Philosophiae Doctor - PhD / Very few systems allow the study of the relationship between structural changes and physical properties in such a clear way as rare earth nickelate ReNi03 perovskites (Re (rare earth) = Pr, Nd, Sm and Gd). Synthesized for the first time by Demazeau et al [1] in 1971 and completely forgotten for almost twenty years, these compounds have regained interest since the discovery of high-temperature superconductivity and giant magnetoresistive effects in other perovskite-related systems. Due to its Metal-Insulator Transition (MIT) and thermochromic properties, the rare earth nickelate perovskite ReNi03 has received a great deal of attention for the past ten years in their thin films form [12]. Such unusual electronic and optical features are all the more interesting since the metal-insulator transition temperature (TMn) can be tuned by changing the Re cation: LaNi03 is metallic. No minimum of the metallic conductivity of Sm0 . ssNd 0.45Ni03, as observed by Gire et al [12] (entropic effect), was reported by Ambrosini and Hamet [11]. It has been suggested by Obradors et al. [13] that changing the rare earth cation in the ReNi03 system, acts as internal chemical pressure (increasing internal pressure by substituting the rare earth cation with another one of larger ionic radius) which can lead, as for the isostatic pressure experiment, to a tunability of the metal-insulator transition temperature [14, 15]. Obradors et al [13] reported on a decrease of T MIT upon increasing isostatic pressure but with remaining metallic properties of PrNi03 and NdNi03 (same magnitude and thermal dependence of the electrical resistivity)

Fusarium head blight (FHB), caused by Fusarium graminearum, is a serious disease of wheat and barley that has caused several billion dollars in crop losses over the last decade in the United States. Spores of F. graminearum are released from corn and small grain residues left-over from the previous growing season and are transported long distances in the atmosphere before being deposited.  Current risk assessment tools consider environmental conditions favorable for disease development, but do not include spore transport. Long distance transport models have been proposed for a number of plant pathogens, but many of these models have not been experimentally validated. In order to predict the atmospheric transport of F. graminearum, the potential source strength (Qpot) of inoculum must be known.  We conducted a series of laboratory and field experiments to estimate Qpot from a field-scale source of inoculum of F. graminearum.  Perithecia were generated on artificial (carrot agar) and natural (corn stalk) substrates.  Artificial substrate (carrot agar) produced 15±0.4 perithecia cm-2, and natural substrate (corn stalk) produced 44±2 perithecia cm-2.  Individual perithecia were excised from both substrate types and allowed to release ascospores every 24 hours.  Perithecia generated from artificial (carrot agar) and natural (corn stalk) substrates released a mean of 104±5 and 276±16 ascospores, respectively.  A volumetric spore trap was placed inside a 3,716 m2 clonal source of inoculum in 2011 and 2012.  Results indicated that ascospores were released under field conditions predominantly (>90%) during the night (1900 to 0700 hours).  Estimates of Qpot for our field-scale sources of inoculum were approximately 4 billion ascospores per 3,716 m2.  Release-recapture studies were conducted from a clonal field-scale source of F. graminearum in 2011 and 2012. Microsatellites were used to identify the released clone of F. graminearum at distances up to 1 km from the source. Dispersal kernels for field observations were compared to results predicted by a Gaussian dispersal-based spore transport model.  In 2011 and 2012, dispersal kernel shape coefficients were similar for both results observed in the field and predicted by the model, with both being dictated by a power law function, indicating that turbulence was the dominant transport factor on the scale we studied (~ 1 km).  Model predictions had a stronger correlation with the number of spores being released when using a time varying q0 emission rate (r= 0.92 in 2011 and r= 0.84 in 2012) than an identical daily pattern q0 emission rate (r= 0.35 in 2011 and r= 0.32 in 2012).  The actual numbers of spores deposited were 3 and 2000 times lower than predicted if Qpot were equal to the actual number of spores released in 2011 and 2012, respectively. Future work should address estimating the actual number of spore released from an inoculated field during any given season, to improve prediction accuracy of the model.  This work should assist in improving current risk assessment tools for FHB and contribute to the development of early warning systems for the spread of F. graminearum. / Ph. D.

Le trafic routier contribue à la pollution atmosphérique aussi bien à proximité des voies avec des polluants tels que le dioxyde d'azote (NO2), les particules (PM) et certains composés organiques volatils (COV) qu'à des échelles spatiales plus grandes (pollution de fond urbaine et régionale) avec des polluants formés dans l'atmosphère tels que l'ozone (O3) et la fraction secondaire des particules. Étant donné les interactions entre pollution de proximité et pollution de fond, il est souhaitable de combiner en un seul outil de calcul des modèles à échelles locale et régionale. Cette méthode de modélisation multi-échelles a été largement utilisée pour simuler l'impact des émissions de cheminées (sources ponctuelles) avec des modèles de panache traités en sous-maille d'un modèle eulérien tri-dimensionnel. Cependant, une telle méthode n'est pas applicable à un réseau routier en raison des temps de calcul prohibitifs associés à la discrétisation d'une source linéique en un ensemble de sources ponctuelles. Par conséquent, une nouvelle méthode de modélisation multi-échelles a été développée, qui traite les panaches émis par des sources linéiques en sous-maille d'un modèle eulérien. Tout d'abord, une formulation améliorée d'un modèle gaussien de panache linéique a été développée. Ce nouveau modèle à ensuite fait l'objet d'une évaluation détaillée avec des mesures en proximité de routes ainsi qu'avec d'autres modèles gaussiens. La combinaison de ce modèle gaussien et d'un modèle eulérien (Polair3D) a été implémentée dans la plate-forme de modélisation Polyphemus. Les performances (temps de calcul et précision) du nouveau modèle de panache en sous-maille ont été évaluées et comparées aux performances des modèles gaussien et eulérien seuls. Ce modèle multi-échelles traite la chimie des oxydes d'azote (NOx) et des principaux COV. Le traitement multi-échelles a un effet important sur les concentrations de certains polluants en termes de pollutions de proximité et de fond urbain / Roadway traffic contributes to atmospheric pollution near roads, with pollutants such as nitrogen dioxide (NO2), particles (PM) along with some volatile organic compounds (VOC), as well as at larger spatial scales (urban and regional background pollution) with pollutants formed in the atmosphere such as ozone (O3) and the secondary fraction of PM. Because of interactions between local and background pollutants, it is desirable to combine into a single computational tool, regional and local scale models. This multi-scale modeling method has been widely used to simulate the impact of chimney emissions (point sources) with a sub-grid treatment of plume or puff models instead within a 3-dimensional Eulerian model. However, such a method is not applicable to a road network because of the prohibitive computations associated with the line source discretization into a set of point sources. Thus, a new multi-scale modeling method was developed, which treats the plumes emitted from line sources as sub-grid components of an Eulerian model. First, an improved formulation of a Gaussian plume model for line sources was developed. This new model was then subject to a detailed evaluation with near roadway measurements along with other Gaussian models. The incorporation of the Gaussian plume model into an Eulerian model (Polair3D) was implemented as part of the modeling platform Polyphemus. The performance (computational effectiveness and precision) of the new multi-scale model (Plume-in-Grid) was evaluated and compared to those of a stand-alone Gaussian and Eulerian models. The multi-scale model treats nitrogen oxide (NOx) chemistry along with major VOC. The multi-scale treatment has an important effect on the concentration of some pollutants in terms of local and urban background pollution

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Whole-rock and mineral compositions of three eruptive deposits from the Twin Falls caldera, associated with the Yellowstone hotspot, provide a window into melt generation and evolution for hot, dry, A-type rhyolites. Three rhyolitic units were sampled via the Kimberly drill-core as a part of project HOTSPOT, a study focused on mantle plume and continental lithosphere interaction. Previous work has been done to collect high resolution U-Pb zircon ages, and Hf- and O-isotopic compositions. This study examined the geochemistry of apatite and zircon along with host rock compositions in the context of this previous work. The Kimberly core sampled the Shoshone Rhyolite (6.06 Ma, 120 m thick), Kimberly Member (7.70 Ma, 169 m thick), and Castleford Crossing Member (7.96 Ma, >1400 m thick). Apatite compositions more closely reflect the composition of their whole rock hosts than zircons. SiO2 content is higher in apatite of the Kimberly Member at (1.1 ± 0.75 wt.%), vs (0.72 ± 0.47 wt.%) for the Castleford Crossing and (0.84 ± 0.27 wt.%) for the Shoshone Rhyolite. REEs compensate for Si substitution in these apatites, with the Kimberly Member most enriched. Volatile contents in the apatites are typical of metaluminous A-type rhyolites, with very low Cl and high F concentrations. Average Ti-in-zircon crystallization temperatures were highest in the Castleford Crossing Member (847 ± 68°C), followed by the Shoshone Rhyolite (806 ± 78°C), and then the Kimberly Member (804 ± 70°C). Oxygen fugacity calculated from zircons has average ΔQFM values for the Shoshone (0.8), Kimberly (-0.2), and Castleford Crossing (0.2). Hf concentrations and Eu anomalies are comparable in zircons from all three units. REE patterns in zircons are also similar and concentrations of REEs in the Shoshone and Kimberly units are similar even though the whole rock compositions of all three units are distinct. Less than 15% of zircons in the Kimberly and Castleford Crossing rhyolites have CL-dark cores enriched in several REEs, U, and Th. These CL-dark cored zircons are likely xenocrysts entrained from chemically evolved granite and then overgrown with less enriched rims prior to eruption. There are several apatite grains with Si-LREE enriched rims in the Kimberly Member, which serves as further evidence of assimilation of silicic igneous rock by the Kimberly Member before eruption. Principal component analysis of the geochemical data distinguishes between the units using both whole-rock and apatite compositions. However, zircon compositions are not statistically distinguishable using PCA. A global comparison of Ti, U, Th, Yb, and Nb concentrations in zircons show that the zircons in the Central Snake River Plain are similar to zircons in Hawaiian basalts, while younger zircons from Yellowstone formed in cooler more differentiated magma. We propose that the zircon and apatite chemical patterns and trends confirm the A-type origin of Snake River Plain rhyolites and make it unlikely that they represent partial melts of felsic continental crust but are instead derived in large part from partial melts of young mafic crust--the midcrustal sill.

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