The magnesium isotope composition of diagenetic dolomites from ODP Hole 112-685A and 201-1230A of the Peru Margin

The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Análisis y diseño de un patrón de ruido térmico de 10 MHz a 26,5 GHz en tecnología coaxial

Esta Tesis Doctoral presenta las investigaciones y los trabajos desarrollados durante los años 2008 a 2012 para el análisis y diseño de un patrón primario de ruido térmico de banda ancha en tecnología coaxial. Para ubicar esta Tesis en su campo científico es necesario tomar conciencia de que la realización de mediciones fiables y trazables forma parte del sostenimiento del bienestar de una sociedad moderna y juega un papel crítico en apoyo de la competitividad económica, la fabricación y el comercio, así como de la calidad de vida. En el mundo moderno actual, una infraestructura de medición bien desarrollada genera confianza en muchas facetas de nuestra vida diaria, porque nos permite el desarrollo y fabricación de productos fiables, innovadores y de alta calidad; porque sustenta la competitividad de las industrias y su producción sostenible; además de contribuir a la eliminación de barreras técnicas y de dar soporte a un comercio justo, garantizar la seguridad y eficacia de la asistencia sanitaria, y por supuesto, dar respuesta a los grandes retos de la sociedad moderna en temas tan complicados como la energía y el medio ambiente. Con todo esto en mente se ha desarrollado un patrón primario de ruido térmico con el fin de aportar al sistema metrológico español un nuevo patrón primario de referencia capaz de ser usado para desarrollar mediciones fiables y trazables en el campo de la medida y calibración de dispositivos de ruido electromagnético de radiofrecuencia y microondas. Este patrón se ha planteado para que cumpla en el rango de 10 MHz a 26,5 GHz con las siguientes especificaciones: Salida nominal de temperatura de ruido aproximada de ~ 83 K. Incertidumbre de temperatura de ruido menor que ± 1 K en todo su rango de frecuencias. Coeficiente de reflexión en todo su ancho de banda de 0,01 a 26,5 GHz lo más bajo posible. Se ha divido esta Tesis Doctoral en tres partes claramente diferenciadas. La primera de ellas, que comprende los capítulos 1, 2, 3, 4 y 5, presenta todo el proceso de simulaciones y ajustes de los parámetros principales del dispositivo con el fin de dejar definidos los que resultan críticos en su construcción. A continuación viene una segunda parte compuesta por el capítulo 6 en donde se desarrollan los cálculos necesarios para obtener la temperatura de ruido a la salida del dispositivo. La tercera y última parte, capítulo 7, se dedica a la estimación de la incertidumbre de la temperatura de ruido del nuevo patrón primario de ruido obtenida en el capítulo anterior. Más concretamente tenemos que en el capítulo 1 se hace una exhaustiva introducción del entorno científico en donde se desarrolla este trabajo de investigación. Además se detallan los objetivos que se persiguen y se presenta la metodología utilizada para conseguirlos. El capítulo 2 describe la caracterización y selección del material dieléctrico para el anillo del interior de la línea de transmisión del patrón que ponga en contacto térmico los dos conductores del coaxial para igualar las temperaturas entre ambos y mantener la impedancia característica de todo el patrón primario de ruido. Además se estudian las propiedades dieléctricas del nitrógeno líquido para evaluar su influencia en la impedancia final de la línea de transmisión. En el capítulo 3 se analiza el comportamiento de dos cargas y una línea de aire comerciales trabajando en condiciones criogénicas. Se pretende con este estudio obtener la variación que se produce en el coeficiente de reflexión al pasar de temperatura ambiente a criogénica y comprobar si estos dispositivos resultan dañados por trabajar a temperaturas criogénicas; además se estudia si se modifica su comportamiento tras sucesivos ciclos de enfriamiento – calentamiento, obteniendo una cota de la variación para poder así seleccionar la carga que proporcione un menor coeficiente de reflexión y una menor variabilidad. En el capítulo 4 se parte del análisis de la estructura del anillo de material dieléctrico utilizada en la nota técnica NBS 1074 del NIST con el fin de obtener sus parámetros de dispersión que nos servirán para calcular el efecto que produce sobre el coeficiente de reflexión de la estructura coaxial completa. Además se realiza un estudio posterior con el fin de mejorar el diseño de la nota técnica NBS 1074 del NIST, donde se analiza el anillo de material dieléctrico, para posteriormente realizar modificaciones en la geometría de la zona donde se encuentra éste con el fin de reducir la reflexión que produce. Concretamente se estudia el ajuste del radio del conductor interior en la zona del anillo para que presente la misma impedancia característica que la línea. Y para finalizar se obtiene analíticamente la relación entre el radio del conductor interior y el radio de la transición de anillo térmico para garantizar en todo punto de esa transición la misma impedancia característica, manteniendo además criterios de robustez del dispositivo y de fabricación realistas. En el capítulo 5 se analiza el comportamiento térmico del patrón de ruido y su influencia en la conductividad de los materiales metálicos. Se plantean las posibilidades de que el nitrógeno líquido sea exterior a la línea o que éste penetre en su interior. En ambos casos, dada la simetría rotacional del problema, se ha simulado térmicamente una sección de la línea coaxial, es decir, se ha resuelto un problema bidimensional, aunque los resultados son aplicables a la estructura real tridimensional. Para la simulación térmica se ha empleado la herramienta PDE Toolbox de Matlab®. En el capítulo 6 se calcula la temperatura de ruido a la salida del dispositivo. Se parte del estudio de la aportación a la temperatura de ruido final de cada sección que compone el patrón. Además se estudia la influencia de las variaciones de determinados parámetros de los elementos que conforman el patrón de ruido sobre las características fundamentales de éste, esto es, el coeficiente de reflexión a lo largo de todo el dispositivo. Una vez descrito el patrón de ruido electromagnético se procede, en el capítulo 7, a describir los pasos seguidos para estimar la incertidumbre de la temperatura de ruido electromagnético a su salida. Para ello se utilizan dos métodos, el clásico de la guía para la estimación de la incertidumbre [GUM95] y el método de simulación de Monte Carlo. En el capítulo 8 se describen las conclusiones y lo logros conseguidos. Durante el desarrollo de esta Tesis Doctoral se ha obtenido un dispositivo novedoso susceptible de ser patentado, que ha sido registrado en la Oficina Española de Patentes y Marcas (O.E.P.M.) en Madrid, de conformidad con lo establecido en el artículo 20 de la Ley 11/1986, de 20 de Marzo, de Patentes, con el título Patrón Primario de Ruido Térmico de Banda Ancha (Referencia P-101061) con fecha 7 de febrero de 2011. ABSTRACT This Ph. D. work describes a number of investigations that were performed along the years 2008 to 2011, as a preparation for the study and design of a coaxial cryogenic reference noise standard. Reliable and traceable measurement underpins the welfare of a modern society and plays a critical role in supporting economic competitiveness, manufacturing and trade as well as quality of life. In our modern world, a well developed measurement infrastructure gives confidence in many aspects of our daily life, for example by enabling the development and manufacturing of reliable, high quality and innovative products; by supporting industry to be competitive and sustainable in its production; by removing technical barriers to trade and supporting fair trade; by ensuring safety and effectiveness of healthcare; by giving response to the major challenges in key sectors such energy and environment, etc. With all this in mind we have developed a primary standard thermal noise with the aim of providing the Spanish metrology system with a new primary standard for noise reference. This standard will allow development of reliable and traceable measurements in the field of calibration and measurement of electromagnetic noise RF and microwave devices. This standard has been designed to work in the frequency range from 10 MHz to 26.5 GHz, meeting the following specifications: 1. Noise temperature output is to be nominally ~ 83 K. 2. Noise temperature uncertainty less than ± 1 K in the frequency range from 0.01 to 26.5 GHz. 3. Broadband performance requires as low a reflection coefficient as possible from 0.01 to 26.5 GHz. The present Ph. D. work is divided into three clearly differentiated parts. The first one, which comprises Chapters 1 to 5, presents the whole process of simulation and adjustment of the main parameters of the device in order to define those of them which are critical for the manufacturing of the device. Next, the second part consists of Chapter 6 where the necessary computations to obtain the output noise temperature of the device are carried out. The third and last part, Chapter 7, is devoted to the estimation of the uncertainty related to the noise temperature of the noise primary standard as obtained in the preceding chapter. More specifically, Chapter 1 provides a thorough introduction to the scientific and technological environment where this research takes place. It also details the objectives to be achieved and presents the methodology used to achieve them. Chapter 2 describes the characterization and selection of the bead dielectric material inside the transmission line, intended to connect the two coaxial conductors equalizing the temperature between the two of them and thus keeping the characteristic impedance constant for the whole standard. In addition the dielectric properties of liquid nitrogen are analyzed in order to assess their influence on the impedance of the transmission line. Chapter 3 analyzes the behavior of two different loads and of a commercial airline when subjected to cryogenic working conditions. This study is intended to obtain the variation in the reflection coefficient when the temperature changes from room to cryogenic temperature, and to check whether these devices can be damaged as a result of working at cryogenic temperatures. Also we try to see whether the load changes its behavior after successive cycles of cooling / heating, in order to obtain a bound for the allowed variation of the reflection coefficient of the load. Chapter 4 analyzes the ring structure of the dielectric material used in the NBS technical note 1074 of NIST, in order to obtain its scattering parameters that will be used for computation of its effect upon the reflection coefficient of the whole coaxial structure. Subsequently, we perform a further investigation with the aim of improving the design of NBS technical note 1074 of NIST, and modifications are introduced in the geometry of the transition area in order to reduce the reflection it produces. We first analyze the ring, specifically the influence of the radius of inner conductor of the bead, and then make changes in its geometry so that it presents the same characteristic impedance as that of the line. Finally we analytically obtain the relationship between the inner conductor radius and the radius of the transition from ring, in order to ensure the heat flow through the transition thus keeping the same reflection coefficient, and at the same time meeting the robustness requirements and the feasibility of manufacturing. Chapter 5 analyzes the thermal behavior of the noise standard and its influence on the conductivity of metallic materials. Both possibilities are raised that the liquid nitrogen is kept outside the line or that it penetrates inside. In both cases, given the rotational symmetry of the structure, we have simulated a section of coaxial line, i.e. the equivalent two-dimensional problem has been resolved, although the results are applicable to the actual three-dimensional structure. For thermal simulation Matlab™ PDE Toolbox has been used. In Chapter 6 we compute the output noise temperature of the device. The starting point is the analysis of the contribution to the overall noise temperature of each section making up the standard. Moreover the influence of the variations in the parameters of all elements of the standard is analyzed, specifically the variation of the reflection coefficient along the entire device. Once the electromagnetic noise standard has been described and analyzed, in Chapter 7 we describe the steps followed to estimate the uncertainty of the output electromagnetic noise temperature. This is done using two methods, the classic analytical approach following the Guide to the Estimation of Uncertainty [GUM95] and numerical simulations made with the Monte Carlo method. Chapter 8 discusses the conclusions and achievements. During the development of this thesis, a novel device was obtained which was potentially patentable, and which was finally registered through the Spanish Patent and Trademark Office (SPTO) in Madrid, in accordance with the provisions of Article 20 of Law 11/1986 about Patents, dated March 20th, 1986. It was registered under the denomination Broadband Thermal Noise Primary Standard (Reference P-101061) dated February 7th, 2011.

Mechanical characterisation of tungsten-1wt.% yttrium oxide as a function of temperature and atmosphere

This study evaluates the mechanical behaviour of an Y2O3-dispersed tungsten (W) alloy and compares it to a pure W reference material. Both materials were processed via mechanical alloying (MA) and subsequent hot isostatic pressing (HIP). We performed non-standard three-point bending (TPB) tests in both an oxidising atmosphere and vacuum across a temperature range from 77 K, obtained via immersion in liquid nitrogen, to 1473 K to determine the mechanical strength, yield strength and fracture toughness. This research aims to evaluate how the mechanical behaviour of the alloy is affected by oxides formed within the material at high temperatures, primarily from 873 K, when the materials undergo a massive thermal degradation. The results indicate that the alloy is brittle to a high temperature (1473 K) under both atmospheres and that the mechanical properties degrade significantly above 873 K. We also used Vickers microhardness tests and the dynamic modulus by impulse excitation technique (IET) to determine the elastic modulus at room temperature. Moreover, we performed nanoindentation tests to determine the effect of size on the hardness and elastic modulus; however, no significant differences were found. Additionally, we calculated the relative density of the samples to assess the porosity of the alloy. Finally, we analysed the microstructure and fracture surfaces of the tested materials via field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). In this way, the relationship between the macroscopic mechanical properties and micromechanisms of failure could be determined based on the temperature and oxides formed

Determinação de vitaminas antioxidantes em suplementos e avaliação da rotulagem nutricional

Introdução: Diante das mudanças nos hábitos de consumo alimentar da população brasileira, suplementos vitamínicos e alimentos enriquecidos são veículos comumente empregados para atender as necessidades de ingestão de micronutrientes. A diversidade de suplementos vitamínicos comercializados atualmente leva à necessidade de desenvolvimento de métodos analíticos de fácil execução e alta produtividade. Informações confiáveis sobre os teores de vitaminas poderão ser obtidas somente com métodos analíticos validados. Objetivos: Validar metodologias analíticas e avaliar o teor de vitaminas antioxidantes em suplementos adquiridos no comércio do município de São Paulo - Brasil, o efeito do armazenamento nestes compostos e confrontar os valores analisados com os valores declarados na rotulagem. Métodos: As metodologias analíticas para determinação de vitaminas antioxidantes por cromatografia líquida de alta eficiência com detector de arranjo de diodos (CLAE-DAD) e de vitamina C por titulação potenciométrica foram validadas para as matrizes sólidas, oleosas e líquidas de suplementos vitamínicos. A estabilidade das vitaminas foi avaliada a cada 6 meses durante 12 meses de armazenamento e a avaliação da rotulagem foi realizada de acordo com as legislações vigentes no Brasil. Resultados: Para os métodos cromatográficos, os limites de detecção (LDs) e de quantificação (LQs) variaram entre 0,3 e 4,3 µg/mL, e entre 0,5 e 14,0 µg/mL respectivamente. As recuperações dos padrões adicionados nas matrizes variaram entre 92 por cento e 109 por cento e entre 86 por cento e 108 por cento no material de referência. A repetitividade foi calculada pelo desvio padrão relativo (RSD), apresentando valores entre 0,2 por cento e 9,6 por cento . Para a determinação de vitamina C pelo método potenciométrico, o LD e o LQ foram respectivamente 1 mg e 3 mg; a recuperação no material de referência foi de 99,8 por cento e a precisão variou entre 0,4 e 3,9 por cento . Das 57 amostras avaliadas, 59 por cento e 35 por cento apresentaram teores de vitaminas A e E respectivamente, abaixo dos valores declarados no rótulo; por outro lado, 20 por cento das amostras apresentaram teores de vitamina E acima dos valores declarados. Em relação aos teores de vitamina C, 60 por cento das amostras estavam de acordo com os valores declarados. O estudo da estabilidade demonstrou degradação significativa das vitaminas A, E e C em aproximadamente 90 por cento das amostras com 12 meses de armazenamento. Na avaliação da rotulagem dos suplementos vitamínicos, 47 das amostras apresentaram uma ou mais irregularidades. Conclusão: Os métodos propostos se mostraram adequados para análise de diferentes matrizes de suplementos vitamínicos. Os resultados das análises de vitaminas nestes produtos mostraram a necessidade urgente de monitoramento em conjunto com ações de fiscalização, pois verificou-se que a maioria das amostras não atenderam a legislação, principalmente quanto aos teores declarados na informação nutricional da rotulagem. A sobredosagem de vitaminas pode ser necessária para manter os teores declarados durante o armazenamento, porém, a quantidade adicional de vitamina a ser incluída no suplemento deve estar dentro de limites seguros e depende de cada amostra, pois além da matriz, diversos fatores relacionados aos compostos e à embalagem também podem influenciar na estabilidade das vitaminas.

Tungsten coil atomic emission spectrometry combined with dispersive liquid–liquid microextraction: A synergistic association for chromium determination in water samples

A novel and environment friendly analytical method is reported for total chromium determination and chromium speciation in water samples, whereby tungsten coil atomic emission spectrometry (WCAES) is combined with in situ ionic liquid formation dispersive liquid–liquid microextraction (in situ IL-DLLME). A two stage multivariate optimization approach has been developed employing a Plackett–Burman design for screening and selection of the significant factor involved in the in situ IL-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were complexant concentration: 0.5% (or 0.1%); complexant type: DDTC; IL anion: View the MathML sourcePF6−; [Hmim][Cl] IL amount: 60 mg; ionic strength: 0% NaCl; pH: 5 (or 2); centrifugation time: 10 min; and centrifugation speed: 1000 rpm. Under the optimized experimental conditions the method was evaluated and proper linearity was obtained with a correlation coefficient of 0.991 (5 calibration standards). Limits of detection and quantification for both chromium species were 3 and 10 µg L−1, respectively. This is a 233-fold improvement when compared with chromium determination by WCAES without using preconcentration. The repeatability of the proposed method was evaluated at two different spiking levels (10 and 50 µg L−1) obtaining coefficients of variation of 11.4% and 3.6% (n=3), respectively. A certified reference material (SRM-1643e NIST) was analyzed in order to determine the accuracy of the method for total chromium determination and 112.3% and 2.5 µg L−1 were the recovery (trueness) and standard deviation values, respectively. Tap, bottled mineral and natural mineral water samples were analyzed at 60 µg L−1 spiking level of total Cr content at two Cr(VI)/Cr(III) ratios, and relative recovery values ranged between 88% and 112% showing that the matrix has a negligible effect. To our knowledge, this is the first time that combines in situ IL-DLLME and WCAES.

Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L−1 of mercury. Standard addition calibration curves using standards between 0 and 20 μg L−1 gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L−1, and from 1.1 to 1.3 μg L−1, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L−1). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L−1 as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).

Historical sea ice of the Baltic Sea (1960/61-78/79)

The Baltic Sea is a seasonally ice-covered, marginal sea in central northern Europe. It is an essential waterway connecting highly industrialised countries. Because ship traffic is intermittently hindered by sea ice, the local weather services have been monitoring sea ice conditions for decades. In the present study we revisit a historical monitoring data set, covering the winters 1960/1961 to 1978/1979. This data set, dubbed Data Bank for Baltic Sea Ice and Sea Surface Temperatures (BASIS) ice, is based on hand-drawn maps that were collected and then digitised in 1981 in a joint project of the Finnish Institute of Marine Research (today the Finnish Meteorological Institute (FMI)) and the Swedish Meteorological and Hydrological Institute (SMHI). BASIS ice was designed for storage on punch cards and all ice information is encoded by five digits. This makes the data hard to access. Here we present a post-processed product based on the original five-digit code. Specifically, we convert to standard ice quantities (including information on ice types), which we distribute in the current and free Network Common Data Format (NetCDF). Our post-processed data set will help to assess numerical ice models and provide easy-to-access unique historical reference material for sea ice in the Baltic Sea. In addition we provide statistics showcasing the data quality. The website http://www.baltic-ocean.org hosts the post-processed data and the conversion code.

Nonlinear speech analysis algorithms mapped to a standard metric achieve clinically useful quantification of average Parkinson's disease symptom severity

The standard reference clinical score quantifying average Parkinson's disease (PD) symptom severity is the Unified Parkinson's Disease Rating Scale (UPDRS). At present, UPDRS is determined by the subjective clinical evaluation of the patient's ability to adequately cope with a range of tasks. In this study, we extend recent findings that UPDRS can be objectively assessed to clinically useful accuracy using simple, self-administered speech tests, without requiring the patient's physical presence in the clinic. We apply a wide range of known speech signal processing algorithms to a large database (approx. 6000 recordings from 42 PD patients, recruited to a six-month, multi-centre trial) and propose a number of novel, nonlinear signal processing algorithms which reveal pathological characteristics in PD more accurately than existing approaches. Robust feature selection algorithms select the optimal subset of these algorithms, which is fed into non-parametric regression and classification algorithms, mapping the signal processing algorithm outputs to UPDRS. We demonstrate rapid, accurate replication of the UPDRS assessment with clinically useful accuracy (about 2 UPDRS points difference from the clinicians' estimates, p < 0.001). This study supports the viability of frequent, remote, cost-effective, objective, accurate UPDRS telemonitoring based on self-administered speech tests. This technology could facilitate large-scale clinical trials into novel PD treatments.

Elemental Analysis of Biological Matrices by Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry (LA-HR-ICP-MS) and High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS)

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

The effect of a reduction of nitrogen and phosphorus to eutrophic and mesotrophic conditions towards silver nanoparticle (AgNP) on freshwater green algae species

We investigated the sensitivity of algae towards silver nanoparticles with OECD test medium and lower nutrient concentrations under standard test conditions to improve comparability and to exclude any other confounding factor aside nutrient levels. Two unicellular freshwater microalgae Desmodesmus subspicatus and Raphidocelis subcapitata were chosen due to their status as standard test organisms for the algae growth inhibition test and the response to changes in nutrient supply was compared. The original medium was used as the reference (standard). For the other four media, the amount of either nitrogen or phosphorus in the medium was lowered from half (50%) to one-fourth (25 %) of that of the OECD guideline, resulting in the following media: 50% N, 25% N, 50% P and 25% P medium. As test substance, the OECD reference material NM-300K was used. For this reason, the characterization of AgNP was done using DLS and Absorption spectra (UV/vis). Actual silver concentrations and ionic silver concentrations were measured at the highest test concentration used (100 µg Ag L-1) in R. subcapitata treatments only to reduce the number of samples. All tests were run according to the OECD guideline 201 with sterilized 50 mL cell culture flask. Each medium was tested using the test conditions for culturing with 3 replicates. Test concentrations for both algae species were 0, 25, 50 and 100 µg Ag L-1 for OECD, 50% P and 25% P while for both N reductions, the silver concentrations were 0, 10, 25 and 100 µg Ag L-1. Samples for determining the algal density were taken at every 24 h.

Desenvolvimento de método empregando DLLME para extração e pré-concentração de ferro em amostras de água com diferentes salinidades

Neste trabalho foi desenvolvido e validado um método analítico para a determinação de Fe total em amostras de água com diferentes salinidades empregando a microextração líquido-líquido dispersiva (DLLME), seguido de determinação espectrofotométrica na região do ultravioleta-visível. Nas extrações por DLLME, o Fe foi complexado com pirrolidina ditiocarbamato de amônio (APDC) e extraído após a injeção de uma mistura composta de 1,2-diclorobenzeno (solvente extrator) e etanol (solvente dispersor). Os fatores que influenciam a eficiência de extração (tipo e volume de solvente extrator e dispersor, concentração de APDC e tempo de extração) e subsequente determinação espectrofotométrica foram otimizados. Após otimização das condições, a curva de calibração foi linear entre 0,02 e 2,0 mg L-1 (r 2 = 0,9998) e os limites de detecção e quantificação do método foram de 6,1 e 18,3 µg L-1 , respectivamente. O fator de pré-concentração foi de 3,3. A exatidão foi avaliada em termos de recuperação, com variação entre 90 e 102% e desvio padrão relativo (RSD) inferiores a 12%. A exatidão do método também foi avaliada utilizando um material de referência certificado (SRM 1643e, Elementos Traço em Água), o qual apresentou concordância de 104% e RSD de 5%. O método foi aplicado para amostras de água com diferentes salinidades, como água mineral, estuarina e de alto mar. Além disso, o método proposto apresentou concordância da ordem de 95%, quando comparado com o método 1,10-fenantrolina para a determinação de Fe total.

In Situ Characterization of Optical Absorption by Carbonaceous Aerosols: Calibration and Measurement

Light absorption by aerosols has a great impact on climate change. A Photoacoustic spectrometer (PA) coupled with aerosol-based classification techniques represents an in situ method that can quantify the light absorption by aerosols in a real time, yet significant differences have been reported using this method versus filter based methods or the so-called difference method based upon light extinction and light scattering measurements. This dissertation focuses on developing calibration techniques for instruments used in measuring the light absorption cross section, including both particle diameter measurements by the differential mobility analyzer (DMA) and light absorption measurements by PA. Appropriate reference materials were explored for the calibration/validation of both measurements. The light absorption of carbonaceous aerosols was also investigated to provide fundamental understanding to the absorption mechanism. The first topic of interest in this dissertation is the development of calibration nanoparticles. In this study, bionanoparticles were confirmed to be a promising reference material for particle diameter as well as ion-mobility. Experimentally, bionanoparticles demonstrated outstanding homogeneity in mobility compared to currently used calibration particles. A numerical method was developed to calculate the true distribution and to explain the broadening of measured distribution. The high stability of bionanoparticles was also confirmed. For PA measurement, three aerosol with spherical or near spherical shapes were investigated as possible candidates for a reference standard: C60, copper and silver. Comparisons were made between experimental photoacoustic absorption data with Mie theory calculations. This resulted in the identification of C60 particles with a mobility diameter of 150 nm to 400 nm as an absorbing standard at wavelengths of 405 nm and 660 nm. Copper particles with a mobility diameter of 80 nm to 300 nm are also shown to be a promising reference candidate at wavelength of 405 nm. The second topic of this dissertation focuses on the investigation of light absorption by carbonaceous particles using PA. Optical absorption spectra of size and mass selected laboratory generated aerosols consisting of black carbon (BC), BC with non-absorbing coating (ammonium sulfate and sodium chloride) and BC with a weakly absorbing coating (brown carbon derived from humic acid) were measured across the visible to near-IR (500 nm to 840 nm). The manner in which BC mixed with each coating material was investigated. The absorption enhancement of BC was determined to be wavelength dependent. Optical absorption spectra were also taken for size and mass selected smoldering smoke produced from six types of commonly seen wood in a laboratory scale apparatus.

Análise comparativa entre as propriedades do gesso obtido de rejeito da produção de sal e gesso comerciais

The environmental impacts, caused by the solid residues generation, are an often quoted concern nowadays. Some of these residues, which are originated from different human activities, can be fully reused, reducing the effects of the poor waste management on the environment. During the salt production process, the first formed crystals are discarded as industrial waste. This is mainly made of gypsum that is a calcium sulfate dihydrate (CaSO4.2H2O). The gypsum in question may go through a calcination process due to the plaster (CaSO4.0,5H2O) production and then the application on the cement industry. Considering the necessity of development and application for these industrial wastes, this paper aims to analyze the plaster, called Salgesso, from the gypsum that was generated during the salt production, and its use viability on the civil construction industry in order to create environmental and economical benefits. For characterization, the following experiments were performed: X-ray Fluorescence (XRF), X-ray Diffraction (XRD), thermal analysis (TG/DTG) and Scanning Electron Microscopy (SEM) with EDS. The following tests were also performed to obtain the mechanical characteristics: Thinness Modulus, Unit Mass, Setting Time and Compressive Resistance. Three commercial plasters used on civil construction were taken as references. All of these tests were performed according to the current standards. It was noticed that although there were some conflicting findings between the salt and commercial plasters in all of the studied properties, the Salgesso has its values within the standard limits. However, there is the possibility to improve them by doing a more effective calcination process. Three commercial plasters, used in construction, were used as reference material. All tests were performed according to standards in force. It was observed that although some tests present conflicting findings between the salt and gypsum plasters commercial properties in all of the studied Salgesso have values within the limits imposed by the standard, but can be improved simply by calcination process more effective

Access to public sector information : law, technology and policy

On the back of the growing capacity of networked digital information technologies to process and visualise large amounts of information in a timely, efficient and user-driven manner we have seen an increasing demand for better access to and re-use of public sector information (PSI). The story is not a new one. Share knowledge and together we can do great things; limit access and we reduce the potential for opportunity. The two volumes of this book seek to explain and analyse this global shift in the way we manage public sector information. In doing so they collect and present papers, reports and submissions on the topic by leading authors and institutions from across the world. These in turn provide people tasked with mapping out and implementing information policy with reference material and practical guidance. Volume 1 draws together papers on the topic by policymakers, academics and practitioners while Volume 2 presents a selection of the key reports and submissions that have been published over the last few years.

Encyclopedia contributions: Entries H-M in Oxford Companion to Australian Gardens

The Oxford Companion to Australian Gardens is the first comprehensive reference book to cover all aspects of Australian gardens, and the history of gardening and garden design in Australia. The book is comprised of over 400 thematic, bibliographic and place based entries, and is extensively illustrated and cross referenced to ensure ease of use and thorough coverage of the field. The Companion contributes to the understanding of gardens and gardening by including entries on designed landscapes, agriculture, architecture, art, botany, ecology, forestry, horticulture, landscape architecture, town planning and viticulture and will become the standard reference on the subject. Herbert,