Self-propagating High-temperature Synthesis (SHS) is the synthesis of solid materials by a reaction wave propagating into the initial reactants, typically two metals, which can alloy exothermically. Typically, experiments are performed with the reactants in powder form, with relatively low density. Recent experiments by Bacciochini et al. revealed much larger flame speeds in densified powders near TMD (theoritical maximum density), obtained by the cold spray process. The present thesis investigates why the flame speed increases dramatically with an increase in density of the powders. The investigation rests on the analytical model formulated by Makino by controlling how the variables are affected by changes in density. Flame speed measurements were performed in mixtures of nickel (Ni) and aluminum (Al) at different initial densities. The density was varied by controlling the cold-pressing of the samples inside metallic channels and tubes. Experiments were also performed in ball-milled powders, in order to permit comparison with the experiments performed by Bacciochini in these mixtures at nearly maximum densities. The measurements revealed that the flame speed increases with the initial density, with a discontinuous transition occurring at approximately 60% theoretical maximum density (TMD). This transition also corresponds to the point where the powders deform plastically during the compaction process, suggesting that the intimate contact between the particles is responsible for the flame speed increase. The flame speed dependence on powder density is attributed to the changes in the heat conductivity of the pressed powders. At high densities, where the powders have plastically deformed, the continuous structure yields conductivities close to the idealized solid matrix. At these high densities, the conductivity was modeled using the Effective Medium Theory (EMT). Analytical predictions of the flame speed, using available thermo-chemical data for the Al-Ni system were found in good agreement with the present experiments at high densities. At low densities, since Al-Ni is a mixture of loose powders, the EMT model is no longer applicable. Thus, the thermal conductivity was experimentally measured and then was fitted using the semi-empirical model suggested by Aivazov. Using this data, Makino's model predicts the correct flame speed dependence observed experimentally. The present thesis has thus established that the dependence of flame speed on density is due mainly to the changes in the structure and thermal conductivity of the powders.

Chemical exposure in humans rarely consists of a single chemical. The everyday exposure is characterized by thousands of chemicals mainly present at low levels. Despite that fact, risk assessment of chemicals is carried out on a chemical-by-chemical basis although there is a consensus that this view is too simplistic. This thesis aims to validate a statistical method to study the impact of mixtures of contaminants and to use that method to investigate the associations between circulating levels of a large number of environmental contaminants and atherosclerosis and the metabolic syndrome in an elderly population. Contaminants measured in the circulation represented various classes, such as persistent organic pollutants, plastic-associated chemicals and metals. There was little co-variation among the contaminants and only two clusters of PCBs could be discerned. Gradient boosted CARTs were used to assess additive and multiplicative associations between atherosclerosis, as measured by the intima-media thickness (IMT) and the echogenicity of the intima-media complex (IM-GSM), and prevalent metabolic syndrome. Systolic blood pressure was the most important predictor of IMT while the influence of the contaminants was marginal. Three phthalate metabolites; MMP, MEHP and MIBP were strongly related to IM-GSM. A synergistic interaction was found for MMP and MIBP, and a small antagonistic interaction was found for MIBP and MEHP. Associations between the contaminants and prevalent metabolic syndrome were modest, but three pesticides; p,p’-DDE, hexachlorbenzene and trans-nonachlor along with PCBs 118 and 209 and mercury were the strongest predictors of prevalent metabolic syndrome. This thesis concludes that many contaminants need to be measured to get a clear picture of the exposure. Boosted CARTs are useful for uncovering interactions. Multiplicative and/or additive effects of certain contaminant mixtures were found for atherosclerosis or the metabolic syndrome.

Thesis (M.S.)--University of Nevada, Reno, 2006. / "May, 2006." Includes bibliographical references (leaves 54-56). Online version available on the World Wide Web.

Thesis (M.S.)--University of Nevada, Reno, 2007. / "December, 2007." Includes bibliographical references (leaves 63-66). Online version available on the World Wide Web.

Thesis (Ph.D.) - Carleton University, 2005. / Includes bibliographical references (p. 250-267). Also available in electronic format on the Internet.

Thesis (Ph. D.)--University of Hong Kong, 1996. / Includes bibliographical references (leaf 159).

Thesis (M.S.)--Brigham Young University. Dept. of Statistics, 2007. / Includes bibliographical references (p. 46-49).

Thesis (Ph.D.) -- McMaster University, 2001. / Includes bibliographical references. Also available via World Wide Web.

O Kraft 36EC® (i.a. abamectina) e o Score 250EC® (i.a. difenoconazol) são agrotóxicos intensamente utilizados nas culturas de morango em regiões de clima tropical, embora sejam compostos classificados como extremamente tóxicos e muito perigosos ao ambiente. Misturas de agrotóxicos são aplicadas nas culturas agrícolas e a presença destes compostos na água pode potencializar os efeitos tóxicos a organismos aquáticos não alvos. A ocorrência do escorrimento superficial (runoff) contaminado com agrotóxico e a contaminação por aspersão direta (spray drift) em ecossistemas tropicais próximo aos corpos hídricos também podem comprometer o ecossistema aquático local devido à toxicidade desses compostos a organismos não alvos. Considerando os riscos ecológicos inerentes ao uso destes agrotóxicos, o objetivo principal desta pesquisa foi avaliar o efeito ambiental dos praguicidas Kraft 36EC® e Score 250EC® e de seus princípios ativos, abamectina e difenoconazol, respectivamente. Foram realizados testes de toxicidade aguda em laboratório a partir de exposições dos compostos isolados e em misturas utilizando como organismo teste embriões e adultos de Danio rerio. Experimentos in situ (mesocosmos) foram realizados a fim de avaliar os efeitos do runoff e spray drift contaminados com os agrotóxicos Kraft 36EC® e Score 250EC®, isolados e em misturas. Tanto nos mesocosmos quanto em experimentos de laboratório analisou-se, além da mortalidade, biomarcadores bioquímicos. Pelos resultados obtidos verifica-se que não foram observadas diferenças significativas entre a toxicidade isolada dos ingredientes ativos e suas respectivas formulações comerciais em testes agudos. Nos testes de toxicidade com as misturas dos ingredientes ativos, observou-se que a mistura de abamectina + difenoconazol promoveu um efeito tóxico sinérgico a adultos de Danio rerio em exposições agudas. Observou-se também a ausência do mesmo efeito nas exposições com as misturas das formulações comerciais neste mesmo estágio de vida. A exposição dos embriões às misturas de Kraft 36EC® e Score 250EC® mostrou um efeito antagônico nas baixas concentrações e efeito sinérgico nas mais altas. Verificou-se um aumento significativo na atividade da enzima de biotransformação 7-etóxiresorufina-0-deetilase (EROD) e nos níveis de malondialdeído MDA nas brânquias de peixes expostos à formulação comercial da abamectina. Houve um aumento na atividade da glutationa-S-transferase (GST), glutationa peroxidase (GPx) e níveis de MDA, e diminuição da glutationa redutase (GR) nas brânquias dos peixes expostos ao difenoconazol e sua formulação comercial. Também foi observado um aumento nas respostas dos biomarcadores analisados nas brânquias dos organismos expostos às misturas tanto dos princípios ativos quanto das formulações comerciais. A exposição ao Kraft 36EC® spray drift em campo promoveu os maiores efeitos deletérios no metabolismo de Danio rerio, seguido das exposições ao runoff contaminado com Kraft 36EC® e Score 250EC®. As formulações comerciais Kraft 36EC® e Score 250EC® e as misturas das mesmas promoveram alterações significativas no metabolismo de detoxificação, e causam estresse oxidativo em peixes. Diferenças no padrão de respostas dos biomarcadores entre os experimentos realizados em mesocosmos e em laboratório ficam evidentes devido à influência das concentrações utilizadas, das interações ecológicas entre as comunidades presentes no meio e das variáveis ambientais nos experimentos em mesocosmos. A avaliação da toxicidade de agrotóxicos, especialmente em países tropicais, e indicações para futuras pesquisas são discutidos. / Kraft 36EC® (a.s. abamectin) and Score 250EC® (a.s. difenoconazole) are intensely used pesticides in strawberry crops in tropical regions, even though they are classified as extremely toxic and very dangerous to the environment. Mixtures of agrochemicals are applied to agricultural crops and the presence of these compounds in water may potentiate toxic effects to non-target aquatic organisms. The contamination of edge-of-field water bodies through runoff and spray drift may compromise the local aquatic ecosystem due to the toxicity of these compounds to non-target organisms. Considering the potential ecological risks related with the use of these pesticides, the main objective of this research was to evaluate the environmental effects of the pesticides Kraft 36EC® and Score 250EC® and its active ingredients abamectin and difenoconazole, respectively. Acute toxicity tests were performed in the laboratory with the isolated compounds and their mixtures using zebrafish (Danio rerio) embryos and adults as test organism. A mesocosm experiment was also performed to evaluate the effects of simulated runoff and spray drift containing Kraft 36EC® and Score 250EC® individually and in mixtures. Besides lethality, selected biomarkers were also evaluated in the fish from the mesocosm and laboratory experiments. No significant differences were observed in effects of the active ingredients and their respective commercial formulations in acute fish tests after single exposure to each test compound. The acute mixture toxicity tests with the active ingredients showed that this mixture exerts a synergistic toxic effect to adult fish. The absence of the synergistic effect on exposures with the commercial formulations mixtures was also observed. Embryo exposure to Kraft 36EC® and Score 250EC® mixtures showed an antagonistic effect at low concentrations and synergistic effect at the highest. A significant increase was observed in the activity of the EROD biotransformation enzyme and in the levels of MDA in fish gills after exposure to Kraft 36EC®. An increase in GST activity, GPx and MDA levels, and a decrease of GR in fish gills was noted after fish exposure to difenoconazole and its commercial formulation. An increase in the responses of the biomarkers analyzed in the gills of the organisms exposed to the mixtures of both the active ingredients and the commercial formulations as compared to single-compound exposure was also observed. Exposure to simulated spray drift of Kraft 36EC® in the mesocosms promotes the greatest deleterious effects on metabolism of Danio rerio followed by exposures to the runoff contaminated with a Kraft 36EC® and Score 250EC® mixture. The commercial formulations Kraft 36EC® and Score 250EC® and their mixtures lead to significant changes in the detoxification metabolism resulting in oxidative stress to fish. Differences in biomarkers responses between the experiments performed in the mesocosms and the laboratory were noted and are due to the different concentrations tested; the ecological interactions between the communities present in the mesocosms and differences in environmental variables. The need and indications for future research related with the evaluation of pesticide toxicity, especially in tropical countries, are discussed.

A number of pharmaceuticals have been shown to have adverse effects on key biological processes of aquatic organisms at low concentrations (ng/l range). Key questions for chemical risk assessment are whether such pharmaceuticals can produce adverse effects on organisms when present in the environment in combination and at low concentrations, whether these can be classified as additive, and under what circumstances can they be predicted. The main purpose of this study was to assess the potential for combination effects of a multicomponent steroid pharmaceutical mixture of dissimilarly acting compounds on an ecologically relevant end point – reproduction, using the existing predictive toxicity models Concentration Addition (CA) and Independent Action (IA). Concentrations of steroids close to those reported in the environment were shown to produce adverse effects on reproduction when present in combination with other steroids. Clear combination effects significantly larger than the effects of the individual compounds were observed when each compound was present at a concentration below the detection limit of the assay, demonstrating a ‘something from nothing’ mixture effect. Furthermore, IA predicted more pronounced effects on egg production that CA, an observation previously unreported from the literature. Actual observed effects were closer to the IA prediction. Additional biomarker and molecular endpoints were examined in subsequent studies to establish the mechanisms of disrupted reproduction in pair-breeding FHMs exposed to the steroid mixture. Results from this study indicate that reproductive impairment of fish exposed to the steroid mixture is likely due to the masculinisation of female fish due to the androgenic activity of the mixture. These results have implications for chemical risk assessment, and in particular, highlight the need for caution when using CA as a worst-case approximation of mixture effects.