Le N-hydroxytétraphénylphtalimide (NHTPPI) présente une activité catalytique sensiblement supérieure à celle du N-hydroxyphtalimide (NHPI) dans l'oxydation aérobie de substrats organiques. Deux nouvelles voies d'accès à des analogues fonctionnalisés du NHTPPI ont été étudiées. La première implique une réaction de Diels-Alder entre des oxydes ou dioxydes de thiophènes polyaromatiques et le maléimide ou l'anhydride maléique. De nombreuses limitations rendent cette approche difficilement généralisable. Dans la deuxième voie, l'étape clé est une cycloaddition entre des tétracyclones ou des acécyclones et le 2-bromomaléimide qui conduit directement au motif phtalimide par décarbonylation et déshydrobromation de l'adduit de Diels-Alder. Cette méthodologie de synthèse très efficace et tolérante a permis d'introduire des groupements variés sur les cycles aromatiques portés par le noyau benzénique central et d'obtenir de nouveaux analogues du NHTPPI ainsi que des N-hydroxydiarylacénaphtophtalimides en seulement trois à cinq étapes. La chiralité axiale a été mise en évidence en série diarylacénaphtophtalimide et la séparation d'énantiomères a été réalisée dans un premier cas, ce qui ouvre la voie vers de nouveaux analogues chiraux du NHPI. Les nouveaux N-hydroxyimides obtenus ont montré d'excellentes performances en catalyse d'oxydation aérobie, dans tous les cas supérieurs à celles du NHPI et, dans certains cas, à celles du NHTPPI. / N-Hydroxytetraphenylphthalimide (NHTPPI) exhibits a better catalytic activity than N-hydroxyphtalimide (NHPI) in the aerobic oxidation of organic substrates. Two new routes to functionalized analogs of NHTPPI have been studied. The first one involves a Diels-Alder reaction between polyaromatic thiophene oxides or dioxides and maleimide or maleic anhydrid. Several limitations make this approach difficult to generalize. In the second approach, the key step is a cycloaddition between tetracyclones or acecyclones and 2-bromomaleimide to directly give the phthalimide framework by decarbonylation and deshydrobromation of the Diels-Alder adduct. This versatile and efficient methodology allowed us to introduce various functional groups on the aromatic cycles borne by the central ring, and thus, new NHTPPI analogs, along with N-hydroxydiarylacenaphthophtalimides, were obtained in only three to five steps. Axial chirality was underlined in the diarylacenaphtophtalimide family and resolution of enantiomers was carried out in one case, which opens a way to new chiral analogs of NHPI. The new N-hydroxyimides exhibit excellent performances as catalysts in aerobic oxidation, superior to NHPI and, in some cases, to NHTPPI.

Towards advancing the indices of hurricane energetics that are associated with potential damage, we develop a new methodology for calculating integrated kinetic energy (IKE) climatology. A simple, observation and dynamical - based radial wind speed model is used with the Extended Best Track Data Set to calculate IKE for North Atlantic Hurricanes from 1988 to 2008. The method is evaluated against previous methods of tropical cyclone intensity analysis, and the results are compared to traditional indices in terms of characterizing storm energetics and relating to storm surge. It is shown that the traditional indices are inaccurate measurements of hurricane energetics, and the assumptions that they are based on are not valid. Furthermore, in analyzing storm surge, it is possible that tropical cyclone damage is more strongly correlated with IKE rather than maximum wind speed.

The eastern North Pacific Ocean has the highest density of tropical cyclone genesis events of any tropical basin in the world, and many of these systems form near land before moving westward. However, despite the level of tropical cyclone activity in this basin, and the proximity of the main genesis region to land, tropical cyclone behavior in the eastern North Pacific has been relatively unexplored. When synoptic conditions are favorable, moisture from northward-moving tropical cyclones can be advected into northern Mexico and the southwestern United States, often leading to the development of summertime thunderstorms during the North American monsoon season. An interaction with a mid-latitude trough produces the most rainfall, and the spatial variability of precipitation is greatly affected by the complex topography of the region. Moisture can be advected from a tropical cyclone around the subtropical ridge in place for much of the eastern North Pacific hurricane season and contribute to precipitation. This ridge, when it extends westward over the Pacific Ocean, can also prevent tropical cyclone moisture from impacting the southwestern United States. Northward-moving tropical cyclones often enter an environment with decreasing sea surface temperatures, increasing vertical wind shear, and meridional air temperature and moisture gradients. These key ingredients for extratropical transition are generally present in the eastern North Pacific, but the subtropical ridge prevents many named systems from moving northward, and only 9% of eastern North Pacific tropical cyclones from 1970 to 2011 complete ET according to cyclone phase space. However, over half of the systems that do not complete ET dissipate as cold core cyclones, a structural change that has yet to be explored in other tropical basins. It is difficult to estimate tropical cyclone intensity in a vast ocean area with few direct measurements available. The deviation angle variance technique, an objective method independent of the current techniques widely used today, was successfully applied to seven years of eastern North Pacific tropical cyclones. The RMS error of 13.5 kt for all seven years is comparable to the RMS errors found for other basins.

When a tropical cyclone (TC) is within 360 nautical miles of Kadena AB, the Air Force's Typhoon Determination (TYDET) program is used to estimate TC-induced winds expected at the base. Best-track data and Joint Typhoon Warning Center (JTWC) forecasts are used to evaluate systematic errors in TYDET. The largest contributors to errors in TYDET are a systematic error by which wind speeds are too large and the lack of size and symmetry parameters. To examine these parameters, best-track and forecasts are used to classify TCs as small or large and symmetric or asymmetric. A linear regression technique is then used to adjust TYDET forecasts based on the best-track and forecast position, size, and symmetry categories. Using independent data, over 65 percent of the overall cross-wind forecasts were improved and more than 60 percent of the cross-wind forecasts were improved when verifying conditions noted a cross-wind of 20 knots or greater. The effectiveness of the corrections and implications for TYDET forecasts are examined in relation to errors in forecast data used to initialize TYDET. A similar approach as developed here for the TYDET model at Kadena AB is proposed for other bases within the Pacific theater.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

<div>A tropical cyclone (TC) vortex is an immense, coherent, organized-convective system. Beneath this large-scale organization, is a litany of azimuthally asymmetric convective motions that exist on a spectrum of scales. These asymmetries are especially dominant during periods when the vortex undergoes critical transitions in its intensity and structure. However, the precise nature of influence of the organization of asymmetries on TC intensity change remains an enigma. The inherent difficulty in predicting their behavior is because asymmetries may arise due to different external or intrinsic sources and occur at different spatial and temporal scales while several complex mechanisms act near-simultaneously to dictate their evolution in time. As a result, multiple pathways are possible for a TC vortex that is influenced by these asymmetries. Our preliminary investigations using numerical models made it apparent that there wasn't a single, unifying way to address this problem. In this thesis, I outline multiple novel techniques of diagnosing and predicting which of the many pathways are likely for a TC vortex that is influenced by azimuthal asymmetries. </div><div> </div><div> First, using three-dimensional numerical simulations of a pair of sheared and non-sheared vortices, I demonstrate the diagnostic potential of the juxtaposition in the azimuthal phasing of: </div><div>(i) the asymmetrically distributed vertical eddy flux of moist-entropy across the top of the boundary layer, and the radial eddy flux of moist-entropy within the boundary layer; and (ii) eddy relative vorticity, eddy moist-entropy, and vertical velocity throughout the depth of the vortex. </div><div> </div><div> Second, I introduce an energetics-based diagnostic framework that computes the energy transactions occurring at asymmetries across various length-scales in the wavenumber domain. By applying it to select cases, this thesis uncovers the relative importance of all the energy pathways that support or disrupt the growth of asymmetries within the vortex. Contrary to the traditional explanations of convective aggregation/disaggregation and axi/asymmetrization through barotropic mean-eddy transactions, my thesis reveals that the growth or disruption of asymmetries are predominantly due to (i) the baroclinic conversion from available potential to kinetic energy at individual scales of asymmetries and (ii) the transactions of kinetic energy across asymmetries of different length scales. </div><div> </div><div>Finally, this thesis introduces two further diagnostic frameworks targeted at tackling the problem of real-time forecasting of TC rapid intensity changes. The first is an empirical framework which examines symmetric and asymmetric convection and other state variables within the vortex, and in the environment across a suite of TCs and identifies a set of `important' variables that are significantly different during time periods that precede a rapid intensification as opposed to a rapid weakening. My framework then ranks the variables identified based on how significantly they influence a rapid intensity change in a TC and the amplification factor of any associated variability. We recommend that future observational, and consequent TC modeling and data assimilation efforts prioritize the highest ranked variables identified here. </div><div><br></div><div>The second is a stochastic model wherein a scale-specific stochastic term is added to the equations describing the energy transactions within the TC vortex. By simulating a stochastic forcing that may arise from any scale, I compute the probability of the vortex transitioning into a rapidly intensifying or a rapidly weakening configuration across an ensemble of scenarios. </div><div><br></div><div>In summary, this thesis introduces and applies a variety of diagnostic techniques that help determine the impact of azimuthal asymmetries on TC intensity evolution.</div>

In this thesis, the role of mid-latitude cyclones in air pollution transport in the Northern Hemisphere is quantified. The storm tracking model, TRACK, is used to study the mechanisms through which pollution, specifically ozone (O3) and carbon monoxide (CO), are vented from the boundary layer to the free troposphere and thus transported over large distances, as well as the introduction of O3 from the stratosphere into the troposphere. The relationship between mid-latitude cyclones and air pollution transport of O3 and CO is explored for the first time using the Monitoring Atmospheric Composition and Climate (MACC) reanalysis, a combined meteorology and composition reanalysis dataset. A comparison between springtime surface ozone measurements at rural background sites on the west coast of Europe and cyclone track frequency in the surrounding regions was used to first establish the correlation between cyclone location and surface air quality. The focus is on spring as it tends to be the season of maximum intercontinental transport of O3. The surface observations were compared to the MACC O3 values at the same locations and case studies of how cyclones can influence surface O3 measurements are described. When cyclones track north of 53°N, there is a significant probability that the surface O3 will be high (> the 75th percentile), due to the close proximity to stratospheric intrusions and the transport at low levels across the North Atlantic Ocean. The most intense spring cyclones (95th percentile) were selected for two regions, the North Atlantic and the North Pacific, for further investigation into the mechanisms which impact O3 and CO concentrations near cyclones. These intense cyclones ( 60 over each region) often tracked over the major emission sources of eastern North America and East Asia. The distributions of MACC O3 and CO within a "typical" intense cyclone are examined by compositing the cyclones together. The cyclone-centered composites were compared to background composites of "average conditions" created by sampling the reanalysis data of the previous year to the cyclone locations. Mid-latitude cyclones are found to redistribute concentrations of O3 and CO horizontally and vertically throughout the cyclone. This is clearly shown to occur through two main mechanisms: (1) vertical lifting of CO-rich and O3-poor air isentropically from near the surface to the mid- to upper-troposphere in the region of the warm conveyor belt; and (2) descent of O3-rich and CO-poor air isentropically in the vicinity of the dry intrusion, from the stratosphere toward the mid-troposphere. This work was expanded to identify the links between teleconnection patterns, mainly the North Atlantic Oscillation (NAO), that affect the major storm track pathways in the North Atlantic sector and the distribution of MACC O3 and CO throughout the troposphere and lower stratosphere. For this analysis, TRACK was used to calculate seasonal weighted-average O3 and CO distribution maps based on the monthly NAO index. During positive NAO phase, the persistence of low pressures over the North Atlantic coupled with the Azores High promotes transport across the North Atlantic throughout the troposphere. During negative NAO phase, blocking high pressure in the eastern North Atlantic are known to occur, which shifts transport pathways to a more southerly zonal flow. This work demonstrates the complex relationship between the horizontal and vertical distribution of pollution, including surface concentrations, and synoptic-scale systems.

Flood frequency analysis over the western United States is complicated by annual peak flow records that frequently contain annual flows generated from distinctly different flood generating mechanisms. Bulletin17B (B17B) and its update Bulletin 17C (B17C) recognized the difficulties in determining flood frequency estimates with streamflow records that contain a mixed population of flood generated peaks, and recommend developing separate frequency curves when the hydrometeorologic mechanisms that generated the annual peak flows can be separated into distinct populations. Yet challenges arise when trying to consistently quantify the physical process that generated the observed flows. This thesis examines the role played by different flood producing mechanisms in generating annual maximum floods throughout the western United States using process-driven mixed populations. First I evaluate the impacts of hydrometeorological processes on flood frequency in the western United States, with emphasis on the spatial and fractional contributions of atmospheric rivers (ARs) and eastern North Pacific tropical cyclones and their remnants (TC events) on annual maximum flows throughout this area. Six main areas in which flooding are impacted by ARs at varying degrees are found throughout the western United States. The Pacific Northwest and the northern California coast have the highest fraction of AR-generated peaks (~80–100%), while eastern Montana, Wyoming, Utah, Colorado, and New Mexico have nearly no impacts from ARs. The individual regions of the central Columbia River Basin in the Pacific Northwest, the Sierra Nevada, the central and southern California coast, and central Arizona all show a mixture of 30–70% AR-generated flood peaks. Analyses related to the largest flood peaks on record highlight the strong impact of ARs on flood hydrology in this region. Conversely, TC events play a limited role in controlling the upper tail of the flood peak distributions across the western United States. Southern California, Arizona, southernmost Nevada and Utah, southern and western New Mexico, central Colorado, and Texas have the highest fractional contributions of TC-event-generated annual maximums flows (~5-14%). I then build on these insights to develop a statistical framework to perform a process-driven flood frequency analysis using the AR/non-AR-generated annual peak flows identified at 43 long-term U.S. Geological Survey (USGS) streamgages in the western United States. I use a simulation framework to perform flood frequency analyses in terms of mixed distributions and quantify the corresponding uncertainties by accounting for mixed populations. Sites with notably different quantile estimates in the upper tail of the distribution between the single (homogeneous) and the weighted (heterogeneous) population methodologies are found when (i) potentially influential low floods (PILFS) are identified and/or (ii) when the composite distribution contains markedly different at-site log-unit skews (shape parameter) among the AR/non-AR subpopulations compared to the single homogeneous population.

Analyzing past tropical cyclone activity enables researchers to recognize patterns of hurricane variability, estimate hurricane return periods, and assess local risk to future storms. This paleotempestology study used original primary data to make the historical record as comprehensive and accurate as possible for three major hurricanes: October 1844, October 1846, and September 1848. This thesis presents the reconstructed storm tracks, assesses the societal impacts, and evaluates the storm intensity of these three major hurricanes for the eastern U.S. and Cuba. The data utilized in this study include ship logbooks, newspapers, diaries, and instrumental meteorological records. A geographic information system (GIS) was used to construct the storm tracks of all three hurricanes and to map synoptic temperature data for the October 1846 and September 1848 storms. The estimated intensity of the tropical cyclones throughout their life cycle was included in the storm tracks, and intensity upon landfall was categorized based on the Saffir-Simpson scale. The results show that the October 1844 storm made landfall in western Cuba as a category 4 hurricane, causing substantial damages to Matanzas and the surrounding area. The October 1846 hurricane struck western Cuba with the intensity of a category 5 hurricane, producing devastating impacts in Havana before transitioning to an extratropical cyclone as it traveled northward across the eastern United States. The September 1848 storm originated in the western Gulf of Mexico and made landfall near Tampa Bay, Florida as a category 4 hurricane. This detailed investigation of individual historical hurricanes is an important step towards a more complete understanding of local-level hurricane risk as well as basin-wide hurricane variability.

Abstract not available