Technical University of Madrid, to which the PhD candidate and her supervisors belong. Furthermore, we have developed a methodology to estimate the error in the volume calculation, which includes a novel technique to calculate the interpolation error for data sets of the type produced by GPR profiling, which show very characteristic data distribution patterns but with very irregular data density. We have derived in this dissertation scaling relationships specific for Svalbard glaciers, exploring the sensitivity of the scaling parameters to different glacier morphologies and adding new variables. In particular, we did experiments aimed to verify whether scaling relationships obtained through characterization of individual glacier shape, slope and size imply significant differences in the estimated volume of the total population of Svalbard glaciers, and whether this partitioning implies any noticeable pattern in the scaling relationship parameters. Our results indicate that, for a fixed value of the factor in the scaling relationship, the exponent of the area in the volume-area relationship decreases as slope and shape increase, whereas size-based classifications do not reveal any clear trend. This means that steep slopes and cirque-type glaciers are less sensitive to changes in glacier area. Moreover, the volumes of the total population of Svalbard glaciers calculated according to partitioning in subgroups by size and slope are smaller (by 1-4%) than that obtained considering all glaciers without partitioning into subgroups, whereas the volumes calculated according to partitioning in subgroups by shape are 3-5% larger. We also did multivariate experiments attempting to optimally predict the volume of Svalbard glaciers from a combination of different predictors. Our results show that a simple power-type V-A model explains 98.6% of the variance. Only the predictor glacier length provides statistical significance when used in addition to the predictor glacier area, though the coefficient of determination decreases as compared with the simpler V-A model. The predictor elevation range did not provide any additional information when used in addition to glacier area. Our estimates of the volume of the entire population of Svalbard glaciers using the different scaling relationships that we have derived along this thesis range within 6890-8106 km3, with estimated relative errors in total volume of the order of 6.6-8.1% The average value of all of our estimates, which could be used as a best estimate for the volume, is 7,504 km3. In terms of sea-level equivalent (SLE), our volume estimates correspond to a potential contribution to sea-level rise within 17-20 mm SLE, averaging 19 _ 2 mm SLE, where the quoted error corresponds to our estimated relative error in volume. For comparison, the estimates using the V-A scaling relations found in the literature range within 13-26 mm SLE, averaging 20 _ 2 mm SLE, where the quoted error represents the standard deviation of the different estimates.

Influencia de la configuración geométrica de placas prefabricadas para forjados en las tensiones originadas por la transferencia del pretensado en elementos realizados con armaduras pretesas ancladas por adherencia

Las piezas pretensadas de hormigón presentan zonas muy solicitadas correspondientes a la zona de transferencia. En muchos casos se ha detectado figuración en tales zonas cuyo origen está ligado a la transferencia de la fuerza de pretensado, pudiendo llegar a causar el rechazo de la pieza. En el caso de las piezas prefabricadas con armaduras pretesas adherentes, no siempre es posible disponer armado transversal para controlar esta fisuración, ya sea por el proceso constructivo, ya sea por disponer en general de secciones transversales muy optimizadas. Recientemente se desarrolló una nueva tipología de piezas de hormigón prefabricado para forjados unidireccionales pretensadas con armadura activa pretesa y sin armadura transversal. La tipología se asimila a una sección en PI invertida, con alas de gran envergadura en comparación con el ancho de nervio, y armadura activa distribuida en las alas. Este diseño parece propenso a la aparición de fisuración en el momento de la transferencia del pretensado. Así, se han producido fallos de carácter frágil: colapso de piezas ya colocadas en obra, separándose la losa inferior de los nervios y cayendo sobre el piso. Las herramientas de análisis usuales han resultado inútiles al aplicarse a la investigación de esta patología. Para afrontar el estudio de los problemas detectados en la tipología, se ha analizado el fenómeno de las tensiones de tracción en la zona de transferencia, usualmente denominadas exfoliación y estallido, así como los métodos de análisis aplicables a elementos pretesos sin armadura transversal. En algunas ocasiones se trata del resultado de trabajos desarrollados para piezas postesadas, o para calcular cuantías de armadura transversal, adaptados a posteriori. También existen métodos desarrollados específicamente para piezas pretesas sin armadura transversal. Junto a los factores considerados en los métodos existentes se han localizado otros, no tenidos en cuenta habitualmente, pero que pueden ser determinantes en piezas no convencionales, como son: la existencia de pretensado superior e inferior, la falta de simetría de la sección transversal, el ancho variable de las piezas, una relación entre el ancho del ala y el espesor de los nervios elevada, la distribución transversal del pretensado en relación al ancho variable. Además, la mayoría de los métodos se han basado en simplificaciones bidimensionales. Para tener en cuenta la influencia de estos factores, se han modelizado piezas en las que varían tanto la geometría de la sección transversal y la cuantía de pretensado, como la ley de adherencia o la distribución de armadura activa en la sección. Estos modelos se han analizado mediante el método de elementos finitos, efectuándose u análisis elástico lineal tridimensional. En general, los métodos existentes no han predicho adecuadamente las tensiones obtenidas mediante elementos finitos. Sobre los resultados obtenidos por elementos finitos se ha desarrollado un ajuste experimental, que presentan un alto grado de correlación y de significación, así como una reducida dispersión y error relativo. En consecuencia, se propone un método de obtención de la tensión máxima de exfoliación, consistente en varias ecuaciones, que tienen en cuenta las peculiaridades de la configuración de las piezas citadas y permiten considerar cualquier ley de adherencia, manteniendo la coherencia con la longitud de transmisión. Las ecuaciones se emplean para la obtención de la tensión máxima de exfoliación en piezas de la tipología estudiada cuya armadura activa se sitúe fuera del núcleo central de la sección transversal. Respecto al estallido, se propone una modificación de los métodos existentes que, comparado con los resultados del análisis por elementos finitos, mejora el valor medio y la dispersión a valores admisibles y del lado de la seguridad. El método considera la geometría de la sección y la distribución del pretensado en la losa inferior. Finalmente, se ofrecen estrategias de diseño para piezas de la tipología o semejantes. End zones of prestressed concrete members are highly stressed. Cracking have often appeared at end zone, and its beginning is related to prestress release. Some members become rejected because of these cracks. Sometimes it is not possible having transverse reinforcement in order to control cracking, when referring to pretensioned precast members. The reason may be the construction process or highly optimized crosssections. A new typology of precast concrete members designed for one-way composite floors was recently developed. The members, without transverse reinforcement, are prestressed with pretensioned wires or strands. This typology is similar to an inverted TT slab, with a large flange related to the web thickness and prestressing reinforcement spread across the flange. This design is highly susceptible to appear cracking at prestress release. Therefore, brittle failures have been reported: fail of slabs laid in place on a construction site, resulting in the separation of the flange from the webs,, and the subsequent fall on the lower floor. Usual analytical methods have been useless to study the failure. End zone tensile stresses have been analysed to study the detected typology problems. These tensile stresses are usually called spalling and bursting (also called splitting in the U.S.). Analysis methods applicable to pretensioned members without transverse reinforcement have been analysed too. Some methods were originally developed for postensioned concrete or for obtaining the amount of transverse reinforcement. In addition, there are methods developed specifically for pretensioned members without transverse reinforcement. Some factors, frequently ignored, have been found, such as lower and upper prestress, lack of symmetry in the cross section, variable width, a high ratio between flange width and web thickness or prestressing reinforcement location related to variable width. They can play a decisive role in non-conventional members. In addition, most methods are based on 2D simplifications. Finite Element modelling has been conducted in order to consider the influence of these factors. A linear 3D approach has been used. The modelled members vary according to cross section geometry, bond behaviour, or prestressing reinforcement location. In general, the obtained tensile stresses don’t agree with existing methods. An experimental adjustment has been conducted on the obtained results, with a high correlation ratio and significance level as well as a low dispersion and relative error. Therefore, a method to obtain the maximum spalling stress is proposed. The proposal consists on some equations that consider the special features of the typology and bond behaviour. Consistency between transmission length and bond behaviour is considered too. The equations are used to calculate maximum spalling stress for the studied typology members whose prestressing reinforcement is located out of the core of the cross section. In relation to bursting, a modification of existing methods is proposed. Compared to finite element results, the proposal improves mean value and dispersion, whose ranges are considered acceptable and secure. The method takes into account cross section geometry and location of prestressing reinforcement across the lower flange. Finally, strategies to design members of this typology or similar are proposed.

Sample size determination in combinatorial chemistry.

Combinatorial chemistry is gaining wide appeal as a technique for generating molecular diversity. Among the many combinatorial protocols, the split/recombine method is quite popular and particularly efficient at generating large libraries of compounds. In this process, polymer beads are equally divided into a series of pools and each pool is treated with a unique fragment; then the beads are recombined, mixed to uniformity, and redivided equally into a new series of pools for the subsequent couplings. The deviation from the ideal equimolar distribution of the final products is assessed by a special overall relative error, which is shown to be related to the Pearson statistic. Although the split/recombine sampling scheme is quite different from those used in analysis of categorical data, the Pearson statistic is shown to still follow a chi2 distribution. This result allows us to derive the required number of beads such that, with 99% confidence, the overall relative error is controlled to be less than a pregiven tolerable limit L1. In this paper, we also discuss another criterion, which determines the required number of beads so that, with 99% confidence, all individual relative errors are controlled to be less than a pregiven tolerable limit L2 (0 < L2 < 1).