La catedral de Ávila : evolución constructiva y análisis estructural

Esta tesis se enmarca en el ámbito de la Historia de la Construcción, se estudia la Catedral de Ávila desde un punto de vista técnico, necesario para completar la visión que de esta catedral se tenía. La interpretación de la documentación de archivo, que se encontraba dispersa e inconexa, ha permitido realizar una cronología revisada y completa de las campañas constructivas para el conjunto de la Catedral, desde el siglo XI al XXI. Mediante el análisis de los Contratos de Obra e Informes, se ha puesto de relieve conocimientos de técnicas constructivas medievales. Se plantean dos hipótesis para el orden en el proceso constructivo. En la zona del Cimorro, en relación con la supresión de la tribuna, colocación de los arbotantes y construcción de la fortificación y triple almenado. En el cuerpo de las naves, referida a la posible existencia de una tribuna, colocación del sistema de contrarresto que vemos actualmente y misión del arco entibo del coro. Se ha analizado la estabilidad estructural de la Catedral bajo el marco teórico del Análisis Límite para Estructuras de Fábrica, utilizando la restitución gráfica procedente del levantamiento topográfico realizado. Estos análisis han servido como comprobación de las hipótesis planteadas, por realizarse tanto para la situación actual como para las diferentes campañas constructivas propuestas. Se ha comprobado la validez de las reglas geométricas tradicionales para el análisis de la estructuras de fábrica en los elementos principales de la estructura gótica. Esta tesis incrementa el conocimiento de la historia mecánica del edificio interpretando el funcionamiento mecánico de sus arbotantes, proyectados de forma atípica, y la colocación de los arcos entibo y codales para conseguir la estabilidad del conjunto. La tesis cuenta con un anexo que recopila una extensa documentación gráfica: planimetría, iconografía y fotografía histórica; la trascripción inédita del Contrato de obra para la Capilla de San Segundo y un anexo de cálculo de la zona del Cimorro y del Cuerpo de Naves. This thesis aims to the field of Construction History. The Cathedral of Ávila is studied from a technical point of view, which was necessary to complete the existing knowledge about this Cathedral. The interpretation of archive documentation, which was disperse and unconnected before this work, has allowed the proposal of a revised and complete chronology of the diverse building stages of the Cathedral, dating from the XI century to the XXI century. The analysis of work contracts and of reports has revealed knowledge of medieval construction techniques. Two hypotheses are presented about the order in the construction process. The first hypothesis concerning the destruction of the tribune, the placing of the flying buttress and the building of the fortification and triple system of battlement in the area of the “Cimorro”. The second hypothesis regarding the naves: the possible existence of a tribune, the placing of the system of counterthrust, which can currently be seen, and the function of the “entibo” arch in the choir. The Structural Stability of the Cathedral has been analysed within the theoretical Framework of Limit Analysis to Masonry Structure, by using of the drawing proceeding from our lifting topographical. These analyses have proven the presented hypotheses, since they have been applied to the current situation as well as to the several building stage proposed in the chronology. The validity of the traditional geometric rules for the analysis of the masonry structure in the core elements of Gothic structures has been verified. This thesis increases the knowledge of the mechanical history of the building by interpreting the mechanical working of the flying buttress in an atypical arrangement and the placing of the “entibo” arch and “codal” arch in order to obtain the stability of the monument. The thesis incorporates supplementary material which can be categorized in three groups: 1) extensive graphic documentation (planning, iconography and history photography); 2) the hitherto unknown transcription of the “CONTRATO DE OBRA PARA LA CAPILLA DE SAN SEGUNDO”; 3) an appendix of Analysis of Calculation for the “Cimorro” and the naves.

La estabilidad del frente de excavación de un túnel en terrenos heterogéneos o con un criterio de rotura no-lineal

El frente de un túnel puede colapsar si la presión aplicada sobre el es inferior a un valor limite denominado presión “critica” o “de colapso”. En este trabajo se desarrolla y presenta un mecanismo de rotura rotacional generado punto a punto para el cálculo de la presión de colapso del frente de túneles excavados en terrenos estratificados o en materiales que siguen un criterio de rotura nolineal. La solución propuesta es una solución de contorno superior en el marco del Análisis Límite y supone una generalización del mecanismo de rotura mas reciente existente en la bibliografía. La presencia de un terreno estratificado o con un criterio de rotura no-lineal implica una variabilidad espacial de las propiedades resistentes. Debido a esto, se generaliza el mecanismo desarrollado por Mollon et al. (2011b) para suelos, de tal forma que se puedan considerar valores locales del ángulo de rozamiento y de la cohesión. Además, la estratificación del terreno permite una rotura parcial del frente, por lo que se implementa esta posibilidad en el mecanismo, siendo la primera solución que emplea un mecanismo de rotura que se ajusta a la estratigrafía del terreno. Por otro lado, la presencia de un material con un criterio de rotura no-lineal exige introducir en el modelo, como variable de estudio, el estado tensional en el frente, el cual se somete al mismo proceso de optimización que las variables geométricas del mecanismo. Se emplea un modelo numérico 3D para validar las predicciones del mecanismo de Análisis Limite, demostrando que proporciona, con un esfuerzo computacional significativamente reducido, buenas predicciones de la presión critica, del tipo de rotura (global o parcial) en terrenos estratificados y de la geometría de fallo. El mecanismo validado se utiliza para realizar diferentes estudios paramétricos sobre la influencia de la estratigrafía en la presión de colapso. Igualmente, se emplea para elaborar cuadros de diseño de la presión de colapso para túneles ejecutados con tuneladora en macizos rocosos de mala calidad y para analizar la influencia en la estabilidad del frente del método constructivo. Asimismo, se lleva a cabo un estudio de fiabilidad de la estabilidad del frente de un túnel excavado en un macizo rocoso altamente fracturado. A partir de el se analiza como afectan las diferentes hipótesis acerca de los tipos de distribución y de las estructuras de correlación a los resultados de fiabilidad. Se investiga también la sensibilidad de los índices de fiabilidad a los cambios en las variables aleatorias, identificando las mas relevantes para el diseño. Por ultimo, se lleva a cabo un estudio experimental mediante un modelo de laboratorio a escala reducida. El modelo representa medio túnel, lo cual permite registrar el movimiento del material mediante una técnica de correlación de imágenes fotográficas. El ensayo se realiza con una arena seca y se controla por deformaciones mediante un pistón que simula el frente. Los resultados obtenidos se comparan con las estimaciones de la solución de Análisis Límite, obteniéndose un ajuste razonable, de acuerdo a la literatura, tanto en la geometría de rotura como en la presión de colapso. A tunnel face may collapse if the applied support pressure is lower than a limit value called the ‘critical’ or ‘collapse’ pressure. In this work, an advanced rotational failure mechanism generated ‘‘point-by-point” is developed to compute the collapse pressure for tunnel faces in layered (or stratified) grounds or in materials that follow a non-linear failure criterion. The proposed solution is an upper bound solution in the framework of limit analysis which extends the most advanced face failure mechanism in the literature. The excavation of the tunnel in a layered ground or in materials with a non-linear failure criterion may lead to a spatial variability of the strength properties. Because of this, the rotational mechanism recently proposed by Mollon et al. (2011b) for Mohr-Coulomb soils is generalized so that it can consider local values of the friction angle and of the cohesion. For layered soils, the mechanism needs to be extended to consider the possibility for partial collapse. The proposed methodology is the first solution with a partial collapse mechanism that can fit to the stratification. Similarly, the use of a nonlinear failure criterion introduces the need to introduce new parameters in the optimization problem to consider the distribution of normal stresses along the failure surface. A 3D numerical model is employed to validate the predictions of the limit analysis mechanism, demonstrating that it provides, with a significantly reduced computational effort, good predictions of critical pressure, of the type of collapse (global or partial) in layered soils, and of its geometry. The mechanism is then employed to conduct parametric studies of the influence of several geometrical and mechanical parameters on face stability of tunnels in layered soils. Similarly, the methodology has been further employed to develop simple design charts that provide the face collapse pressure of tunnels driven by TBM in low quality rock masses and to study the influence of the construction method. Finally, a reliability analysis of the stability of a tunnel face driven in a highly fractured rock mass is performed. The objective is to analyze how different assumptions about distributions types and correlation structures affect the reliability results. In addition, the sensitivity of the reliability index to changes in the random variables is studied, identifying the most relevant variables for engineering design. Finally, an experimental study is carried out using a small-scale laboratory model. The problem is modeled in half, cutting through the tunnel axis vertically, so that displacements of soil particles can be recorded by a digital image correlation technique. The tests were performed with dry sand and displacements are controlled by a piston that supports the soil. The results of the model are compared with the predictions of the Limit Analysis mechanism. A reasonable agreement, according to literature, is obtained between the shapes of the failure surfaces and between the collapse pressures observed in the model tests and computed with the analytical solution.

Caracterización estructural de los rellenos situados en el trasdós de bóvedas de edificios históricos

El papel esencial de los rellenos en el comportamiento y la estabilidad de las construcciones de fábrica ha sido sorprendentemente ignorado en la bibliografía técnica, contribuyendo este trabajo a cubrir esta laguna del conocimiento. Se presenta en primer lugar la configuración morfológica de los rellenos del trasdós de bóvedas en la Península Ibérica en tres periodos histórico-técnicos: la construcción romana, la románica y la gótica. La clasificación se ha realizado en base a inspecciones visuales de diferentes edificios. En sendos anexos se presentan análisis comparados de la base de datos que se ha reunido y las fichas de las construcciones consideradas. En segundo lugar se ha caracterizado el papel estructural de los rellenos, identificándose las características intrínsecas que se estiman más significativas de dichos rellenos en relación tanto con su propia configuración como con su función estructural. Muy en particular se proponen unas leyes de empujes coherentes con la naturaleza y con las condiciones de contorno de los rellenos y las bóvedas. En esta tesis se ha desarrollado una sencilla, potente y suficiente herramienta de análisis que considera las principales variables que intervienen en el comportamiento de una estructura de fábrica, incluyendo muy particularmente los rellenos. Para ello se ha planteado una herramienta basada en el análisis límite que incluye la comprobación tensional de los diferentes esfuerzos, normales o tangenciales, así como la interfaz entre bóvedas y rellenos, dotándose a los técnicos de una herramienta que permite entender estas estructuras, de complejo funcionamiento. La herramienta propuesta incluye consideraciones energéticas para encontrar la solución más cercana al funcionamiento real. La herramienta se ha calibrado con ejemplos analizados por otros autores con diferentes procedimientos, poniéndose de manifiesto su suficiente precisión y eficacia, especialmente si se tiene en cuenta que requiere sólo de unos datos mínimos. La calibración se ha extendido al ensayo en modelo reducido de este tipo de estructuras en el Laboratorio de Estructuras de la Escuela de Ingenieros de Caminos, Canales y Puertos de Madrid. Fruto de esa calibración, se ha realizado un amplio estudio paramétrico que permite cuantificar la influencia que tienen en el comportamiento estructural variables como el apuntamiento de las bóvedas (relación luz/flecha), su esbeltez (relación luz/canto en clave), la altura de los rellenos rígidos, la altura de los rellenos granulares, etc. Ese estudio ha permitido identificar los puntos críticos, las ratios características que condicionan el comportamiento y, en fin, los aspectos clave del análisis estructural de estas construcciones desde el punto de vista de la interrelación, hasta ahora desconocida, de estructura y relleno, que también es estructura. Ello permitirá orientar de mejor manera las inspecciones de estas estructuras y sus análisis estructurales. Finalmente, la tesis concluye con el desarrollo de tres ejemplos, correspondientes cada uno de ellos a los periodos históricos referidos, en los que se pone de manifiesto el papel crucial de los rellenos en la estabilidad no sólo de las bóvedas sino del resto de elementos estructurales que componen un edificio (pilares, muros, botareles, etc.). Al final se presentan las conclusiones del trabajo y se enumeran las muchas líneas de trabajo que quedan abiertas tras esta tesis. It is surprising that the essential role of the backfill at the extrados of masonry vaults and domes has been ignored or misunderstood in the technical literature. The main purpose of this work is to contribute to overcome such a lacuna. Firstly, the morphological configuration of backfill that can be found in the Iberian Peninsula in Roman, Romanesque and Gothic buildings is also presented. Two annexes are devoted to show the collected database and the result of its analysis. Then, the structural role of backfill is characterised, as well as the intrinsic and most significant properties related both to its configuration and structural function. Thus, specific thrust values are proposed to analyse such structures, taking into account the nature and boundary conditions of walls and vaults. The simple, powerful and sufficient tool of analysis that has been developed is also presented, including the main variables involved, especially the backfill. The limit analysis method, followed by a stress verification, including the extrados of vaults and backfill interface, and an enhanced algorithm based on energetic considerations, are used to provide technicians a tool to understand this type of structures efficiently, in a balanced situation between the rather scarce amount of information and sufficient accuracy and liability. The tool was calibrated by comparing the experimental and theoretical results provided by different authors regarding several examples, as well as our own experimental campaign carried out at the Civil Engineering School of Madrid. A parametric study is also developed, providing original information about the structural importance of several parameters, as the span-to-depth or span-to-rise ratios, relative height of backfill, etc. As a result of this analysis, critical points and tendencies of structural behaviour were detected, helping technicians to inspect and analyse these constructions, also revealing some particularities related to their construction. Furthermore, a set of three examples corresponding to the three structural typologies analysed (Roman, Romanesque and Gothic) is studied. The crucial importance of backfill is then highlighted, not only for the stability of vaults or domes, but also for the equilibrium of walls, pillars and buttresses. Finally, the conclusions of the study and the future research fields are also presented.

Shape and chemically anisotropic colloidal particles: A theoretical study of their structure, phase behavior, and slow dynamics

A detailed non-equilibrium state diagram of shape-anisotropic particle fluids is constructed. The effects of particle shape are explored using Naive Mode Coupling Theory (NMCT), and a single particle Non-linear Langevin Equation (NLE) theory. The dynamical behavior of non-ergodic fluids are discussed. We employ a rotationally frozen approach to NMCT in order to determine a transition to center of mass (translational) localization. Both ideal and kinetic glass transitions are found to be highly shape dependent, and uniformly increase with particle dimensionality. The glass transition volume fraction of quasi 1- and 2- dimensional particles fall monotonically with the number of sites (aspect ratio), while 3-dimensional particles display a non-monotonic dependence of glassy vitrification on the number of sites. Introducing interparticle attractions results in a far more complex state diagram. The ideal non-ergodic boundary shows a glass-fluid-gel re-entrance previously predicted for spherical particle fluids. The non-ergodic region of the state diagram presents qualitatively different dynamics in different regimes. They are qualified by the different behaviors of the NLE dynamic free energy. The caging dominated, repulsive glass regime is characterized by long localization lengths and barrier locations, dictated by repulsive hard core interactions, while the bonding dominated gel region has short localization lengths (commensurate with the attraction range), and barrier locations. There exists a small region of the state diagram which is qualified by both glassy and gel localization lengths in the dynamic free energy. A much larger (high volume fraction, and high attraction strength) region of phase space is characterized by short gel-like localization lengths, and long barrier locations. The region is called the attractive glass and represents a 2-step relaxation process whereby a particle first breaks attractive physical bonds, and then escapes its topological cage. The dynamic fragility of fluids are highly particle shape dependent. It increases with particle dimensionality and falls with aspect ratio for quasi 1- and 2- dimentional particles. An ultralocal limit analysis of the NLE theory predicts universalities in the behavior of relaxation times, and elastic moduli. The equlibrium phase diagram of chemically anisotropic Janus spheres and Janus rods are calculated employing a mean field Random Phase Approximation. The calculations for Janus rods are corroborated by the full liquid state Reference Interaction Site Model theory. The Janus particles consist of attractive and repulsive regions. Both rods and spheres display rich phase behavior. The phase diagrams of these systems display fluid, macrophase separated, attraction driven microphase separated, repulsion driven microphase separated and crystalline regimes. Macrophase separation is predicted in highly attractive low volume fraction systems. Attraction driven microphase separation is charaterized by long length scale divergences, where the ordering length scale determines the microphase ordered structures. The ordering length scale of repulsion driven microphase separation is determined by the repulsive range. At the high volume fractions, particles forgo the enthalpic considerations of attractions and repulsions to satisfy hard core constraints and maximize vibrational entropy. This results in site length scale ordering in rods, and the sphere length scale ordering in Janus spheres, i.e., crystallization. A change in the Janus balance of both rods and spheres results in quantitative changes in spinodal temperatures and the position of phase boundaries. However, a change in the block sequence of Janus rods causes qualitative changes in the type of microphase ordered state, and induces prominent features (such as the Lifshitz point) in the phase diagrams of these systems. A detailed study of the number of nearest neighbors in Janus rod systems reflect a deep connection between this local measure of structure, and the structure factor which represents the most global measure of order.

Fukushima-derived radionuclides in sediments of the Japanese Pacific Ocean coast and various Japanese water samples (seawater, tap water, and coolant water of Fukushima Daiichi reactor unit 5)

We investigated Ocean sediments and seawater from inside the Fukushima exclusion zone and found radiocesium (134Cs and 137Cs) up to 800 Bq kg-1 as well as 90Sr up to 5.6 Bq kg-1. This is one of the first reports on radiostrontium in sea sediments from the Fukushima exclusion zone. Seawater exhibited contamination levels up to 5.3 Bq kg-1 radiocesium. Tap water from Tokyo from weeks after the accident exhibited detectable but harmless activities of radiocesium (well below the regulatory limit). Analysis of the Unit 5 reactor coolant (finding only 3H and even low 129I) leads to the conclusion that the purification techniques for reactor coolant employed at Fukushima Daiichi are very effective.

Spectral analysis and limit behaviours in a spring-mass system

We consider a model for a damped spring-mass system that is a strongly damped wave equation with dynamic boundary conditions. In a previous paper we showed that for some values of the parameters of the model, the large time behaviour of the solutions is the same as for a classical spring-mass damper ODE. Here we use spectral analysis to show that for other values of the parameters, still of physical relevance and related to the effect of the spring inner viscosity, the limit behaviours are very different from that classical ODE

Slope stability analysis of the Pacaya Volcano, Guatemala, using limit equilibrium and finite element method

The Pacaya volcanic complex is part of the Central American volcanic arc, which is associated with the subduction of the Cocos tectonic plate under the Caribbean plate. Located 30 km south of Guatemala City, Pacaya is situated on the southern rim of the Amatitlan Caldera. It is the largest post-caldera volcano, and has been one of Central America’s most active volcanoes over the last 500 years. Between 400 and 2000 years B.P, the Pacaya volcano had experienced a huge collapse, which resulted in the formation of horseshoe-shaped scarp that is still visible. In the recent years, several smaller collapses have been associated with the activity of the volcano (in 1961 and 2010) affecting its northwestern flanks, which are likely to be induced by the local and regional stress changes. The similar orientation of dry and volcanic fissures and the distribution of new vents would likely explain the reactivation of the pre-existing stress configuration responsible for the old-collapse. This paper presents the first stability analysis of the Pacaya volcanic flank. The inputs for the geological and geotechnical models were defined based on the stratigraphical, lithological, structural data, and material properties obtained from field survey and lab tests. According to the mechanical characteristics, three lithotechnical units were defined: Lava, Lava-Breccia and Breccia-Lava. The Hoek and Brown’s failure criterion was applied for each lithotechnical unit and the rock mass friction angle, apparent cohesion, and strength and deformation characteristics were computed in a specified stress range. Further, the stability of the volcano was evaluated by two-dimensional analysis performed by Limit Equilibrium (LEM, ROCSCIENCE) and Finite Element Method (FEM, PHASE 2 7.0). The stability analysis mainly focused on the modern Pacaya volcano built inside the collapse amphitheatre of “Old Pacaya”. The volcanic instability was assessed based on the variability of safety factor using deterministic, sensitivity, and probabilistic analysis considering the gravitational instability and the effects of external forces such as magma pressure and seismicity as potential triggering mechanisms of lateral collapse. The preliminary results from the analysis provide two insights: first, the least stable sector is on the south-western flank of the volcano; second, the lowest safety factor value suggests that the edifice is stable under gravity alone, and the external triggering mechanism can represent a likely destabilizing factor.

Asymptotic analysis of vertical geothermal boreholes in the limit of slowly varyng heat injection rates

Theoretical models for the thermal response of vertical geothermal boreholes often assume that the characteristic time of variation of the heat injection rate is much larger than the characteristic diffusion time across the borehole. In this case, heat transfer inside the borehole and in its immediate surroundings is quasi-steady in the first approximation, while unsteady effects enter only in the far field. Previous studies have exploited this disparity of time scales, incorporating approximate matching conditions to couple the near-borehole region with the outer unsteady temperatura field. In the present work matched asymptotic expansion techniques are used to analyze the heat transfer problem, delivering a rigorous derivation of the true matching condition between the two regions and of the correct definition of the network of thermal resistances that represents the quasi-steady solution near the borehole. Additionally, an apparent temperature due to the unsteady far field is identified that needs to be taken into account by the near-borehole region for the correct computation of the heat injection rate. This temperature differs from the usual mean borehole temperature employed in the literatura.

The effects of the new 65 mile-per-hour speed limit on rural highway fatalities: a state-by-state analysis. Final grant report.

National Highway Traffic Safety Administration, Office of Research and Development, Washington, D.C.

RELIBILITY ANALYSIS OF SIMPLE SLOPES AND SOIL-STRUCTURES WITH LINEAR LIMIT STATES

The first objective of this research was to develop closed-form and numerical probabilistic methods of analysis that can be applied to otherwise conventional methods of unreinforced and geosynthetic reinforced slopes and walls. These probabilistic methods explicitly include random variability of soil and reinforcement, spatial variability of the soil, and cross-correlation between soil input parameters on probability of failure. The quantitative impact of simultaneously considering the influence of random and/or spatial variability in soil properties in combination with cross-correlation in soil properties is investigated for the first time in the research literature. Depending on the magnitude of these statistical descriptors, margins of safety based on conventional notions of safety may be very different from margins of safety expressed in terms of probability of failure (or reliability index). The thesis work also shows that intuitive notions of margin of safety using conventional factor of safety and probability of failure can be brought into alignment when cross-correlation between soil properties is considered in a rigorous manner. The second objective of this thesis work was to develop a general closed-form solution to compute the true probability of failure (or reliability index) of a simple linear limit state function with one load term and one resistance term expressed first in general probabilistic terms and then migrated to a LRFD format for the purpose of LRFD calibration. The formulation considers contributions to probability of failure due to model type, uncertainty in bias values, bias dependencies, uncertainty in estimates of nominal values for correlated and uncorrelated load and resistance terms, and average margin of safety expressed as the operational factor of safety (OFS). Bias is defined as the ratio of measured to predicted value. Parametric analyses were carried out to show that ignoring possible correlations between random variables can lead to conservative (safe) values of resistance factor in some cases and in other cases to non-conservative (unsafe) values. Example LRFD calibrations were carried out using different load and resistance models for the pullout internal stability limit state of steel strip and geosynthetic reinforced soil walls together with matching bias data reported in the literature.

Assessment Of Robustness On Analysis Using Headspace Solid-phase Microextraction And Comprehensive Two-dimensional Gas Chromatography Through Experimental Designs.

Plackett-Burman experimental design was applied for the robustness assessment of GC×GC-qMS (Comprehensive Two-Dimensional Gas Chromatography with Fast Quadrupolar Mass Spectrometric Detection) in quantitative and qualitative analysis of volatiles compounds from chocolate samples isolated by headspace solid-phase microextraction (HS-SPME). The influence of small changes around the nominal level of six factors deemed as important on peak areas (carrier gas flow rate, modulation period, temperature of ionic source, MS photomultiplier power, injector temperature and interface temperature) and of four factors considered as potentially influential on spectral quality (minimum and maximum limits of the scanned mass ranges, ions source temperature and photomultiplier power). The analytes selected for the study were 2,3,5-trimethylpyrazine, 2-octanone, octanal, 2-pentyl-furan, 2,3,5,6-tetramethylpyrazine, and 2-nonanone e nonanal. The factors pointed out as important on the robustness of the system were photomultiplier power for quantitative analysis and lower limit of mass scanning range for qualitative analysis.

Detection Of Explosives On The Surface Of Banknotes By Raman Hyperspectral Imaging And Independent Component Analysis.

The aim of this study was to develop a methodology using Raman hyperspectral imaging and chemometric methods for identification of pre- and post-blast explosive residues on banknote surfaces. The explosives studied were of military, commercial and propellant uses. After the acquisition of the hyperspectral imaging, independent component analysis (ICA) was applied to extract the pure spectra and the distribution of the corresponding image constituents. The performance of the methodology was evaluated by the explained variance and the lack of fit of the models, by comparing the ICA recovered spectra with the reference spectra using correlation coefficients and by the presence of rotational ambiguity in the ICA solutions. The methodology was applied to forensic samples to solve an automated teller machine explosion case. Independent component analysis proved to be a suitable method of resolving curves, achieving equivalent performance with the multivariate curve resolution with alternating least squares (MCR-ALS) method. At low concentrations, MCR-ALS presents some limitations, as it did not provide the correct solution. The detection limit of the methodology presented in this study was 50μgcm(-2).

Flow injection green method for the quantitative analysis of ketoconazole in pharmaceutical preparations

A flow injection method for the quantitative analysis of ketoconazole in tablets, based on the reaction with iron (III) ions, is presented. Ketoconazole forms a red complex with iron ions in an acid medium, with maximum absorbance at 495 nm. The detection limit was estimated to be 1×10--4 mol L-1; the quantitation limit is about 3×10--4 mol L-1 and approximately 30 determinations can be performed in an hour. The results were compared with those obtained with a reference HPLC method. Statistical comparisons were done using the Student's t procedure and the F test. Complete agreement was found at the 0.95 significance level between the proposed flow injection and the HPLC procedures. The two methods present similar precision, i.e., for HPLC the mean relative standard deviation was ca. 1.2% and for FIA ca. 1.6%.

An Environmental Friendly Procedure for Photometric Determination of Hypochlorite in Tap Water Employing a Miniaturized Multicommuted Flow Analysis Setup

A photometric procedure for the determination of ClO(-) in tap water employing a miniaturized multicommuted flow analysis setup and an LED-based photometer is described. The analytical procedure was implemented using leucocrystal violet (LCV; 4,4', 4 ''-methylidynetris (N, N-dimethylaniline), C(25)H(31)N(3)) as a chromogenic reagent. Solenoid micropumps employed for solutions propelling were assembled together with the photometer in order to compose a compact unit of small dimensions. After control variables optimization, the system was applied for the determination of ClO(-) in samples of tap water, and aiming accuracy assessment samples were also analyzed using an independent method. Applying the paired t-test between results obtained using both methods, no significant difference at the 95% confidence level was observed. Other useful features include low reagent consumption, 2.4 mu g of LCV per determination, a linear response ranging from 0.02 up to 2.0 mg L(-1) ClO(-), a relative standard deviation of 1.0% (n = 11) for samples containing 0.2 mg L(-1) ClO(-), a detection limit of 6.0 mu g L(-1) ClO(-), a sampling throughput of 84 determinations per hour, and a waste generation of 432 mu L per determination.

Limit on the diffuse flux of ultrahigh energy tau neutrinos with the surface detector of the Pierre Auger Observatory

Data collected at the Pierre Auger Observatory are used to establish an upper limit on the diffuse flux of tau neutrinos in the cosmic radiation. Earth-skimming nu(tau) may interact in the Earth's crust and produce a tau lepton by means of charged-current interactions. The tau lepton may emerge from the Earth and decay in the atmosphere to produce a nearly horizontal shower with a typical signature, a persistent electromagnetic component even at very large atmospheric depths. The search procedure to select events induced by tau decays against the background of normal showers induced by cosmic rays is described. The method used to compute the exposure for a detector continuously growing with time is detailed. Systematic uncertainties in the exposure from the detector, the analysis, and the involved physics are discussed. No tau neutrino candidates have been found. For neutrinos in the energy range 2x10(17) eV < E(nu)< 2x10(19) eV, assuming a diffuse spectrum of the form E(nu)(-2), data collected between 1 January 2004 and 30 April 2008 yield a 90% confidence-level upper limit of E(nu)(2)dN(nu tau)/dE(nu)< 9x10(-8) GeV cm(-2) s(-1) sr(-1).