<p> A neutron activation analysis procedure for the simultaneous determination of Ru, Pd, Os, Ir, Pt and Au has been developed. It consists principally of distillation, anion exchange, solvent extraction and precipitation steps and was used to determine all of these metals in meteorites as well as Pd, Ir and Au in sulphide minerals from the Sudbury Nickel Irruptive. The accuracy of the method was checked against G-1 and W-1 and a sulphide standard. A literature survey of the geology of the Sudbury Nickel Irruptive and a description of the geology of the Strathcona mine are presented. A detailed description of the inorganic chemistr! and its bearing on the geochemistry of the precious metals, with special reference to basic rocks is given. Analytical results for Pd, Ir and Au in a large number of pyrrhotite and chalcopyrite samples and a smaller number of sulphide and oxide minerals and an ultramafic xenolith are presented. Arsenic was determined in 15 of the sulphide samples and found to be highly correlated with Pd. The genesis of the Strathcona ores is discussed and the differential behaviour of the precious metals during fractionation or a sulphide-rich basic magma is described. </p> <p> Seven carbonaceous and two enstatite chondrites were analysed and the data evaluated with respect to estimation of the cosmic abundances of these metals. </p> / Thesis / Doctor of Philosophy (PhD)

<p> Though Neutron Activation Analysis is one of the most sensitive multielement analysis methods, Compton interference in complex sample matrices usually presents a problem when choosing irradiation and decay times for analysis. While various scientists have attempted to solve the problem, the approaches taken to date have the drawbacks of either requiring standard spectra of the sample components or not giving the optimum times automatically and simultaneously. The purpose of this thesis was to find a method to automatically and simultaneously obtain the optimum times for Instrumental Neutron Activation Analysis using the Modified Simplex Method to evaluate the best figure of merit calculated from an advance predicted spectrum of the sample.</p> / Thesis / Master of Science (MSc)

<p> A rapid and simple radiochemical neutron activation technique involving tellurium coprecipitation of Au, lr, Pd and Pt was evaluated using the U.S.G.S. standards PCC-1 (peridotite) and DTS-1 (dunite) as well as a house standard, JHC-6 (spinifex zone of a komati itic peridotite). It was then applied to the analysis of samples of Archean greenstone from the Red Lake area.</p> <p> The technique gives detection limits of 0.01-0.02, 0.02, 0.1-0.4 and 1-2 ppb for Au, Ir, Pd and Pt respectively and precisions of <25-35%. The method can be successfully applied to the analysis of PGE levels in sulphur-poor rocks, and large numbers of samples can be processed in a short period of time.</p> <p> A comparison of PGE content between several types of mafic rocks was made as well as an investigation of possible secular trends (Archean vs. Phanerozoic) in PGE concentration.</p> / Thesis / Master of Science (MSc)

<p> This work was the first study at the beam port # 4 at the McMaster Nuclear Reactor, involving prompt gamma in vivo neutron activation analysis. The project consisted of experimental and computational parts. The computational part was done using MCNP program, which simulates the neutron and photon transport in the medium. The first thing assessed was the energy dependent neutron fluence rate in the collimated neutron beam, at the site. This was done in order to figure out the complete source (sdef) card for further MCNP calculations. This was combined experimental and computational work. For the experimental part, various activation foils were used and computational part was done by using MCNP programming.</p> <p> The second part of the project involved experimental prompt gamma in vivo activation analysis using 7 different phantoms, ranging from 30 mL to 2 L. Three different elements were observed. The prompt gamma in vivo detection of cadmium was the preliminary calibration study and the experiments were done with all seven phantoms. The calibration lines and MDL were assessed for all phantoms, with concentration ranging from 0 to 50 ppm. The prompt gamma in vivo detection of boron and mercury was done using 30 mL phantoms. Calibration lines and MDL for both elements were assessed as well.</p> <p> MCNP experimental simulations for 30 mL water phantoms were done and they were in close agreement with the experimental results. Furthermore, the MCNP gamma and neutron dose survey in the cave was done.</p> <p> The results obtained showed that there are numerous open possibilities for improvement in terms of in vivo prompt gamma analysis at the site. It predominantly includes the improvements in prompt gamma detection techniques and MCNP source definition. Furthermore, it was found that MCNP programming is the ideal tool for assessment and control of the experimental results in this case. It means that in the future research, the MCNP modeling will be the essential part of the in vivo prompt gamma activation analysis at this beam port.</p> / Thesis / Master of Science (MSc)

<p> This project was undertaken with the aim of studying the distribution of copper, manganese and zinc in brain and to gain same information on the possible presence of soluble metallo-proteins in this tissue. The distribution of copper, manganese and zinc has been determined by neutron activation analysis. Soluble metallo-proteins of these three elements have been identified by the combination of gel chromatography and neutron activation analysis. In addition, in vivo and in vitro radioisotopic labelling techniques have been used occasionally.</p> / Thesis / Doctor of Philosophy (PhD)

<p> With the increasing concern about pollution the need has arisen for accurate trace analysis of hazardous or toxic trace elements such as cadmium. While the modern analytical chemist has at his disposal a great many different techniques for analysis, surveys of inter-laboratory analyses have often produced serious discrepancies among results done by different methods and/or workers. The purpose of this thesis will be to review the different methods for trace analysis of cadmium in biological samples and to experimentally compare two of these, atomic-absorption spectrometry and neutron-activation analysis.</p> / Thesis / Master of Science (MSc)

Non-invasive techniques to measure bone fluorine levels in vivo are few and not well studied. These techniques would prove useful for longitudinal studies of fluorine accumulation and treatment optimization for patients with poor bone health. Two measurement techniques were analyzed and improvements to each technique attempted with bone samples and bone-mimicking phantoms. The first method analyzed was neutron activation analysis (NAA), a technique previously studied in our laboratory. A previous detector setup consisting of nine sodium iodide detectors was re-tested and a new detector setup consisting of two high-purity germanium detectors was also tested. The detection limit of the sodium iodide setup was found to be higher than previously reported by a factor of 4, and the new high-purity germanium detector setup was found to result in a higher detection limit by a factor of 5 compared to the sodium iodide setup. The second method analyzed was nuclear magnetic resonance (NMR). Magic angle spinning was performed on a human bone sample, and a novel probe was constructed for future in vivo measurements. MAS NMR measurement of the human bone sample showed it to have an appropriate chemical shift and shape consistent with previous research on substances similar to bone. The constructed probe successfully resonated at the appropriate frequency, however there were potential contamination problems which prevented a measurable fluorine signal from being obtained. Both the NAA and NMR techniques may be optimized further, though with the results obtained, NAA remains the more sensitive technique for measuring bone fluorine in vivo. / Thesis / Master of Science (MSc) / Fluorine is an element which accumulates in bones and teeth. High levels of fluorine have been shown to be unhealthy, causing both dental and skeletal fluorosis. Low levels of fluorine have been shown to reduce dental cavities, however, their effect on bone health is not well understood. Currently, fluorine can be measured in bone samples from either biopsies or cadavers. Having a non-invasive way to measure fluorine concentrations in living humans without the need for surgery would be invaluable. These measurements could be used to optimize treatment for osteoporosis patients or to determine if emergency measures are necessary in cases of high accidental doses to members of the public. Additionally, long-term studies examining fluorine metabolism and bone health could be performed on population groups of interest. For these reasons, two different non-invasive methods for determining fluorine content in bone were analyzed and enhancements to each measurement technique attempted.

Nesse trabalho foi desenvolvido um sistema de aquisição &gamma;&gamma; que possibilita realizar medidas de Análise por Ativação Neutrônica Instrumental por espectroscopia gama unidimensional e em coincidência simultaneamente para os elementos As, Co, Cs, La, Sc, Se e Sm. Para tal foram realizadas medidas preliminares em sistemas de aquisição &gamma;&gamma; baseados em instrumentação analógica e digital a fim de se verificar a eficiência da técnica a partir de medições de padrões sintéticos e análises de materiais de referência certificados. Essas medidas também auxiliaram na escolha do tipo de instrumentação mais apropriada para o desenvolvimento do sistema de aquisição no Laboratório de Física Nuclear Aplicada (LFNA) do IPEN. O sistema montado no LFNA é composto de uma placa digitalizadora da marca CAEN modelo v1724 e dois detectores de germânio hiperpuro. A aquisição dos dados é controlada pelo software MC2Analyzer, que fornece dados brutos de energia e tempo dos pulsos registrados. Foram desenvolvidos dois programas de redução de dados que selecionam os eventos em coincidência a partir dos espectros unidimensionais: o DPP que prepara os dados para serem analisados em programas de análise de espectros bidimensionais; e o AnalisaCaen que trata os dados para sejam analisados em programas de análises de espectros unidimensionais. Foram realizadas análises de materiais de referência certificados biológicos e geológicos, e também padrões sintéticos utilizando-se as técnicas de Análise por Ativação Neutrônica convencional e em coincidência. Os resultados permitiram verificar a confiabilidade dos valores das concentrações dos elementos As, Co, Cs, La, Sc, Se e Sm obtidos com o sistema de coincidência desenvolvido. Os resultados obtidos por ambas as técnicas, Análise por Ativação Neutrônica Convencional e Análise por Ativação Neutrônica em Coincidência, foram comparados e valiados em termos de precisão e exatidão pelo critério de Enscore. Em alguns casos, os resultados de concentração obtidos por meio das medidas de coincidência forneceram melhores do que os resultados obtidos pela espectroscopia gama convencional. / In this study was the developed a &gamma;&gamma; acquisition system that make possible to perform Neutron Activation Analysis by single gamma spectroscopy and coincidence &gamma;&gamma; spectroscospy simultaneously for the elements As, Co, Cs, La, Sc, Se e Sm. In order to achieve this main goal preliminary measurements in &gamma;&gamma; acquisition systems with analogical and digital instrumentation were performed to check the efficiency of technique through measurements of synthetic standard and certified reference material. These measurements also helped to choose the most suitable instrumentation for the development of the acquisition system in the Applied Nuclear Physics Laboratory (LFNA) located at IPEN. The developed system is composed by a CAEN v1724 digitizer board and two hyperpure Germanium detectors. The data acquisition is controled by MC2Analyzer software, which provide raw data of energy and time information of the recorded pulses.Two softwares for data reduction that allow the set the coincident events from single spectra were developed: DPP which prepare the data to be analyzed with softwares for bidimensional espectra.; and AnalisaCaen which handle the data to be analyzed with softwares for single spectra. Determination of the concentration for some elements in certified reference materials and sytnhetic standards were performed applying the conventional and coincidence Neutron Activation Analysis methods. Accuracy and precision of the results obtained by Instrumental Neutron Activation Analysis and Coincidence Instrumental Neutron Activation Analysis were performed by Enscore criteria. The results obtained with this system allowed to check the reliability on the determination for the elements As, Co, Cs, La, Sc, Se and Sm. In some cases the concentration results obtained with coincidence measurements were better than the results from single spectroscopy.

Suite aux séismes et au tsunami qui ont frappé les côtes japonaises le 11 mars 2011, d’importantes quantités de radionucléides ont été émises par la centrale de Fukushima Dai-Ichi. Une part non négligeable (20%) du radiocésium rejeté s’est ensuite déposée sur les sols de la Préfecture de Fukushima. Cette étude vise à développer des méthodes de traçage sédimentaire originales afin de comprendre la dispersion des particules contaminées. L’étude se concentre sur 3 bassins versants côtiers situés au nord de la centrale (bassins de la Mano – 175 km², Niida – 270 km² et Ota – 75 km²) et drainant la partie la plus contaminée du panache de pollution radioactive. Cette région connaît un climat particulièrement érosif, avec des crues printanières et le passage de typhons entre juin et octobre. Pour étudier la dispersion de la contamination radioactive initiale, des sols et des laisses de crues ont été collectés au cours de 6 campagnes de terrain (organisées tous les 6 mois entre novembre 2011 et mai 2014 après les crues printanières et les typhons estivaux). L’activité des principaux radionucléides a été mesurée par spectrométrie gamma et une sélection d’échantillons a également été analysée par activation neutronique afin de déterminer leur teneur en une vingtaine d’éléments. L’analyse de l’activité en 137Cs dans 10 carottes de sols collectées dans des rizières a confirmé la faible migration du césium en profondeur dans les sols de la région. Plus de 90 % de la contamination étaient concentrés dans les 2 cm superficiels des sols en novembre 2013. Cette contamination située à la surface du sol reste donc potentiellement mobilisable par l’érosion. Par ailleurs, la détection d’argent-110 métastable (110mAg) et le fait que ce radioisotope ait un comportement similaire à celui du césium, ont permis de l’utiliser pour tracer la dispersion de la contamination dans le bassin versant de la Niida. En effet, le rapport d’activités 110mAg/137Cs dans les sols de ce bassin est significativement différent à l’amont et à l’aval de celui-ci. L’utilisation de ce rapport et d’un modèle de mélange binaire a permis d’identifier l’occurrence de cycles d’érosion et de dispersion saisonniers de la contamination. Cependant, 110mAg ayant une demi-vie de 250 jours, il a rapidement décru et l’activité est devenue inférieure aux limites de détection à compter de mai 2013. Pour pallier sa disparition, la contribution des sols des plateaux montagneux aux sédiments transitant dans la plaine côtière a été quantifiée à partir de leur signature en 137Cs. En utilisant un modèle de mélange binaire basé sur les distributions du 137Cs à l’amont (> 20 kBq/m²) et à l’aval (< 20 kBq/m²) des bassins versants, les résultats montrent que la contribution de la zone amont diffère en fonction du bassin versant. Elle fournit une part non négligeable (≈46%) des sédiments à la rivière Niida, qui est dépourvue de barrage, à la différence de la rivière Mano (≈20 %) qui en est équipée. Ces résultats montrent donc l’impact de ce type d’ouvrage qui génère une dysconnectivité sédimentaire. Afin de préciser l’origine spatiale des sédiments contaminés transportés par ces rivières, la carte des sols des bassins versants a été utilisée. Les principaux types de sols (Andosols, Cambisols et Fluvisols) ont été caractérisés par leurs teneurs en éléments chimiques, et Sc et Yb se sont révélés être le couple d’éléments le plus discriminant. Les distributions de ces deux éléments dans les trois sources ont ensuite été utilisées dans un modèle de mélange. Les résultats montrent une contribution majoritaire (> 70 %) des Fluvisols dans les sédiments. La forte contribution de ce type de sol, que l’on trouve principalement dans les rizières, confirme donc l’érodabilité accrue de ces zones agricoles. Pour poursuivre ces travaux, l’ensemble des données acquises pourrait être utilisé pour améliorer les modèles d’érosion des sols opérant à l’échelle des bassins versants. / Large quantities of radionuclides were released into the atmosphere by the Fukushima Dai-Ichi Nuclear Power Plant (FDNPP) after the earthquake-triggered tsunami devastated the eastern coast of Japan on March 11, 2011. Many of these radionuclides (20%) were deposited on soils of the Fukushima Prefecture. This PhD thesis develops original fingerprinting methods to track the dispersion of contaminated particles following this accident. The study focuses on 3 coastal catchments north of the FDNPP (Mano — 175km², Niida — 270km² and Ota — 75km²) draining heavily contaminated areas of the radioactive plume. The Fukushima Prefecture is characterized by an erosive climate, with the occurrence of spring floods and summer typhoons. To study the dispersion of the radioactive contamination, soil samples and sediment drape deposits were collected during 6 sampling campaigns (every six months between November 2011 and May 2014; i.e., after the major flood events). Each sample was analyzed by gamma spectrometry to determine radionuclide activities, and several soil and sediment samples were also analyzed by neutron activation analysis to determine their geochemistry. First, the analysis of 137Cs activity in 10 soil cores collected in paddy fields confirmed the limited migration of radiocesium with depth in the soils of the coastal catchments. More than 90% of the contamination was still concentrated in the uppermost 2cm of the soils by November 2013. Particles contaminated were therefore available for mobilization and transport downstream by processes that govern soil erosion. Second, metastable silver-110 (110mAg) was detected in most of the samples collected between November 2011 and November 2012, and our investigation showed that this radionuclide has a similar behavior as 137Cs in soil and sediment. Consequently, we used 110mAg to track the dispersion of the contamination as the 110mAg/137Cs activity ratio in soils of the Niida catchment showed significant differences between upstream and downstream locations. The use of a binary mixing model allowed the identification of a seasonal cycle of erosion and dispersion of particles. However, as 110mAg has a short half-life (250 days), it rapidly decayed and could not be detected anymore by May 2013. To overcome its disappearance, the contribution of soils located on the mountainous plateaus to the sediment transiting the river in the coastal plains was quantified based on their 137Cs signature. Binary mixing models were used, based on the distributions of 137Cs in mountainous areas (> 20 kBq/m²) and in coastal plains (< 20 kBq/m²). The results demonstrated that the contribution of the mountainous area varied in the different catchments. In the Niida catchment where no dam has been built, the mountainous area supplies more sediment to the river (≈46%) than in the Mano catchment that has a dam (≈20%). These results show the impact of dams generating a sediment disconnectivity. Finally, the soil map of the region was used in order to identify the soil types that may supply sediment to the rivers. The main soil types (Andosols, Cambisols and Fluvisols) were characterized by their geochemical composition, and Sc and Yb were identified as the most discriminant elements. The distributions of these elements in the three sources were used in a mixing model. Results show that Fluvisols are the main source supplying >70% of sediment to the rivers in both catchments. This soil type is mainly found in paddy fields, which confirms the enhanced erodibility of these cultivated areas. In the future, the dataset compiled could be used to improve soil erosion model operating at the catchment scale. Moreover, the impact of the ongoing decontamination works on the dispersion of contaminated sediments should be investigated.

Tillandsia usneoides L. é uma bromélia que vive em árvores ou em outros substratos inertes, absorvendo água e nutrientes diretamente do ambiente, sem apresentar raízes. Devido às suas características morfológicas e fisiológicas, esta espécie acumula os poluentes presentes na atmosfera. No presente trabalho, Tillandsia usneoides foi usada como biomonitor de poluição atmosférica por metais em São Paulo, Brasil, que é a maior cidade da América do Sul, com uma população de cerca de 18 milhões de habitantes e uma forte atividade industrial. A área urbana é poluída por emissões industriais mas, de acordo com a Companhia de Tecnologia de Saneamento Ambiental do Estado de São Paulo (CETESB), a agência governamental de controle de qualidade do ar, emissões regulares de cerca de 7,8 milhões de veículos motores são a principal fonte de poluição do ar. As amostras de Tillandsia foram coletadas em um local considerado não poluído e foram expostas por períodos de dois meses em 10 locais da cidade com diferentes níveis de poluição, e em um local de controle. Após a exposição, os metais foram analisados na planta por análise por ativação com nêutrons e por ICP-MS (Pb, Cd, Co, Cu, Ni, Sb e V). Os resultados obtidos mostraram uma concentração notável de Co e Ni nas plantas expostas em uma área industrial, onde existe uma indústria de processamento de metal, que produz cerca de 600 ton/ano de Co e 16.000 ton/ano de Ni. Cobre e crômio se apresentaram igualmente distribuídos em regiões industriais e em locais próximos a avenidas com tráfego intenso, sugerindo que estes elementos podem ser associados tanto a fontes veiculares como industriais. O acúmulo de Cd verificado nas plantas expostas em áreas industriais indica as atividades intrópicas como a principal fonte desse elemento. Não foram identificadas fontes evidentes para o Pb, uma vez que este elemento se apresentou igualmente espalhado por todos os locais de monitoramento. Elementos ligados ao tráfego, como Zn, Ba and Sb apresentaram altas concentrações em plantas expostas em locais situados próximos a avenidas com tráfego pesado (carros, ônibus e caminhões) e podem ser associados a fontes veiculares. Para Zn, os maiores teores foram relacionados a zonas industriais, e este elemento pode ser também associado à presença de fontes de emissão antrópicas. Os elementos terras raras, Fe e Rb, provavelmente têm as partículas de solo como principal fonte. / Tillandsia usneoides L. is an epiphytic bromeliad that lives on trees or other kinds of inert substrates, absorbing water and nutrients directly from the environment without roots. Due to its morphological and physiological characteristics, this species accumulates the pollutants present in the atmosphere. In the present work, Tillandsia usneoides was used as a biomonitor of metal atmospheric pollution in São Paulo, Brazil, which is the biggest city in South America with a population of 18 million inhabitants and a strong industrial activity. The urban area is polluted by industrial emissions but, according to the Environmental Protection Agency of the State of São Paulo (CETESB), the governmental agency of air quality control, regularly occurring emissions from about 7.8 million motor vehicles provide the principal source of air pollution. The Tillandsia samples were collected from an unpolluted area and were exposed bimonthly in 10 sites of the city with different pollution levels and in a control site. After exposure, trace metals were analyzed in the plant by instrumental neutron activation analysis and ICP-MS (Pb, Cd, Co, Cu, Ni, Sb e V). The results of the investigation showed a notable concentration of Co and Ni in the plants exposed in an industrial area where there is a metal processing plant, which produces about 600 tons/year of Co and 16,000 tons/year of Ni. Copper and chromium were equally distributed in industrial regions and in sites near heavy traffic avenues, suggesting that these elements can be associated to both vehicular and industrial sources. A high accumulation of Cd in the plant exposed in industrial areas indicates industrial activities as the main source of this element. For Pb, no evident sources could be identified so far as it was spread evenly along the monitoring sites. Traffic-related elements such as Zn, Ba and Sb presented high concentrations in plants exposed in sites near to heavy traffic avenues (cars, buses and trucks) and may be associated to vehicular sources. For Zn, the highest contents were related to industrial zones and this element can be associated to the presence of anthropogenic emission sources. The rare earth elements, Fe and Rb, probably have soil particles as main source.