The geology and mining industries rely heavily on reliable quantitative data on the elemental composition of various rocks and minerals. The analytical accuracy of the best measurement systems are, however, limited to the accuracy with which the composition of a generally accepted reference sample is known, which serves to calibrate an instrument or validate a method. Thus, there is an established market for well-characterised reference materials which trade internationally as value added commodities. International organisations prepare strict procedures for the preparation and certification of these reference materials. ISO/REMCO is the ISO Committee on Reference Materials that carries out and encourages a broad international effort for the harmonisation and promotion of reference materials, their production and their application. In view of recent developments in ISO/REMCO related to updated guides and changes in definitions, SARM 1 to 6 (the NIMROCs) are in danger of losing their status as certified reference materials (CRMs). Due to the continued popularity of the NIMROCs and the availability of bulk sample, the National Metrology Institute of South Africa (NMISA) embarked on a project to re-certify three materials from the suite of six igneous rock samples, i.e. SARM 2 (Syenite), SARM 3 (Lujavrite) and SARM 4 (Norite). The aim of the re-certification project was to re-certify the materials with a single primary reference measurement procedure in a single laboratory to comply with one of the possible routes to the establishment of metrological traceability as described in ISO Guide 34. Eight elements (Ba, Sr, Cd, Mo, Cu, Ni, Pb and Zn) of SARM 2, SARM 3 and SARM 4 were value assigned during this study to ensure that they comply with the ISO Guide 30 and ISO GUM requirements for traceability and measurement uncertainty. Traceability to the SI units of mass and amount of substance at the highest level of accuracy was established by employing the definitive technique of double isotope dilution ICP-MS, with primary assay standards traceable to the NIST SRM 3100 series and gravimetrically prepared samples. For the first time assigned values with uncertainty statements for these elements in these reference materials were calculated according to the ISO GUM and CITAC/EURACHEM guidelines for expression of the uncertainty of measurement. The uncertainties of the assigned values for all elements were within the target of 5% relative set during the development of the methodology, except for elements in concentrations below 10 mg.kg-1. The ID-ICP-MS results are supported by good comparability with results reported in the literature since 1978, as well as the original certified values published in 1978. The results from this study for all elements in these reference materials have the potential to become new certified values in accordance with the requirements of ISO Guides 34 and 35. This will improve the usefulness of these reference materials to the South African and international geology and mining communities for the purposes of analytical quality control and method validation in exploration and geochemical analysis. Confirmation of the homogeneity and stability of the remaining units of the reference materials is considered necessary to complete the re-certification project. / Thesis (PhD)--University of Pretoria, 2010. / Chemistry / unrestricted

Elemental analysis can become an important piece of evidence to assist the solution of a case. The work presented in this dissertation aims to evaluate the evidential value of the elemental composition of three particular matrices: ink, paper and glass. In the first part of this study, the analytical performance of LIBS and LA-ICP-MS methods was evaluated for paper, writing inks and printing inks. A total of 350 ink specimens were examined including black and blue gel inks, ballpoint inks, inkjets and toners originating from several manufacturing sources and/or batches. The paper collection set consisted of over 200 paper specimens originating from 20 different paper sources produced by 10 different plants. Micro-homogeneity studies show smaller variation of elemental compositions within a single source (i.e., sheet, pen or cartridge) than the observed variation between different sources (i.e., brands, types, batches). Significant and detectable differences in the elemental profile of the inks and paper were observed between samples originating from different sources (discrimination of 87 – 100% of samples, depending on the sample set under investigation and the method applied). These results support the use of elemental analysis, using LA-ICP-MS and LIBS, for the examination of documents and provide additional discrimination to the currently used techniques in document examination. In the second part of this study, a direct comparison between four analytical methods (µ-XRF, solution-ICP-MS, LA-ICP-MS and LIBS) was conducted for glass analyses using interlaboratory studies. The data provided by 21 participants were used to assess the performance of the analytical methods in associating glass samples from the same source and differentiating different sources, as well as the use of different match criteria (confidence interval (±6s, ±5s, ±4s, ±3s, ±2s), modified confidence interval, t-test (sequential univariate, p=0.05 and p=0.01), t-test with Bonferroni correction (for multivariate comparisons), range overlap, and Hotelling’s T2 tests. Error rates (Type 1 and Type 2) are reported for the use of each of these match criteria and depend on the heterogeneity of the glass sources, the repeatability between analytical measurements, and the number of elements that were measured. The study provided recommendations for analytical performance-based parameters for µ-XRF and LA-ICP-MS as well as the best performing match criteria for both analytical techniques, which can be applied now by forensic glass examiners.

Los efectos de escala espacial son un tema de relevancia en Hidrología dada la necesidad de vincular las disparidades de escala entre los procesos, las observaciones y las modelaciones. La existencia de procesos dominantes a diferentes escalas, el funcionamiento no lineal de los sistemas hidrológicos y la fuerte variabilidad espacio-temporal son los principales factores que controlan los problemas de escala y condicionan los métodos de escalado. La generación de conocimiento relacionado con este tema es importante para mejorar la comprensión y representación de los procesos hidrológicos. En la primera parte de esta tesis se estudia el problema de la agregación espacial de parámetros hidrológicos, la importancia de la organización espacial para la formulación de una separación de escalas espaciales utilizando el concepto de área elemental representativa (REA) y su relación con la definición de un tamaño de celda óptimo para la modelación hidrológica distribuida. Para dicho análisis se ha utilizado la conceptualización del proceso de infiltración del modelo hidrológico distribuido (TETIS) y se han desarrollado experimentos sintéticos utilizando campos de parámetros correlacionados espacialmente. Los resultados de los experimentos numéricos mostraron que al escalar los parámetros efectivos de la microescala a la mesoescala, sus valores dependen en las variables de entrada, variables de estado y la heterogeneidad de los parámetros en la microescala. Las simulaciones han demostrado que la varianza de los parámetros efectivos estimados en la mesoescala disminuye cuando aumenta el ratio entre el tamaño de celda en la mesoescala y la longitud de correlación. Esta propiedad es fundamental para identificar un tamaño de celda con las características de REA y que minimice la propagación de la incertidumbre de los parámetros. / Barrios Peña, MI. (2011). ESTUDIO DEL EFECTO DE ESCALA ESPACIAL EN UN MODELO HIDROLÓGICO DISTRIBUIDO [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/14180 / Palancia

The widespread use of titanium and its alloys in structural applications has been limited to few highend applications. The dominant reason for this being cost implications. These high costs arise from extracting titanium from its mineral form as well as that of the manufacturing processes to develop a final product. Since producing titanium products includes expensive starting stock, high machinability costs and high wastage, a need for a process that may minimize one or more of these factors is necessary. One such technology that exists is a branch of powder metallurgy (PM), direct powder rolling (DPR) which allows for a continuous approach to produce strip or sheet metal. Products developed by this process are however known to possess inferior properties to its wrought counterpart. The present study comprises of a parametric study observing how two different blends of powder differ in the development of Ti-6Al-4V strip by employing the blended elemental (BE) approach to direct powder rolling. The objectives of this work include predicting the compaction behavior of the two respective blends during powder rolling to inform the production of high density green strip and to compare the outcomes of the prediction method to experimentally determined results using a gravity-fed laboratory-scale rolling mill with roll diameter of 265 mm and roll width of 150 mm. Johanson’s rolling theory was applied to predict rolling outcomes and a fixed set of rolling parameters were implemented for the simulation and experimental segment of this dissertation. The two blends being investigated include blending titanium powder with an elemental blend consisting of aluminium and vanadium powders (B1) and a master alloy blend of a 60Al-40V master alloy (B2). These two blends were used to validate the Johanson simulated rolling data. Fixed parameters applied to the rolling mill included using a roll speed of 14 rpm, roll face width of 65 mm and gravity-fed hopper outlet diameter of 25 mm. Variable roll gaps of 0.5, 1 and 1.5 mm were studied. Average relative green densities of B1 and B2 strips achieved at a roll gap of 1 mm were 77% and 73% respectively. Rolling performance of the B1 powder blend were higher than that of B2, reaching higher green densities and showing superior formability, as rolling at smaller roll gaps was achievable for B1 and not B2. Green strength of B1 and B2 strips at a roll gap of 1 mm reflected similar outcomes where B1 strips required a greater breaking load to fracture samples when compared to B2 indicating a stronger self-supporting compact. Furthermore, the Johanson rolling model proved to overestimate reasonable roll pressure values, although, the general trend of compactibility between B1 and B2 powder blends was reasonably predicted showing B1 to be more compressible than B2 during powder rolling. iv Subsequent sintering at 1200 °C for 3 hours in a vacuum environment was applied to green strips to further densify and homogenize strips. Average relative sintered densities achieved for B1 and B2 strips rolled at a roll gap of 1 mm were 78% and 87% respectively. While green densities of B1 strips were higher than that of B2 strips, it was evident that the addition of the 60Al-40V master alloy to blend B2 resulted in superior sinterability as final sintered densities surpassed that of B1, even when starting at a lower green density after rolling. SEM/EDX was used to evaluate what effect sintering had on homogenization. A standard wrought Ti-6Al-4V specimen was used as the benchmark to compare homogenization results. B2 strips homogenized more than B1 strips when comparing to the baseline wrought sample. It was concluded that both B1 and B2 powders used to create Ti-6Al-4V strip by direct powder rolling (DPR) exhibited high levels of porosity and a subsequent step is necessary to fully densify the material. While B1 strips exhibit superior rollability with higher green densities and green strength; after applying a sintering practice to both B1 and B2 strips, B2 sintered densities surpassed those of B1 and prove to homogenize to a greater degree than B1 strips. The superior roll compaction ability and inferior sinterability for B1 powders was attributed to the elemental powder, aluminium. While the addition of ductile aluminium to B1 aids roll compaction, its low melting point results in large pores evolving at sintering temperatures almost twice its melting point.

This work is a research on the topic of reactive nanoparticles and their agitation into the solder paste, which it also describes. It describes in detail the properties of each solder alloys. It explains the creation of intermetallic layers in the soldering process and examines their structure. It also focuses on the evaluation and methodology of testing the properties of solder pastes. In the practical part, individual tests are performed with PF606 and PF610 solder paste.

Presented master thesis dealt with the analysis of garlic and onion samples and tried to find correlations between chemical composition and country of origin. The parameters examined were dry content, crude protein content, concentration of phenolic compunds, carbohydrate content (fructose, glucose), alliin content and concentration of selected elements (P, Mg, Ca, Na, K, Fe, Zn). Average content of dry matter of fresh samples was 35,84 ±2,12 g/100 g and of dehydrated samples was 90,61 ±2,90 g/100 g. Concentration of phenolic compounds was measured spectrophotometrically with Folin-Ciocault reagent. Average phenolic compounds content of samples was 0,1840 ±0,1286 GAE g/100 g. Crude protein content was measured by Kjeldahl method, and calculated from total nitrogen content. Carbohydrates were measured by HPLC-ELSD after hydrolysis of fructans. Average content of fructose of garlic samples was 57,014 ±0,863 g/100 g, of onion samples was 33,718 ±1,168 g/100 g. Average content of glucose of onion samples was 22,633 ±0,405 g/100 g. Alliin content was measured by HPLC-DAD method. Average alliin content of fresh samples was 4,644 ±0,446 g/100 g and of dehydrated samples was 1,962 ±0,180 g/100 g. Elemental analysis was conducted by ICP-OES method. Average concentration of selected elements was: P 2,15 ±0,11 mg/g, Mg 0,638 ±0,03 mg/g, Ca 1,246 ±0,05 mg/g, Na 0,550 ±0,08 mg/g, K 7,49 ±0,41 mg/g, Fe 79,3 ±6,16 mg/kg, Zn 11,4 ±3,33 mg/kg. Obtained data were statistically processed on significance level 0,05. Based on the principal components analysis, it was found, that the best parameters to differentiate samples from Czechia, Poland and Ukraine from other countries were content of nitrogen, phosphorus, magnesium, sodium and calcium. It was also discovered, that genus differences between onion and garlic have greater significance than geographical differences.

This diploma thesis deals with the elemental analysis of soft fruit species such as currants and gooseberries. The theoretical part contains botanical description of both species, then description of nutritional properties of the individual analyzed elements and ends with a list of analytical methods suitable for elemental analysis in the food science and with a description of preparation. The experimental part deals with sample preparation and its analysis afterwards with spectroscopic techniques. Samples of different varieties of gooseberries, black, red and white currant from “Výzkumný a šlechtitelský ústav ovocnářský v Holovousích, s.r.o.” have been used for the analysis. Samples were mineralized in concentrated HNO3 and analyzed by ICP-OES technique. Difference in resultant concentrations of the analyzed elements (Ca, Cu, Fe, K, Mg, Mn, Na, P, Zn) between individual varieties were statistically compared by Tukey’s multiple comparison method and results achieved have been as well compared with the results reported in available literature.

This Master’s thesis deals with the determination of selected micro and macro elements in bottled water purchased in retail chains Czech Republic. There are described macro elements and micro elements that occur in the waters, bottled waters legislation and the most frequent used instrumental methods for elemental analysis. In this work for the analysis of bottled water were used methods optical emission spectrometry with inductively coupled plasma (ICP-OES) and ion chromatography (IC). Elemental composition of bottled water after analysis corresponded to the composition indicated on the labels, there were recorded only minor deviations from the reported concentrations. All bottled water meets the conditions of the legislation of the Czech Republic. The measured data were statistically processed in the XL Stat program and by multivariate data analysis was examined whether it is possible to individual bottled water from each other based on the analyzes differentiate, which can help in verifying the authenticity of bottled water and in the detection of adulteration of bottled water for profit.

This master thesis deals with the analysis of nutritional properties of paprika condiment with different geographic origin. The theoretical part contains botanical description of red pepper (Capsicum annuum L.), its chemical composition, process of production of paprika and then they are described analytical methods suitable for determination of fundamental nutrional properties. Experimental part is focused on the preparation of samples and their analysis. In total, 11 samples were selected for the experiment, 5 of them had a protected designation of origin. These samples were from Slovakia, Hungary, Bulgary, Romania, Turkey and Spain. The Soxhlet extraction was used for the analysis of the fat content, Kjeldahl method was used to determine gross protein. High-performance liquid chromatography (HPLC) was chosen to determine carbohydrates and capsaicin. Induction-coupled plasma emission spectroscopy (ICP-OES) was used for elemental analysis. The results were compared with each other and with available databases and literature. For comparing and finding certain connections, the principal component analysis (PCA) was selected.

Determina si los niños de 5 años de una IEI pública de la UGEL 07 en Lima reducirían significativamente su latencia de acceso al léxico oral e incrementarían su vocabulario comprensivo oral, luego de participar en el PRACLO. El estudio tuvo un alcance explicativo y un diseño de tipo cuasiexperimental con pretest-postest y grupos intactos. Los participantes fueron 23 alumnos en el grupo experimental y 18 alumnos en el grupo control. Se concluye que el PRACLO reduce la latencia y mejora la precisión de acceso al léxico, así como el vocabulario comprensivo. En ese sentido, se aceptaron diez de las doce hipótesis (83%) planteadas, apreciándose que el tamaño del efecto de los cambios en los alumnos fluctuó de pequeño a grande. / Tesis