Dissertations / Theses on the topic 'Hydrothermal time'

"The increasing global demands for materials and energy directly contributes to the devastating ecological, toxicological, and climate consequences currently observed. Biomass-derived energy and materials offers a sustainable option to meeting current needs and developing novel materials. Hydrothermal carbonization is a promising green platform to valorize biomass by forming Hydrochar, a carbon solid. Hydrothermal carbonization converts biomass using liquid phase water at elevated temperatures (180-350 °C), forming organic intermediates, which dehydrate and polymerize to form the solid material on time scales of several hours. Hydrochar shows promise for a wide variety of applications, including aqueous heavy-metal adsorption. The complexity of the hydrochar prevents reliable characterization, hindering a full understanding of how to optimize the material. The focus of this study was to develop spectroscopic methods better understand the material as it changes with reaction time (ex-situ). This study developed IR and Raman Spectroscopy and Mass Spectrometry (MS) methods. Hydrochars were prepared from glucose (a model for biomass) and were prepared at different reaction times between 3 and 24 hours to understand the formation of the material and how it matures under process conditions (180 °C, autogenous pressure). IR and MS identified hydroxyl and ketone functionalities and aliphatic, furanic, and aromatic moieties, and both techniques indicated decreasing hydroxyl and furan content and increasing methyl and aromatic content. The Raman spectra were consistent with aldehyde-functionalized 1- and 2-ring arenes and aldehyde-functionalized furans, and indicated increasing 2-ring arene content relative to 1-ring arenes. MS showed a significant increase in the aromatic to furan ratio, and MS confirmed the increase in 2-ring arenes relative to 1-ring arenes seen in the Raman. These spectroscopic methods are in good agreement and will allow for greater chemical information in the hydrochar, which will inform the link between material modification under process conditions and application performance."

After-ripening, the process of seed dormancy loss in dry storage is associated with a decrease in the mean base water potential, one of the parameters of hydrothermal time. The rate of change of the mean base water potential is assumed to be a linear function of temperature above a specific base temperature and as a result can be described by a thermal after-ripening (TAR) time model, an extension of hydrothermal modelling. The thermal requirement for after-ripening is the thermal time necessary for the modelling base water potential of the seed to shift from its original value to its final value. In order to include the effects of water potential on the rate of dormancy loss, a hydrothermal after-ripening (HTAR) time model was developed. Laboratory and field studies were conducted using seeds of Bromus tectorum. These studies identified four important ranges of water potential that influence the rate of dormancy loss. The ranges are identified as follows: seeds experiencing soil water potentials seeds experiencing soil water potentials <-400 MPa do not after-ripen, between -400 MPa and -150 MPa seeds after-ripen as a function of temperature (T) and water potential (Ψ), seeds experiencing water potentials >-150 MPa after-ripen as a linear function of temperature, and somewhere above -40 MPa seeds are too wet to after-ripen. These ranges suggest that specific reaction thresholds associated with non-fully imbibed seeds also apply to the process of after-ripening. The HTAR model for B. tectorum seeds generally improved predictions of dormancy loss in the field under soil conditions that were too dry for TAR alone. Reduced after-ripening rate under extremely dry conditions is ecologically relevant in explaining how seeds may prolong dormancy under high soil temperature conditions.

Buddleia davidii is a weed naturalized in New Zealand. It invades radiata pine plantations and causes major growth reduction and economic losses. Modelling its germination for predicting its occurrence will help foresters minimise its influence in forest plantations. Germination experiments have been carried out in laboratory to assess the influence of seed origin, defoliation, temperature and water stress on germination. Defoliation treatments did not significantly affect germination. The pattern of germination for seeds from four different places within New Zealand revealed so little difference that there is no need to define different models according to the site considered. However this similarity in germination pattern is limited to New Zealand and cannot be generalised to other countries where germination appears to be significantly different. The germination of Buddleia davidii seed appeared to be a function of hydrothermal time. The base, optimum and ceiling temperatures for Buddleia are respectively 9, 25 and from 30 to 35?, and Buddleia seed germinate between 0 and approximately -6 bars. In constant conditions, the predicted germination for Buddleia davidii with the thermal time model was limited to sub-optimal temperatures and the hydrotime and hydrothermal time models described well the germination pattern at any temperature and water potential. The modified hydrothermal time model proposed by Alvarado and Bradford (2002) most accurately predicted germination although it tended to overestimate the asymptotes. Overall the hydrothermal time model allowed prediction of actual timing of germination with much accuracy. This threshold model can therefore be used for modelling the germination of Buddleia davidii subjected to constant temperature and water potential conditions.

Germination rates and germination fractions of seeds can be predicted well by the hydrothermal time (HTT) model. Its four parameters hydrothermal time, minimum soil temperature, minimum soil moisture, and variation of minimum soil moisture, however, must be determined by lengthy germination experiments at combinations of several levels of soil temperature and moisture. For some applications of the HTT model it is more important to have approximate estimates for many species rather than exact values for only a few species. We suggest that minimum temperature and variation of minimum moisture can be estimated from literature data and expert knowledge. This allows to derive hydrothermal time and minimum moisture from existing data from germination experiments with one level of temperature and moisture. We applied our approach to a germination experiment comparing germination fractions of wild annual species along an aridity gradient in Israel. Using this simplified approach we estimated hydrothermal time and minimum moisture of 36 species. Comparison with exact data for three species shows that our method is a simple but effective method for obtaining parameters for the HTT model. Hydrothermal time and minimum moisture supposedly indicate climate related germination strategies. We tested whether these two parameters varied with the climate at the site where the seeds had been collected. We found no consistent variation with climate across species, suggesting that variation is more strongly controlled by site-specific factors.
Keimungsgeschwindigkeit und Anteil gekeimter Samen lassen sich gut mit dem Hydrothermalzeit-Modell bestimmen. Dessen vier Parameter Hydrothermalzeit, Mindesttemperatur, Mindestbodenfeuchte und Streuung der Mindestbodenfeuchte müssen jedoch durch aufwendige Keimungsversuche bei Kombinationen von mehreren Temperatur- und Feuchtigkeitsstufen bestimmt werden. Für manche Anwendungen des Hydrothermalzeit-Modells sind aber ungefähre Werte für viele Arten wichtiger als genaue Werte für wenige Arten. Wenn die Mindesttemperatur und die Streuung der Mindestfeuchte aus Veröffentlichungen und Expertenwissen geschätzt würde, können die Hydrothermalzeit und Mindestbodenfeuchte aus vorhandenen Daten von Keimungsversuchen mit nur einer Temperatur- und Feuchtigkeitsstufe berechnet werden. Wir haben unseren Ansatz auf einen Keimungsversuch zum Vergleich der Keimungsquote wilder einjähriger Arten entlang eines Trockenheitsgradienten in Israel angewendet. Mit diesem Ansatz bestimmten wir die Hydrothermalzeit und Mindestfeuchtigkeit von 36 Arten. Der Vergleich mit genauen Werten für drei Arten zeigt, dass mit unserem Ansatz Hydrothermalzeit-Parameter einfach und effektiv bestimmt werden können. Hydrothermalzeit und Mindestfeuchtigkeit sollten auch bestimmte klimabedingte Keimungsstrategien anzeigen. Deshalb testeten wir, ob diese zwei Parameter mit dem Klima am Ursprungsort der Samen zusammenhängen. Wir fanden jedoch keinen für alle Arten übereinstimmenden Zusammenhang, so dass die Unterschiede vermutlich stärker durch standörtliche als durch klimatische Ursachen hervorgerufen werden.

Abstract The aim of this thesis is the knowledge of the most relevant deactivation mechanisms of Pd/Rh three-way catalysts under different ageing conditions, the deactivation correlation of laboratory scale ageing and engine bench/vehicle ageings, and the evaluation of the deactivation correlation. In the literature review, the phenomena involved in the three-way catalyst operation and its deactivation are considered. In the experimental section, ageing-induced phenomena in the catalyst are studied and deactivation correlations between laboratory scale and engine bench/vehicle ageings are presented, based on the results of several surface characterization techniques. The effects of ageing atmosphere and temperature, and time are considered in particular. Fresh and aged catalysts used in this study were metallic monoliths designed for Euro IV emission limits. Thermal ageings were carried out in the reductive, oxidative and inert atmospheres in the temperature range of 800°C to 1200°C, and in the presence of water vapour (hydrothermal ageing). The engine ageing was carried out in the exhaust gas stream of a V8 engine during a 40 hour period. The ageing procedure composed of rich and stoichiometric air-to-fuel ratios carried out consecutively. The vehicle ageing was accomplished under real driving conditions (100 000 kilometres). According to the results, deactivation of a Pd/Rh monolith is a combination of several ageing phenomena. The most important deactivation mechanisms are the sintering of active phase, the collapse in surface area and ageing-induced solid-solid phase transitions in the bulk washcoat. Furthermore, poisoning is a relevant deactivation mechanism of the vehicle-aged catalyst. High ageing temperature, gas phase composition and exposure time are essential variables to the deactivation of a Pd/Rh three-way catalyst. This thesis presents an approach to discover the deactivation correlation between the laboratory scale ageing and under the vehicle's operation in an engine bench or on-road. Based on the characterization results, the accelerated laboratory scale air ageing does not correspond to the ageing-induced changes in the catalyst under the vehicle's operation. Therefore, there is a need for a modified ageing cycle and according to the results, a deactivation correlation between the laboratory scale ageing and the engine bench ageing can be presented as a function of ageing temperature and atmosphere, and time. Instead, after the vehicle operation, the deactivation correlation cannot be presented based solely on the studied variables because, after 100 000 kilometres of driving, the role of poisoning should be taken into account in the ageing cycle. The results of this thesis can be utilized and applied in the development of laboratory scale ageing cycles, which corresponds closely to the ageing-induced changes in the catalyst during the vehicle operation. This enables a rather fast testing of the catalyst's performance and reduces the cost during the manufacturing of catalysts.

Cette thèse présente une étude détaillée de la composition des fluides de haute température du champ hydrothermal de Lucky Strike (37°N, dorsale médio atlantique) s'appuyant sur 3 campagnes d'échantillonnage réalisées dans le cadre de l'observatoire fond de mer EMSO-Açores. Ce champ hydrothermal s'est développé autour d'un lac de lave fossile bordé au Nord-Ouest, Nord Est et Sud Est par des cônes volcaniques plus anciens. En 2013, la découverte du site hydrothermal de Capelinhos à l'Est, et présentant des compositions de fluides inédites à Lucky Strike (concentration faible en Cl et forte en Fe et Mn), nous permet de proposer un nouveau modèle de circulation hydrothermale basé sur l'application de géothermobaromètres (Si ; Si-Cl ; Fe-Mn) chimiques sur 13 évents hydrothermaux. Nous avons défini 5 groupes de sites selon leur chlorinité et leur position par rapport au lac de lave. Les fluides de Capelinhos, dominés par la phase vapeur, sont rapidement extraits de la zone de séparation de phase (estimée à 2600 m sous le plancher océanique). Les fluides à proximité du lac de lave, avec des chlorinités variables, suggèrent un rééquilibrage à des pressions et températures plus faibles qu'à Capelinhos, cohérent avec des processus de refroidissement conductif et/ou d'entrainement de saumures prenant place lors de la remontée des fluides jusqu'à la base de la couche 2A. La fluctuation de la chlorinité témoigne de la variabilité du temps de résidence du fluide dans la zone de remontée, et ses relations avec les caractéristiques physiques de la croûte océanique. Nous avons évalué la variabilité temporelle de la composition des fluides collectés au cours des campagnes effectuées entre 2009 et 2015. Deux échelles de temps sont mises en évidence. (1) l'échelle de l'échantillonnage, i.e. de l'heure, répond à des phénomènes de subsurface, et révèle qu'un fluide hydrothermal refroidi conductivement (T<150°C) est stocké dans la roche poreuse entourant le site de décharge. (2) l'échelle de temps pluri-annuelle montre une fluctuation des conditions de P et T apparentes de la zone de séparation de phase et du degré d'altération du substratum dans la zone de réaction. Les variations intersites du rapport Ca/Na (indicateur du degré d'albitisation) sont dues à la séparation de phase, à l'exception des sites du Sud-Est du lac de lave qui indiquent un degré d'altération plus élevé. La concentration en Li et sa composition isotopique indiquent que le basalte du substratum est relativement frais avec des rapports W/R proches de 1 pour tous les groupes, avec des d7Li du fluide identiques au substratum. Pour le Sr nous calculons des rapports W/R plus élevés, autour de 7-8, qui sont dus au Sr de l'eau de mer initiale qui est partiellement stocké et à la formation de minéraux secondaires(l'albite et l'anhydrite) lors des interactions eau-roche dans le faciès schiste vert. La faible teneur en métaux des fluides situés autour du lac de lave est probablement due à un piégeage en subsurface, équivalent à ~65% du Fe mobilisé dans la zone de réaction (basé sur les teneurs des fluides de Capelinhos). La variabilité de chlorinité des fluides de Lucky Strike offre l'opportunité d'étudier le comportement des terres rares à l'échelle d'un site hydrothermal. Ainsi, nous montrons l'effet de la séparation de phase sur les terres rares légères et lourdes ainsi que le lien entre l'Eu et le cycle géochimique du Sr. Les terres rares dissoutes dans le panache hydrothermal montrent une perte au cours du mélange ainsi que des phénomènes de redissolution visible via la signature isotopique en Nd. Cette modification des compositions isotopiques en Nd de l'eau de mer profonde est similaire au " boundary exchange " observé aux interfaces océan-plateforme continentale. Au vue de la répartition des champs hydrothermaux sur les dorsales océaniques, ce phénomène pourrait avoir un impact sur le bilan océanique du Nd et donner lieu à un phénomène de " ridge exchange "
This thesis present a detailed study of the composition of high temperature fluid from the Lucky Strike hydrothermal field (37°N, Mid Ocean Ridge) collected during three sampling campaigns within the framework of the deep sea observatory EMSO-Azores. The hydrothermal field has developped around a fossil lava lake framed by three ancient volcanic cones. In 2013, the discovery of a new active site to the East of the system, and presenting an unprecedented fluid composition at Lucky Strike (low Cl concentration and high Fe and Mn concentration), lead to a new model of hydrothermal circulation based on chemical geothermobarometer (Si; Si-Cl) and geothermometer (Fe-Mn) applied to 13 venting sites. We defined 5 groups of sites based on their chlorinity and location around the lava lake. It appears that vapor-dominated Capelinhos fluids were extracted relatively fast from the phase separation zone (estimated at ~2600mbsf). Nevertheless, fluids in the vicinity of the lava lake, both vapor and brine dominated, display P and T conditions of equilibration lower than for Capelinhos fluids. This highlights on-going equilibration process through conductive cooling and/or brine entrainment in the upflow zone up to the layer 2A of the oceanic crust. Chlorinity variations highlight the varying residence time in the upflow of the fluids between vents which depends on physical characteristics of the crust. We studied the temporal variability of fluid composition collected between 2009 and 2015. Two time scales have been evidenced. The first is the sampling scale, i.e. ~1h, and corresponds to subsurface processes indicating that a hydrothermal fluid, conductively cooled (T<150°C), was stored in the porous substratum close to the discharge. The second is at the scale of the year. It shows fluctuations of P and T conditions in the phase separation and different degree of alteration of the substratum in the reaction zone. Intersites variations of Ca/Na ratios (proxies for albitisation) are related to phase separation expected the South Eastern sites that display a more altered substratum. To avoid this issue, we use Li and Sr isotopes which are not affected phase separation. Li concentration and isotopic composition indicates that basalt substratum is relatively fresh with W/R ratio close to 1 calculated for all groups with d7Li of fluid equivalent to substratum. Sr concentration and isotopic composition suggest higher W/R ratio (~7-8) because of seawater Sr partially removed in the recharge. Moreover, other parameters are at play such as secondary mineral formation (albite, anhydrite) during water rock interaction in the greenschist facies. Because the basalt is relatively fresh, the low metal content in the fluid around the lava lake is due to storage, in the subsurface, of approximately ~60-70% of Fe that is mobilized in the reaction zone compared to Fe-Mn rich Capelinhos fluids. Furthermore, the Cl variability from the fluids at Lucky Strike brings a unique opportunity to study the REE distribution from the reaction zone to the discharge into the deep ocean. We show that the LREE are preferentially concentrated into the brine phase. Furthermore, the Eu is linked to the Sr geochemical cycle. Dissolved REE from buoyant plume fluids highlight a scavenging effect. The Nd isotopic compositions indicate redissolution process. This Nd isotopes modification of the deep seawater is similar to the process of "boundary exchange" that occurs at the ocean/continents interface. Considering the global distribution of submarine hydrothermalism, the Nd modification at the ridge could have an impact on the global Nd cycle in the oceans and act as a "ridge exchange"

Background: This study seeks to model aspects of the regeneration of radiata pine (Pinus radiata D.Don) seedlings under a range of environmental conditions. This study investigated whether “hybrid” mechanistic models, which predict plant growth and development using empirical representations of plant physiological responses to the environment, could provide a realistic alternative to conventional empirical regeneration models. Objectives: The objectives of this study were to 1) identify the functional relationships between the environmental conditions controlling germination, establishment and growth of radiata pine seedlings, under a range of those environmental conditions as specified by temperature and available light and soil water; and 2) specify those functional relationships in hybrid mechanistic (“hybrid”) models. Methods: Radiata pine seedling germination and growth were measured under controlled environmental conditions (incubators for seed germination, growth cabinets for seedlings), and results used to adapt, parameterise and test two published hybrid models; one for germination (the hydrothermal time model); and one for seedling growth in the first six months after germination, based on plant radiation use efficiency (RUE). The hydrothermal model was tested by incubating commercial radiata pine seeds under factorial combinations of temperature and water potentials where germination was likely to occur (12.5 ºC to 32.5 ºC and 0 MPa to –1.2 MPa.). 100 seeds were germinated for each factorial combination. The hydrothermal germination model was fitted to the germination data using non-linear regression modles, will allowed simultaneous estimation of all modle parameters. Seedlings were grown in controlled growth cabinets, and their RUE was calculated as the ratio of net primary production (NPP, specified in terms of an increase in oven dry biomass), to PAR intercepted or absorbed by a seedling. Estimation of seedling RUE required development of novel techniques for non-destructive estimation of seedling oven dry weight, and measurement of PAR interception by seedlings. The effect of varying PAR flux density on RUE was tested by measuring RUE of seedlings grown at 125, 250 and 500 µmol m⁻² s⁻¹. In a second experiment, the effect of deficits in available soil water on RUE was tested by measuring RUE of seedlings grown under 250 µmol m⁻² s⁻¹ PAR flux, and at different levels of available soil water. Available soil water was specified by a soil moisture modifier factor (ƒθ) which ranges between 1 for moist soils and 0 for soils where there is insufficient water for seedling growth. This soil moisture modifier had not previously been applied in studies of tree seedling growth. Temperatures for both seedling experiments were a constant 17.5 ºC (day) and 12.5 ºC (night). Results: Hydrothermal time models accurately described radiata pine seed germination. Model predictions were closely correlated with actual seed germination over the full range of temperature and water potentials where germination was likely to occur (12.5 ºC to 32.5 ºC and 0 MPa to –1.2 MPa. The minimum temperature for germination (base temperature) was 9.0 ºC. Optimum temperatures for germination ranged from ~20ºC for slow-germinating seeds to ~27 ºC for the fastest germinating seeds. The minimum water potential for seed germination varied within the seed population, with an approximately normal distribution (base water potential = –1.38 MPa, standard deviation of 0.48 MPa). In the process of developing the model, a novel explanation for the decline in germination rates at supra-optimal temperatures was developed (Section 3.4.6), based on earlier models proposed by Alvarado & Bradford (2002) and Rowse & Finch-Savage (2003). This explanation was that the decline in germination rate was not driven just by temperature, but by accumulated hydrothermal time above the base temperature for germination (T₀). This in turn raised the base soil water potential (Ψb) towards 0, so that the reduction in germination rate arose from a reduced accumulation of hydro-time, rather than from thermal denaturation of enzymes facilitating germination – the conventional explanation for non-linear accumulation of thermal time at supra-optimal temperatures for plant development. Upwards adjustment (towards 0 MPa) of base water potentials of germinating seeds occurred also at very cold temperatures in combination with high water potentials. In both cases (very cold or else supra-optimal temperatures) this upwards adjustment in base water potentials prevented germination of part of the seed population, and is proposed as a mechanism which enables seed populations to “hedge their bets” when germinating under less than ideal germination conditions. RUE of young germinated radiata pine seedlings growing in a controlled growth cabinet was not significantly different over a range of constant PAR flux densities. Mean RUE’s were 3.22, 2.82 and 2.58 g MJ⁻¹ at 125, 250 and 500 µmol m⁻² s⁻¹ respectively. In the second experiment, the novel use of a soil moisture modifier (ƒθ) to predict RUE of seedlings subjected to water stress proved successful within a limited range of soil water stress conditions. Measured seedling transpiration and stomatal conductance were closely correlated but seedling photosynthesis was less correlated with available soil water. This result suggests that photosynthesis was not coupled with stomatal conductance when PAR flux was 250 µmol m⁻² s⁻¹, which is well below saturating irradiance for C₃ plants. Conclusions: The use of hybrid, quasi-mechanistic models to describe tree seedling growth has been seldom explored, which necessitated the development of novel experimental and analytical techniques for this study. These included a predictive model of germination decline at sub- and supra-optimal temperatures; a method for accurately estimating seedling dry weights under a range of PAR flux densities; and a novel method for estimating light interception by small seedlings. The work reported in this thesis showed that existing hybrid models (the hydrothermal time germination model and the RUE model) can be adapted to model germination and growth of radiata pine seedlings under controlled environmental conditions. Nonetheless, further research is needed before the models can be confidently used as an alternative to conventional empirical models to model regeneration in “real-world” forests. Research priorities are the performance of hydrothermal germination models under variable field conditions, and the use of the soil moisture modifier for seedlings growing on a range of soil textures and under a range of PAR fluxes.

L'évolution des réserves de pétrole implique l'utilisation en raffinerie de pétroles bruts non conventionnels, bien souvent plus lourds et donc difficiles à caractériser. Les produits pétroliers sont en effet des mélanges chimiques extrêmement complexes. La partie légère et volatile peut être analysée par chromatographie en phase gazeuse couplée à la spectrométrie de masse (GC/MS), permettant l'identification des composés par l'utilisation de mesures de masses précises et de modèles de fragmentation. Cependant ces techniques sont inadaptées à l'analyse des fractions lourdes. Dans la pratique, la caractérisation des mélanges les plus complexes implique l'utilisation de spectromètres de masse à ultra-haute résolution généralement par analyse directe sans séparation chromatographique. La technique de référence est aujourd’hui la spectrométrie de masse à transformée de Fourier par résonance cyclotronique des ions (FTICR). Grâce à une résolution supérieure à 106 et à une précision de mesure de masse inférieure à 0,1 ppm, cet instrument permet de séparer toutes les espèces présentes dans un produit pétrolier et d'attribuer à chaque valeur de m/z une composition élémentaire unique. Ceci permet d'obtenir très facilement des cartes moléculaires qui peuvent être présentées graphiquement en utilisant le diagramme de Kendrick, le diagramme de van Krevelen ou le nombre d'insaturations (DBE) en fonction du nombre de carbones. Ce travail de thèse a permis grâce à la caractérisation moléculaire de produits pétroliers (Vacuum Gas Oil, Pétroles Bruts, Matériel Interfacial, Asphaltènes et Bio-Oil…) d'aborder la complexité de leur traitement dans l’outil de raffinage. Des protocoles d'analyses des échantillons ont été développés, à l'aide de différentes sources d'ionisation à pression atmosphérique (ESI, APCI et APPI) ainsi que par désorption/ionisation laser (LDI) sur le spectromètre de masse FTICR 12T. Les informations sur le contenu isomérique des produits pétroliers ont ensuite été déterminées grâce à l'apport de la spectrométrie de mobilité ionique (IMS)
The evolution of oil reserves requires the use in refineries of unconventional crude oils, which are often heavier and therefore difficult to characterize. Petroleum products are in fact extremely complex chemical mixtures. The light and volatile part can be analysed by gas chromatography coupled with mass spectrometry (GC/MS), allowing the identification of compounds by using precise mass measurements and fragmentation models. However, these techniques are inappropriate for the analysis of heavy fractions. In practice, the characterization of the most complex mixtures involves the use of ultra-high-resolution mass spectrometers generally by direct analysis without chromatographic separation. The reference technique today is Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR). With a resolution of more than 106 and a mass measurement accuracy of less than 0.1 ppm, this instrument can separate all the species present in a petroleum product and assign a unique elemental composition to each m/z value. This makes it very easy to obtain molecular maps that can be presented graphically using the Kendrick diagram, the van Krevelen diagram or the number of unsaturations (DBE) as a function of the number of carbons. This thesis work has allowed thanks to the molecular characterization of petroleum products (Vacuum Gas Oil, Crude Oil, Interfacial Material, Asphaltenes and Bio-Oil...) addressing the complexity of their treatment in the refining tool. Protocols for sample analysis have been developed, using different sources of ionization at atmospheric pressure (ESI, APCI and APPI) as well as laser desorption/ionization (LDI) on the FTICR 12T mass spectrometer. Information on the isomeric content of petroleum products was then determined using ion mobility spectrometry (IMS)

This study utilizes recent advances in the analysis of neodymium (Nd) and samarium (Sm) by thermal ionization mass spectrometry (TIMS) to constrain timescales of heating and fluid flow within the lithosphere. Garnet grows during metamorphism and can be linked to its pressure and temperature of growth, while carbonate mineralization ages can be linked to hydrothermal fluid flow. The ability to date these common minerals makes it possible to unravel the timing and duration of tectonometamorphic processes. Garnet from the Eoarchean Nuvvuagittuq Supracrustal Belt (NSB) in Québec, Canada yields an age of 2574.66 ± 0.72 Ma. This is the most precise Neoarchean age reported for this terrane and was achieved through a modified partial dissolution procedure designed to remove the effects of much older (up to 3.8 Ga) inherited mineral growth. An accurate age for the most recent metamorphic garnet in the NSB is critical, as the (controversial) Hadean Nd model age calculations for this terrane depend on the time at which the 147Sm/144Nd systematics were last altered. Carbonate mineralization ages are explored for a diverse group of thirty samples using a novel sequential acid extraction procedure. Through this procedure it is possible to constrain carbonate mineralization in a variety of geologic settings (metamorphic fluid flow, hydrothermal and ore-forming systems) to ± 20 Myr. Zoned and bulk garnet geochronology at ten sites within a unusually localized area (~5 km2) of high temperature granulite-facies metamorphism in Bristol, New Hampshire reveals multiple brief (<1 Myr) periods of garnet growth focused between 393 and 386 Ma, at peak temperatures of 730-850°C. Comparison with garnet growth ages and temperatures , in central Massachusetts (364 Ma at 950°C) and Connecticut (341 Ma at 1000°C) reveal a regional trend of pulsed high temperature garnet growth spanning ~60 Myr from north to south, the same time span bracketed by associated igneous rocks dated via zircon geochronology. Ultrahigh metamorphic temperatures were achieved during the Acadian Orogeny in New England in localized, short pulses, likely related to igneous heating and/or associated fluid flow above and beyond the regional heating due to tectonic overthickening.