Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Total nitrogen from solid phase in the Jena Experiment (Block 2 Main Experiment up to 100cm depth, year 2007)

This data set contains measurements of total nitrogen from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Stratified soil sampling to a depth of 1m was repeated in April 2007 (as had been done before sowing in April 2002). Three independent samples per plot were taken of all plots in block 2 using a motor-driven soil column cylinder (Cobra, Eijkelkamp, 8.3 cm in diameter). Soil samples were dried at 40°C and segmented to a depth resolution of 5 cm giving 20 depth subsamples per core. All samples were analyzed independently. All soil samples were passed through a sieve with a mesh size of 2 mm. Because of much higher proportions of roots in the soil, the samples in 2007 were further sieved to 1 mm according to common root removal methods. No additional mineral particles were removed by this procedure. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Total nitrogen from solid phase in the Jena Experiment (Main Experiment up to 30cm depth, year 2006)

This data set contains measurements of total nitrogen from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Stratified soil sampling was performed in April 2006 to a depth of 30 cm. Three independent samples per plot were taken using a split tube sampler with an inner diameter of 4.8 cm (Eijkelkamp Agrisearch Equipment, Giesbeek, the Netherlands). Soil samples were segmented to a depth resolution of 5 cm in the field, giving six depth subsamples per core, and made into composite samples per depth. Sampling locations were less than 30 cm apart from sampling locations in other years. Samples were dried at 40°C. All soil samples were passed through a sieve with a mesh size of 2 mm. Because of much higher proportions of roots in the soil, the samples were further sieved to 1 mm according to common root removal methods. No additional mineral particles were removed by this procedure. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Total nitrogen from solid phase in the Jena Experiment (Main Experiment up to 30cm depth, year 2002)

This data set contains measurements of total nitrogen from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Stratified soil sampling was performed before sowing in April 2002. Five independent samples per plot were taken using a split tube sampler with an inner diameter of 4.8 cm (Eijkelkamp Agrisearch Equipment, Giesbeek, the Netherlands). Soil samples were dried at 40°C and then segmented to a depth resolution of 5 cm giving six depth subsamples per core. All samples were analyzed independently and averaged values per depth layer are reported. Sampling locations were less than 30 cm apart from sampling locations in other years. Subsequently, samples were dried at 40°C. All soil samples were passed through a sieve with a mesh size of 2 mm. Rarely present visible plant remains were removed using tweezers. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Prospects for Development of the Garment Industry in Developing Countries: What Has Happened Since the MFA Phase-Out?

On January 1, 2005, the controlled trade regime on textiles and clothing which was based on the Multi-Fiber Arrangement (MFA) made in 1974 was abolished. This institutional change wrought great impacts on the world market for textiles and clothing.This paper reviews the impacts of the changes on the main markets and examines the prospects for the markets and the source countries. The main conclusions are as follows: (1) after the renewal of quantitative restrictions on Chinese garment exports were agreed with the US and the EU, the post-MFA surge in Chinese garment exports was significantly attenuated; (2) instead, the growth in garment exports from other Asian low-income countries to the two markets was revived in 2006; (3) the Japanese market has been kept almost intact from the impact of the regime shift; (4) some developing countries, such as Bangladesh and Cambodia, not only survived the liberalization but also have steadily expanded their garment exports throughout the transition; and (5) an indicative fact is that the profitability of the garment industry in Bangladesh and Cambodia was high on average according to surveys conducted in 2003, which might have bolstered the steady growth of garment exports in the past, and possibly future growth, too.

Geotechnical Analysis of Contaminated Sand by Light Non-Aquous Phase Liquids

Contaminated soil reuse was investigated, with higher profusion, throughout the early 90’s, coinciding with the 1991 Gulf War, when efforts to amend large crude oil releases began in geotechnical assessment of contaminated soils. Isolated works referring to geotechnical testing with hydrocarbon ground contaminants are described in the state-of-the-art, which have been extended to other type of contaminated soil references. Contaminated soils by light non-aquous phase liquids (LNAPL) bearing capacity reduction has been previously investigated from a forensic point of view. To date, all the research works have been published based on the assumption of constant contaminant saturation for the entire soil mass. In contrast, the actual LNAPLs distribution plumes exhibit complex flow patterns which are subject to physical and chemical changes with time and distance travelled from the release source. This aspect has been considered along the present text. A typical Madrid arkosic soil formation is commonly known as Miga sand. Geotechnical tests have been carried out, with Miga sand specimens, in incremental series of LNAPL concentrations in order to observe the soil engineering properties variation due to a contamination increase. Results are discussed in relation with previous studies and as a matter of fact, soil mechanics parameters change in the presence of LNAPL, showing different tendencies according to each test and depending on the LNAPL content, as well as to the specimen’s initially planned relative density, dense or loose. Geotechnical practical implications are also commented on and analyzed. Variation on geotechnical properties may occur only within the external contour of contamination distribution plume. This scope has motivated the author to develop a physical model based on transparent soil technology. The model aims to reproduce the distribution of LNAPL into the ground due to an accidental release from a storage facility. Preliminary results indicate that the model is a potentially complementary tool for hydrogeological applications, site-characterization and remediation treatment testing within the framework of soil pollution events. A description of the test setup of an innovative three dimensional physical model for the flow of two or more phases, in porous media, is presented herein, along with a summary of the advantages, limitations and future applications for modeling with transparent material. En los primeros años de la década de los años 90, del siglo pasado, coincidiendo con la Guerra del Golfo en 1991, se investigó intensamente sobre la reutilización de suelos afectados por grandes volúmenes de vertidos de crudo, fomentándose la evaluación geotécnica de los suelos contaminados. Se describen, en el estado del arte de esta tésis, una serie de trabajos aislados en relación con la caracterización geotécnica de suelos contaminados con hidrocarburos, descripción ampliada mediante referencias relacionadas con otros tipos de contaminación de suelos. Existen estudios previos de patología de cimentaciones que analizan la reducción de la capacidad portante de suelos contaminados por hidrocarburos líquidos ligeros en fase no acuosa (acrónimo en inglés: LNAPL de “Liquid Non-Aquous Phase Liquid”). A fecha de redacción de la tesis, todas las publicaciones anteriores estaban basadas en la consideración de una saturación del contaminante constante en toda la extensión del terreno de cimentación. La distribución real de las plumas de contaminante muestra, por el contrario, complejas trayectorias de flujo que están sujetas a cambios físico-químicos en función del tiempo y la distancia recorrida desde su origen de vertido. Éste aspecto ha sido considerado y tratado en el presente texto. La arena de Miga es una formación geológica típica de Madrid. En el ámbito de esta tesis se han desarrollado ensayos geotécnicos con series de muestras de arena de Miga contaminadas con distintas concentraciones de LNAPL con el objeto de estimar la variación de sus propiedades geotécnicas debido a un incremento de contaminación. Se ha realizado una evaluación de resultados de los ensayos en comparación con otros estudios previamente analizados, resultando que las propiedades mecánicas del suelo, efectivamente, varían en función del contenido de LNAPL y de la densidad relativa con la que se prepare la muestra, densa o floja. Se analizan y comentan las implicaciones de carácter práctico que supone la mencionada variación de propiedades geotécnicas. El autor ha desarrollado un modelo físico basado en la tecnología de suelos transparentes, considerando que las variaciones de propiedades geotécnicas únicamente deben producirse en el ámbito interior del contorno de la pluma contaminante. El objeto del modelo es el de reproducir la distribución de un LNAPL en un terreno dado, causada por el vertido accidental de una instalación de almecenamiento de combustible. Los resultados preliminares indican que el modelo podría emplearse como una herramienta complementaria para el estudio de eventos contaminantes, permitiendo el desarrollo de aplicaciones de carácter hidrogeológico, caracterización de suelos contaminados y experimentación de tratamientos de remediación. Como aportación de carácter innovadora, se presenta y describe un modelo físico tridimensional de flujo de dos o más fases a través de un medio poroso transparente, analizándose sus ventajas e inconvenientes así como sus limitaciones y futuras aplicaciones.

Response timing in the lunge and target change in elite versus medium-level fencers.

The aim of the present work is to examine the differences between two groups of fencers with different levels of competition, elite and medium level. The timing parameters of the response reaction have been compared together with the kinetic variables which determine the sequence of segmented participation used during the lunge with a change in target during movement. A total of 30 male sword fencers participated, 13 elite and 17 medium level. Two force platforms recorded the horizontal component of the force and the start of the movement. One system filmed the movement in 3D, recording the spatial positions of 11 markers, while another system projected a mobile target over a screen. For synchronisation, an electronic signal enabled all the systems to be started simultaneously. Among the timing parameters of the reaction response, the choice reaction time (CRT) to the target change during the lunge was measured. The results revealed differences between the groups regarding the flight time, horizontal velocity at the end of the acceleration phase, and the length of the lunge, these being higher for the elite group, as well as other variables related to the temporal sequence of movement. No significant differences have been found in the simple reaction time or in CRT. According to the literature, the CRT appears to improve with sports practice, although this factor did not differentiate the elite from medium-level fencers. The coordination of fencing movements, that is, the right technique, constitutes a factor that differentiates elite fencers from medium-level ones.

Influence of aluminium on dimensional change of sintered 430 Ferritic Stainless Steel

Aluminium is added to decrease matrix chromium losses on 430 stainless steel sintered on nitrogen atmosphere. Three different ways were used to add a 3% (in weight) aluminium: as elemental powder, as prealloyed powder, and as intermetallic Fe-AI compound. After die pressing at densities between 6.1-6.5 g/cm3, samples were sintered on vacuum and on N2-5%H2 atmosphere in a dilatometric furnace. Therefore, dimensional change was recorded during sintering. Weight gain was obtained after nitrogen sintering on all materials due to nitrides formation. Sample expansion was obtained on all nitrogen sintered steels with Al additions. Microstructure showed a dispersion of aluminium nitrides when pre-alloyed powders are used. On the contrary, aluminium nitride areas can be found when aluminium is added as elemental powders or as Fe-AI intermetallics. Also nitrogen atmosphere leads to austenite formation and hence, on cooling, dilatometric results showed a dimensional change at austenitic-ferritic phase transformation temperature.

Characterisation of the operation & maintenance phase in PV rural electrification programmes

Con 1.300 millones de personas en el mundo sin acceso a la electricidad (la mayoría en entornos rurales de países empobrecidos), la energía solar fotovoltaica constituye una solución viable técnica y económicamente para electrificar las zonas más remotas del planeta donde las redes eléctricas convencionales no llegan. Casi todos los países en el mundo han desarrollado algún tipo de programa de electrificación fotovoltaica rural durante los últimos 40 años, principalmente los países más pobres, donde a través de diferentes modelos de financiación, se han instalado millones de sistemas solares domiciliarios (pequeños sistemas fotovoltaicos para uso doméstico). Durante este largo período, se han ido superando muchas barreras, como la mejora de la calidad de los sistemas fotovoltaicos, la reducción de costes, la optimización del diseño y del dimensionado de los sistemas, la disponibilidad financiera para implantar programas de electrificación rural, etc. Gracias a esto, la electrificación rural descentralizada ha experimentado recientemente un salto de escala caracterizada por la implantación de grandes programas con miles de sistemas solares domiciliarios e integrando largos períodos de mantenimiento. Muchos de estos grandes programas se están llevando a cabo con limitado éxito, ya que generalmente parten de supuestos e hipótesis poco contrastadas con la realidad, comprometiendo así un retorno económico que permita el desarrollo de esta actividad a largo plazo. En este escenario surge un nuevo reto: el de cómo garantizar la sostenibilidad de los grandes programas de electrificación rural fotovoltaica. Se argumenta que la principal causa de esta falta de rentabilidad es el imprevisto alto coste de la fase de operación y mantenimiento. Cuestiones clave tales como la estructura de costes de operación y mantenimiento o la fiabilidad de los componentes del sistema fotovoltaico no están bien caracterizados hoy en día. Esta situación limita la capacidad de diseñar estructuras de mantenimiento capaces de asegurar la sostenibilidad y la rentabilidad del servicio de operación y mantenimiento en estos programas. Esta tesis doctoral tiene como objetivo responder a estas cuestiones. Se ha realizado varios estudios sobre la base de un gran programa de electrificación rural fotovoltaica real llevado a cabo en Marruecos con más de 13.000 sistemas solares domiciliarios instalados. Sobre la base de este programa se ha hecho una evaluación en profundidad de la fiabilidad de los sistemas solares a partir de los datos de mantenimiento recogidos durante 5 años con más de 80.000 inputs. Los resultados han permitido establecer las funciones de fiabilidad de los equipos tal y como se comportan en condiciones reales de operación, las tasas de fallos y los tiempos medios hasta el fallo para los principales componentes del sistema, siendo este el primer caso de divulgación de resultados de este tipo en el campo de la electrificación rural fotovoltaica. Los dos principales componentes del sistema solar domiciliario, la batería y el módulo fotovoltaico, han sido analizados en campo a través de una muestra de 41 sistemas trabajando en condiciones reales pertenecientes al programa solar marroquí. Por un lado se ha estudiado la degradación de la capacidad de las baterías y por otro la degradación de potencia de los módulos fotovoltaicos. En el caso de las baterías, los resultados nos han permitido caracterizar la curva de degradación en capacidad llegando a obtener una propuesta de nueva definición del umbral de vida útil de las baterías en electrificación rural. También sobre la base del programa solar de Marruecos se ha llevado a cabo un estudio de caracterización de los costes reales de operación y mantenimiento a partir de la base de datos de contabilidad del programa registrados durante 5 años. Los resultados del estudio han permitido definir cuáles son costes que más incidencia tienen en el coste global. Se han obtenido los costes unitarios por sistema instalado y se han calculado los montantes de las cuotas de mantenimiento de los usuarios para garantizar la rentabilidad de la operación y mantenimiento. Finalmente, se propone un modelo de optimización matemática para diseñar estructuras de mantenimiento basado en los resultados de los estudios anteriores. La herramienta, elaborada mediante programación lineal entera mixta, se ha aplicado al programa marroquí con el fin de validar el modelo propuesto. ABSTRACT With 1,300 million people worldwide deprived of access to electricity (mostly in rural environments), photovoltaic solar energy has proven to be a cost‐effective solution and the only hope for electrifying the most remote inhabitants of the planet, where conventional electric grids do not reach because they are unaffordable. Almost all countries in the world have had some kind of rural photovoltaic electrification programme during the past 40 years, mainly the poorer countries, where through different organizational models, millions of solar home systems (small photovoltaic systems for domestic use) have been installed. During this long period, many barriers have been overcome, such as quality enhancement, cost reduction, the optimization of designing and sizing, financial availability, etc. Thanks to this, decentralized rural electrification has recently experienced a change of scale characterized by new programmes with thousands of solar home systems and long maintenance periods. Many of these large programmes are being developed with limited success, as they have generally been based on assumptions that do not correspond to reality, compromising the economic return that allows long term activity. In this scenario a new challenge emerges, which approaches the sustainability of large programmes. It is argued that the main cause of unprofitability is the unexpected high cost of the operation and maintenance of the solar systems. In fact, the lack of a paradigm in decentralized rural services has led to many private companies to carry out decentralized electrification programmes blindly. Issues such as the operation and maintenance cost structure or the reliability of the solar home system components have still not been characterized. This situation does not allow optimized maintenance structure to be designed to assure the sustainability and profitability of the operation and maintenance service. This PhD thesis aims to respond to these needs. Several studies have been carried out based on a real and large photovoltaic rural electrification programme carried out in Morocco with more than 13,000 solar home systems. An in‐depth reliability assessment has been made from a 5‐year maintenance database with more than 80,000 maintenance inputs. The results have allowed us to establish the real reliability functions, the failure rate and the main time to failure of the main components of the system, reporting these findings for the first time in the field of rural electrification. Both in‐field experiments on the capacity degradation of batteries and power degradation of photovoltaic modules have been carried out. During the experiments both samples of batteries and modules were operating under real conditions integrated into the solar home systems of the Moroccan programme. In the case of the batteries, the results have enabled us to obtain a proposal of definition of death of batteries in rural electrification. A cost assessment of the Moroccan experience based on a 5‐year accounting database has been carried out to characterize the cost structure of the programme. The results have allowed the major costs of the photovoltaic electrification to be defined. The overall cost ratio per installed system has been calculated together with the necessary fees that users would have to pay to make the operation and maintenance affordable. Finally, a mathematical optimization model has been proposed to design maintenance structures based on the previous study results. The tool has been applied to the Moroccan programme with the aim of validating the model.

Stationary-phase mutation in the bacterial chromosome: Recombination protein and DNA polymerase IV dependence

Several microbial systems have been shown to yield advantageous mutations in slowly growing or nongrowing cultures. In one assay system, the stationary-phase mutation mechanism differs from growth-dependent mutation, demonstrating that the two are different processes. This system assays reversion of a lac frameshift allele on an F′ plasmid in Escherichia coli. The stationary-phase mutation mechanism at lac requires recombination proteins of the RecBCD double-strand-break repair system and the inducible error-prone DNA polymerase IV, and the mutations are mostly −1 deletions in small mononucleotide repeats. This mutation mechanism is proposed to occur by DNA polymerase errors made during replication primed by recombinational double-strand-break repair. It has been suggested that this mechanism is confined to the F plasmid. However, the cells that acquire the adaptive mutations show hypermutation of unrelated chromosomal genes, suggesting that chromosomal sites also might experience recombination protein-dependent stationary-phase mutation. Here we test directly whether the stationary-phase mutations in the bacterial chromosome also occur via a recombination protein- and pol IV-dependent mechanism. We describe an assay for chromosomal mutation in cells carrying the F′ lac. We show that the chromosomal mutation is recombination protein- and pol IV-dependent and also is associated with general hypermutation. The data indicate that, at least in these male cells, recombination protein-dependent stationary-phase mutation is a mechanism of general inducible genetic change capable of affecting genes in the bacterial chromosome.

Progress toward chemical accuracy in the computer simulation of condensed phase reactions.

We describe a procedure for the generation of chemically accurate computer-simulation models to study chemical reactions in the condensed phase. The process involves (i) the use of a coupled semiempirical quantum and classical molecular mechanics method to represent solutes and solvent, respectively; (ii) the optimization of semiempirical quantum mechanics (QM) parameters to produce a computationally efficient and chemically accurate QM model; (iii) the calibration of a quantum/classical microsolvation model using ab initio quantum theory; and (iv) the use of statistical mechanical principles and methods to simulate, on massively parallel computers, the thermodynamic properties of chemical reactions in aqueous solution. The utility of this process is demonstrated by the calculation of the enthalpy of reaction in vacuum and free energy change in aqueous solution for a proton transfer involving methanol, methoxide, imidazole, and imidazolium, which are functional groups involved with proton transfers in many biochemical systems. An optimized semiempirical QM model is produced, which results in the calculation of heats of formation of the above chemical species to within 1.0 kcal/mol (1 kcal = 4.18 kJ) of experimental values. The use of the calibrated QM and microsolvation QM/MM (molecular mechanics) models for the simulation of a proton transfer in aqueous solution gives a calculated free energy that is within 1.0 kcal/mol (12.2 calculated vs. 12.8 experimental) of a value estimated from experimental pKa values of the reacting species.

Examining the Alliance-Outcome Relationship: Reverse Causation, Third Variables, and Treatment Phase Artifacts

Psychotherapy research reveals consistent associations between therapeutic alliance and treatment outcomes in the youth and adult literatures. Despite these consistent findings, prospective associations are not sufficient to support the claim that the alliance is a change mechanism in psychotherapy. The current study examined the direction of effect of the alliance- outcome relationship, the contribution of early symptom change in treatment to the development of therapeutic alliance, and the potential for pretreatment interpersonal functioning characteristics to be third variables that account for the association between alliance and outcome. Participants were adolescents with depression and a history of interpersonal trauma that presented to a community mental health center for treatment. Findings demonstrated that a more positive therapeutic alliance predicted greater subsequent symptom improvement, even after removing symptom change occurring before the measurement of alliance. Results also suggested that early change only slightly contributed to alliance development. Finally, though pretreatment interpersonal functioning was related to the first session alliance, these pretreatment client characteristics were not related to later alliance or symptom change. Overall, results provided some support for therapeutic alliance as a mechanism of change in psychotherapy. Methodological and clinical issues are discussed.