published_or_final_version / Chemistry / Master / Master of Philosophy

High-pressure homogenization using a new flat valve homogenizer in combination with enzymatic digestion with a crude protease was investigated as a means of releasing Se compounds from zoological and botanical matrices prior to slurry introduction GF-AAS. Timed trials with four zoological certified reference materials (CRMs), three botanical reference materials (RMs), and a food crop indicated that Se release was quantitative after homogenization or became quantitative within 1 h of digestion at 60°C. / The same technique was employed on five animal feed samples. / A new model of homogenizer equipped with ceramic homogenizing valve was evaluated in terms of analyte metal contamination levels within the final sample dispersion. / Five animal feed samples and four wood pulp samples, were investigated for their content of Cu, Fe and Mn using high-pressure homogenization as the sample preparation technique prior to GF-AAS. Dispersions of dried animal feeds were sub-sampled reliably after 7 days of storage at 4°C. Trials on pulp samples indicated that pulps could be sub-sampled reliably after 1 day of storage. (Abstract shortened by UMI.)

In this thesis, new approaches to direct trace metals analysis of solid samples by inductively coupled plasma spectroscopy were investigated using laser ablation and thermal vaporization systems for solid sample introduction of biological, environmental, and pharmaceutical samples. / Laser ablation with inductively coupled plasma atomic emission spectroscopy (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) was applied to pharmaceutical tablets. Precision of analysis depended on laser parameters and could be improved using signal ratios. The feasibility of using laser ablation-ICP-MS for detecting natural levels of mercury along a single human hair strand was also demonstrated. / As well, the use of an induction-heating electrothermal vaporizer (IH-ETV) coupled to an ICP-MS was successful in determining mercury concentrations in a single human hair strand. Methodologies for multielement analysis of powdered hair were also explored using IH-ETV-ICP-MS. While calibration by reference hair materials showed promise, calibration methods by liquid standards were not suitable for any element. Detection limits achieved for most elements were below natural levels found in human hair. / IH-ETV-ICP-AES was also applied to the analysis of analyze-laden chromatographic powder. This study showed potential problems that may arise due to the methodology taken to analyze such materials. Finally, recommendations for future investigations and methodologies for laser ablation and thermal vaporization are discussed.

The scope of these studies was two-fold: to evaluate high pressure homogenized slurries as a rapid means of screening wood pulps for their Cu, Mn and Fe content and to evaluate the high pressure homogenization in combination with chelating agents or enzymatic digestion for the liberation/extraction of metal ions from this matrix. / Cu, Mn and Fe were determined successfully in pulp samples using high-pressure homogenization prior to slurry introduction-GF-AAS. The analysis time of the method from sample acquisition to determination was of the order of a few minutes per sample. / Different cellulose swelling/dissolution agents were evaluated for the generation of quasi-stable pulp suspensions, rich in cellulose. High-pressure homogenization alone or in combination with chelating agents or enzymatic digestion was also investigated as a means of quantitatively releasing these metal ions into the liquid phases. / A new model of homogenizer equipped with ceramic homogenizing valve with a few modifications was evaluated in terms of metal contamination levels within the final sample dispersion. (Abstract shortened by UMI.)

Fifty fragments of young, fresh basalts from the Explorer Ridge, Paul Revere Ridge (Fracture Zone), Dellwood Knolls, and the J. Tuzo Wilson Knolls have been analysed for 12 major and minor elements, as well as 11 trace elements, by X-ray fluorescence spectrometry. Rare earth element concentrations in 25 of the samples have been determined by instrumental neutron activation, and Sr⁸⁷/Sr⁸⁶ ratios have been obtained for 11 of the basalts. The Explorer Ridge basalts have major element compositions similar to most mid-ocean ridge basalts (MORB), and can be classified as ferrobasalts, similar to those of the southern Juan de Fuca Ridge. The incompatible minor and trace elements K, Ti, Rb, Zr, and Nb are weakly to strongly enriched in the Explorer samples, with respect to MORB, part of which is the result of crystal fractionation. The observed trace element and light rare earth element (LREE) enrichment of many of the samples, particularly those from Explorer Deep, suggest that a weak hotspot may exist beneath the Explorer Deep. The adjacent ridge segments, Explorer Rift and the Southern Explorer Ridge, are erupting basalts both enriched and depleted in incompatible elements, which could be an indicator of a chemically heterogenous mantle source, or may be the result of intermittent injection of enriched magmas from the postulated hotspot beneath Explorer Deep into areas producing normal MORB. The enriched basalts do not have significantly different Sr⁸⁷/Sr⁸⁶ ratios from the depleted basalts. All the samples fall within the range of values typical for Juan de Fuca and Gorda Ridge basalts, and East Pacific Rise tholeiites in general. Thus, although the source areas for the 2 basalt types may differ chemically, they are similar radiogenically, unlike-other hypothetically plume-influenced areas such as the Mid-Atlantic Ridge at 45°N and the FAMOUS area. The basalts from the northwest and southeast Dellwood Knolls appear to be related by crystal fractionation, based on major element analysis. However, the very different REE patterns and Sr⁸⁷/Sr⁸⁶ ratios exhibited by the two knolls suggest that they have different mantle sources, one typically depleted (northwest knoll) and one chemically and radiogenically enriched (southeast knoll). In terms of their major and trace element chemistry, the J. Tuzo Wilson Knolls basalts are typical of late-stage volcanism on ocean islands associated with mantle plumes. The hawaiites strongly resemble alkali basalts dredged from several seamounts in the Pratt-Welker Chain, which are co-latitudinal with the J. Tuzo Wilson Knolls on a small circle about the Pacific-Hotspot pole of rotation. Geochronological evidence questions the hypothesis that the mantle plume responsible for Pratt-Welker volcanism is also the source for the J. Tuzo Wilson basalts. The existence of a second mantle plume, 300 km southeast of the first, would explain minor chemical and physiographical differences between the Knolls and the other Pratt-Welker seamounts, as well as the evidence for two phases of volcanism on the southeastern seamounts of the chain. A second plume also explains the coeval volcanism of Bowie Seamount and the J. Tuzo Wilson Knolls. Recent geophysical evidence suggests that the J. Tuzo Wilson Knolls are also part of the Explorer-Dellwood spreading system. Although the JTW basalts are plume-type basalts chemically, the situation appears to be somewhat analagous to other ridge segments where plumes are coincident with the ridge itself. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

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One of the first concerns for forensic anthropologists in dealing with skeletal remains in the Australian context is the determination of whether the remains are of anthropological, historical or archaeological interest. If fewer than 75 years have elapsed since death, remains are classified as anthropological and of forensic interest. However, an accurate and reliable method for estimating time since death (TSD) from human skeletal remains has thus far eluded forensic anthropologists. This study investigates the application in an Australian context of a novel approach proposed by Swift (2001) to dating skeletal remains from their contained levels of radioisotopes 210Po, 238U and 226Ra and trace elements. Radionuclide activity concentrations were determined using alpha and gamma spectrometry. Trace element concentrations were measured on three separate occasions using inductively coupled plasma mass spectrometry (ICP-MS). Discriminant analysis of the combination of activity concentration values for 210Po, 238U and 226Ra indicated the possibility of separation of bones derived from individuals who had died in the three eras of interest. Additionally, variations in the concentration levels of specific trace elements and certain inter-element relationships between elements also showed significant correlations with TSD. The study could not be exhaustive as access to human skeletal material was limited and additionally, the archaeological material had a different origin and post-death history to material from the more recent past. However, trend lines for inter-relationships between specific metals and for radionuclides indicated that all material fitted the same generally projected trends and as such, inferences with respect to variations of trace elements and radionuclides could be made with confidence. Bone radionuclide activity and calcium concentrations were all significantly higher in bones from the archaeological era than those from more recent eras, while trace lead concentrations contained in samples from the more recent historical era were significantly higher than those from other eras. Barium, lanthanum, rubidium, strontium, cerium and neodymium concentrations were all significantly correlated with one another and with radionuclide activity concentrations. Differences were found between the patterns of radionuclide activity and trace element concentrations between the skull and femur. The results of this study lend support to suggestions that multivariate analysis of trace element concentrations and radionuclide activity levels could aid in the estimation of time since death from skeletal remains in Australia. Although this study made use of only a limited amount of material, results clearly indicated the need to take into account variations arising from lifetime activities, diagenesis and bone type in applying the techniques to estimations of time since death. It highlights the need for a large-scale study using bone of known ages that systematically examines these influences on the estimation of time since death.

Orientadores: Jacinta Enzweiler, Otávio Augusto Boni Licht / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-22T23:05:18Z (GMT). No. of bitstreams: 1 Barros_FernandaCeciliaDias_M.pdf: 7061274 bytes, checksum: fb0d51f8e86e9f4450483280c29b5fc9 (MD5) Previous issue date: 2012 / Resumo: O uso da geoquímica de gases ou emanometria é um método com grande potencial em prospecção mineral de depósitos não aflorantes e/ou encobertos por rochas não-mineralizadas, porém ainda é pouco utilizado. A temperatura de formação da mineralização é um fator determinante à presença de alguns elementos- traço, dentre eles o Hg. Existe uma predileção do Hg por depósitos de zinco de baixa temperatura do tipo epitermal e stratabound. O depósito de Zn-Pb-Cu de Santa Maria, localizado na Bacia do Camaquã, município de Caçapava do Sul (RS) contém Hg associado à mineralização e, por isso, foi escolhido como área piloto para testes de emanometria. O objetivo desta pesquisa foi medir a concentração de Hg gasoso in situ e avaliar a sua potencialidade na prospecção de depósitos sulfetados de zinco. A concentração de Hg gasoso no ar foi medida ao longo de um percurso de 11 km com um espectrômetro portátil de absorção atômica a fim de definir a concentração de Hg atmosférico local, que variou de 2 a 10 ng/m3. O Hg gasoso no solo foi medido em buracos escavados em profundidades de 30 e 50 cm e a sucção do ar para o interior do espectrômetro, atingindo valor máximo de 19 ng/m3 acima da mineralização. Amostras de solo e de duas espécies de vegetação também foram analisadas. O tratamento estatístico dos resultados mostrou que o background de Hg medido nas amostras de solo variou entre 3,9 e 28 ng/g Hg, enquanto o background obtido para as amostras de carqueja (Baccharis trimera) variou entre 10,5 e 38 ng/g Hg. Os valores de background local e o padrão de anomalia gerado demonstraram que o Hg atmosférico, o Hg gasoso (especialmente em 30 cm) e a carqueja foram os meios amostrais mais eficientes para detectar a mineralização pela medição do mercúrio. As amostras de solo e vassourinha (Dodonea viscous) geraram uma fraca resposta geoquímica da mineralização. A localização e a dimensão das anomalias de Hg puderam ser associadas à mineralização sulfetada de Santa Maria, ao sistema de Falha Três Figueiras e atividades antrópicas na área / Abstract: The use of gas geochemistry or emanometry is a method with great potential in mineral exploration of deep ore deposits covered by non-mineralized rocks, although rarely used. The temperature of the mineralization is a determinant factor for the presence of certain trace elements, including Hg. There is an affinity of Hg for low temperature zinc deposits, especially epithermal and stratabounds type deposits. The Zn-Pb-Cu deposit of Santa Maria, located in Camaquã Basin, Caçapava do Sul (RS) contains Hg associated to the mineralization and was chosen as pilot area to test emanometry. The objective of this research was to measure gaseous Hg in situ and to evaluate the potentiality of its use in prospection of zinc sulfide deposits. The air Hg gas concentration was measured along a trajectory of 11 km with a portable atomic absorption spectrometer, resulting in atmospheric Hg concentrations that varied between 2 to 10 ng/m3. The Hg gas in soil was measured in holes excavated at depths of 30 and 50 cm by air suction into the spectrometer, attaining 19 ng/m3 over de mineralization. Soils and two species of vegetation were also sampled and analyzed. The statistical treatment of data showed that background Hg in soils samples varied between 3.9 and 28 ng/g, while the Hg in gorse (Baccharis trimera) varied between 10.5 and 38 ng/g. The local background values and the pattern of the anomaly showed that atmospheric Hg, gas Hg in soil (especially at 30 cm depth) and gorse were the most efficient sample media to detect the mineralization by using Hg. The soil and florida hopbush (Dodonea viscous) produced a weak geochemical response of the mineralization. The location and the dimension of Hg anomalies could be associated to the Santa Maria deposit, to the Três Figueiras fault system and to anthropogenic activities in the area / Mestrado / Geologia e Recursos Naturais / Mestra em Geociências