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Variações paleoambientais e paleoclimáticas durante o holoceno no Rio Grande do Norte a partir do estudo de registros geoquímicos de sedimentos de lagos e cavernas / Paleoenvironmental and paleoclimatic variations during the Holocene at Rio Grande do Norte inferred from studies about sediment geochemistry of lakes and cavesGiselle Utida 22 January 2016 (has links)
A porção norte da região Nordeste do Brasil é uma das áreas mais interessantes para estudo dos mecanismos e processos relacionados à variação de pluviosidade dos trópicos, pois a maior parte da precipitação anual está associada à migração meridional da Zona de Convergência Intertropical do Atlântico (ZCIT). O clima no Nordeste sofreu alterações durante o Holoceno, no entanto, as interpretações paleoclimáticas são ainda muito controversas devido a pequena quantidade de estudos. De forma a contribuir para a discussão sobre mudanças paleoclimáticas e paleoambientais do Nordeste brasileiro, este estudo realizou análises geoquímicas, micropaleontológicas, biogeoquímica e de isótopos de deuterium e carbono em sedimentos lacustres e guano, e análises de isótopos de oxigênio e carbono em espeleotemas do Holoceno Médio e Tardio. Os estudos da Lagoa do Boqueirão sugeriram que sua formação ocorreu devido a dinâmica fluvio-eólica, que resultou em barramentos dos canais fluviais durante o período úmido do Holoceno. A transição entre o sistema fluvial e lacustre, que marca o barramento, foi definido em torno de 4.500 anos BP pela substituição de espículas de esponjas, tipicamente fluviais, pelas diatomáceas lacustres, predominantemente Mastogloia smithii var. lacustres. Foi demonstrado que a formação e as flutuações da profundidade da Lagoa do Boqueirão não estavam associadas a precipitação regional. As variações paleoclimáticas da Lagoa do Boqueirão e da Caverna do Trapiá puderam ser acessadas através dos dados de \'delta\'D em ácidos n-alcanóicos de 28 carbonos, produzidos por vegetação terrestre e macrófitas aquáticas, e dados de \'\'delta\'POT.18\'O dos espeleotemas. Valores mais positivos (negativos) desses isótopos indicaram que durante o MCA (LIA) a região apresentava condições de seca (umidade), devido ao posicionamento mais ao Norte (Sul) da ZCIT, que migrou em direção ao Hemisfério mais aquecido de acordo com a correlação observada com a Oscilação Multidecadal do Atlântico (OMA). A porção norte do NEB apresentou paleoclima diferente em relação ao da porção sul do NEB durante o LIA, que estava seco devido ao deslocamento da Zona de Convergência do Atlântico Sul (ZCAS) mais para sul, assim como a ZCIT, que não afetou a porção sul do NEB. Mudanças paleoambientais foram também definidas com base na idade de sequências sedimentares clásticas datadas por LOI e pelos depósitos de guano em condutos de cavernas em Felipe Guerra-RN. A deposição de sedimentos terrígenos na caverna Urubu entre 7 to 4 ky B.P. cave foi cronologicamente associada a clima mais úmido, o que é apoiado pelo baixos valores de \'\'delta\' POT.18\'O values de espeleotemas. Esse período também foi marcado pelo aumento da contribuição de de carbono orgânico do solo como indicado por valores mais baixos de \'\'delta\'POT.13\'C dos mesmos espeleotemas. Uma transição abrupta para clima mais seco pode está associada ao final da sedimentação clástica na caverna por volta de 4.2 ky devido a interrupção do fluxo do rio subterrâneo e completa erosão do solo ao redor da caverna. A erosão do solo é ressaltada por altos valores de \'\'delta\'POT.13\'C dos espeleotemas próximos aos da rocha encaixante (~0 %0). Estes resultados demonstraram uma relação entre preenchimento sedimentar da caverna Urubu com a formação e erosão de solo na sua volta. Esse aumento de aridez, particularmente nos últimos três mil anos na região, foi também importante para preservação de depósitos de guano sobre os sedimentos clásticos, visto que esse material é bastante solúvel. As idades das camadas de guano foram utilizadas para definir períodos de alta ocupação das cavernas por morcegos entre 1730 and 677 cal. anos A.P. e 200 cal anos A.P. até o recente. Durante o evento MCA houve redução na acumulação de guano que levou a um hiato deposicional por conta que o clima seco desfavoreceu a sobrevivência dos morcegos na região. A acumulação de guano voltou a ocorrer a 200 anos atrás, provavelmente porque a população de morcegos foi reestabelecida, devido a clima mais úmido. / The northern sector of Nordeste of Brazil (NEB) is one of the most interesting regions to study mechanisms and processes related to fluctuations tropical rainfall, as the majority of annual precipitation is associated to the meridional migration of Intertropical Convergence Zone (ITCZ). Climate in NEB changed during the Holocene, although paleoclimatic interpretations are still controversial due to small number of studies. This study contribute to the discussion about paleoclimatic and paleoenvironmental changes of NEB by using geochemistry, micropaleontological, biogeochemistry and deuterium and carbon isotope analyses in lacustrine sediments and bat guano, and also speleothem isotope records from middle to late Holocene. Studies from Boqueirão Lake suggested that its formation occurred due to the fluvio-eolian dynamic, which resulted in blockage of fluvial channels during the holocenic humid period. Transition between fluvial and lacustrine system recorded the barrage formation and was defined around 4,500 years BP and suggested by the substitution of fluvial sponge spicules to lacustrine diatoms, mainly Mastogloia smithii var. lacustres, preserved in sediments. These data demonstrated that depth fluctuations of Boqueirão Lake were not associated to local precipitation accumulation. Paleoclimatic changes were reconstructed from Boqueirão Lake and Trapiá Cave based on \'delta\'D of n-alkanoic acids of 28 carbons, which are produced by terrestrial vegetation and macrophytes, and from \'\'delta\'POT.18\'O of speleothems. More positive (negative) isotope ratios indicate persistent dry (wet) climatic conditions during the MCA (LIA) there, due to a north (south) displacement of ITCZ. This climate system migrated toward the warmest ocean according to the correlation with Atlantic Multidecal Oscillation (AMO). The northern portion of the NEB (nNEB) presented different paleoclimate conditions when compared to the southern NEB portion (sNEB) during the LIA. LIA in sNEB was dry due to the displacement of the South Atlantic Convergence Zone (SACZ) to a southernmost position. Paleoenvironmental changes were attested by determining the age of clastic sequences filling cave conduits dated by OSL method and also by radiocarbon in bat guano. The deposition of terrigenous sediments in Urubu cave from 7 to 4 ky B.P. cave was chronologically associated with more humid climate indicated by low \'\'delta\'POT.8\'O values in speleothems. In addition, this period was marked by increased contribution of organic carbon from soil indicated by negative values of \'\'delta\'POT.13\'C of the same speleothems. An abrupt transition to dry climate was indicated by the end of clastic sedimentation at about 4.2 ky because interruption of underground river flow and complete erosion of soil surrounding the cave as indicated by abrupt enrichment of \'\'delta\'POT.13\'C values of speleothems, reaching values similar to the carbonate bedrock (~0 %o). These data demonstrated the relationship between the sedimentary filling of the Urubu Cave and the formation and soil erosion in the region. These predominant dry conditions during last three millenniums in the region were also important for preservation ofbat Guano deposits above terrigenous sediments. The chronological data of guano was also used to indicate two periods of high accumulation associated with intense occupation of caves by bat colonies between 1,730 and 677 years cal BP and 200 cal years BP until recently. During the MCA occurred a reduction in guano accumulation until a complete hiatus, because dry conditions did not favor bats survival. Guano deposit accumulated again only 200 years ago, when the population of bats restored with stabilization of relatively humid conditions.
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First investigation of electromagnetic coupling of the d*(2380) hexaquarkKay, Stephen John Donald January 2018 (has links)
This thesis presents the first measurement of the d*(2380) (hexaquark) electromagnetic coupling, extracted from the deuteron photodisintegration (~γd → d* → ~np) reaction. The experiment was carried out at the Mainzer Microtron (MAMI) facility in the Institut für Kernphysik in Mainz, Germany. A racetrack microtron at the MAMI facility provided a 1557 MeV longitudinally polarised electron beam. This electron beam was directed onto a thin radiator to produce a bremsstrahlung photon beam. Diamond and amorphous (metallic) radiators were used to produce linearly and circularly polarised photons respectively. The produced bremsstrahlung photon beam was energy 'tagged' with a resolution of ~4 MeV over the photon-energy range of 150-1400 MeV using the Glasgow Photon Tagger. The tagged photons were incident on a 10 cm long liquid deuterium target. This target was surrounded by a new nucleon recoil polarimeter apparatus and placed within the Crystal Ball calorimeter at MAMI. An array of PbWO4 and BaF2 detectors (TAPS) was used to provide calorimetry at forward angles. The newly constructed large acceptance recoil polarimeter measures the polarisation of the nucleons in the final state. The combination of this new apparatus with the polarised photon beam facility gives access to a number of single and double polarisation observables. The photon beam asymmetry, Σ, and the double polarisation observable, Cx', were examined in measurements of the reaction d(→γ,→n→p) over a large range of energies with a close to full angular coverage. The observable Cx' is determined for the neutron produced in deuteron photodisintegration for the first time. The new data constrains mechanisms of deuteron photodisintegration and assesses the existence and contribution of the d*(2380) resonance.
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Comportement du deutérium dans les matériaux d’intérêt pour la fusion thermonucléaire / Deuterium behavior in first-wall materials for nuclear fusionBernard, Elodie 31 October 2012 (has links)
Dans la conception des futurs réacteurs de fusion, l’impact des interactions plasma – paroi pèse grandement sur le choix des matériaux à utiliser en première interface. L’utilisation du tritium en tant que combustible impose de plus des limites de sécurité quant à la quantité totale contenue dans le réacteur. L’analyse d’échantillons de parois de Tokamaks a montré une pénétration et une rétention du deutérium (utilisé à la place du tritium) au sein des matériaux carbonés; cette rétention est problématique car contrairement à la rétention dans les couches co-déposées, on ne peut espérer l’éliminer facilement. De part l’accès difficile aux échantillons réels, l’étude de ce phénomène se limite souvent à des analyses post-mortem.Afin d’accéder à la dynamique du phénomène et de s’affranchir de potentielles redistributions des éléments lors du stockage, un dispositif couplant micro analyse nucléaire (µNRA) et implantation basse énergie simultanée, visant à reproduire l’interaction entre le deutérium et les matériaux de la première paroi, a été mis en place. L’analyse µNRA permet de caractériser les profils de répartition en trois dimensions du deutérium en temps réel, à des échelles micrométriques. Des tests ont permis de confirmer le caractère non-perturbateur du faisceau d’analyse.On observe sur l’ensemble des données obtenues que la surface de l’échantillon (0-1 µm) présente une teneur en deutérium élevée et quasi constante ; la répartition du deutérium y est uniforme. A contrario, le deutérium piégé en profondeur (1-11 µm) se concentre dans des sites préférentiels liés à la microstructure du matériau. L’inventaire deutérium en profondeur semble augmenter avec la fluence incidente, malgré une grande dispersion des données attribuée à la variation de structure des zones étudiées. La saturation surfacique comme la migration en profondeur sont instantanées ; le stockage sous vide entraine une légère désorption du deutérium.Les observations faites par µNRA ont été croisées avec celles obtenues via d’autres techniques expérimentales. La µtomographie X a permis d’identifier clairement les porosités comme sites de localisation préférentielle du deutérium en profondeur. La micro-spectrométrie Raman a révélé la formation d’une couche amorphe fine (~30 nm) et saturée en deutérium à la surface du CFC suite à l’exposition au faisceau de deutérium. Enfin, la caractérisation expérimentale de la migration du deutérium dans les CFC obtenue est confrontée aux modèles existants, et un modèle simplifié original est proposé. Considérant que le dépôt en profondeur se produit par le biais de l’implantation et de la diffusion coulombienne du deutérium à la surface des porosités, il permet de reproduire qualitativement les profils de migration observés. / Plasma-wall interactions play an important part while choosing materials for the first wall in future fusion reactors. Moreover, the use of tritium as a fuel will impose safety limits regarding the total amount present in the tokamak. Previous analyses of first-wall samples exposed to fusion plasma highlighted an in-bulk migration of deuterium (used as an analog to tritium) in carbon materials. Despite its limited value, this retention is problematic: contrary to co-deposited layers, it seems very unlikely to recover easily the deuterium retained in such a way. Because of the difficult access to in situ samples, most published studies on the subject were carried out using post-mortem sample analysis.In order to access to the dynamic of the phenomenon and come apart potential element redistribution during storage, we set up a bench intended for simultaneous low energy ion implantation, reproducing the deuterium interaction with first-wall materials, and high energy microbeam analysis. Nuclear reaction analysis performed at the micrometric scale (µNRA) allows characterizing deuterium repartition profiles in situ. This analysis technique was checked to be non-perturbative.We observed from the experimental data set that the material surface (depth 0-1 µm) displays a high and nearly constant deuterium content, with a uniform distribution. On the contrary, in-bulk deuterium (1-11 µm) localizes in preferential trapping sites related to the material microstructure. In-bulk deuterium inventory seems to increase with the incident fluence, in spite of the wide data scattering attributed to the structure variation of studied regions. Deuterium saturation at the surface as well as in-depth migration is instantaneous; in-vacuum storage leads only to a small deuterium global desorption.Observations made via µNRA were combined with results from other characterization techniques. X-ray µtomography allowed identifying porosities as the preferential trapping sites for in-depth deuterium retention. Raman µspectrometry disclosed the formation of an amorphous layer at the surface, very thin (~30 nm) and deuterium saturated, following deuterium irradiation.At last, we confronted the experimental characterization obtained with existing models for deuterium behaviour in carbon materials and proposed a simple and original one. Considering that in-depth retention is due to deuterium implantation and Coulombian diffusion at the open porosity surfaces, it allows reproducing qualitatively the observed experimental profiles.
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Cosmology with the Lyman alpha forestLiske, Jochen, Physics, Faculty of Science, UNSW January 2000 (has links)
In this thesis we investigate the large-scale distribution of Ly alpha forest absorption, the effect of ionizing radiation from QSOs on their surrounding intergalactic medium and the primordial abundance of deuterium. We develop a new technique for detecting structure on Mpc scales in the Ly alpha forest. This technique does not rely on identifying individual absorption lines but is rather based on the statistics of the transmitted flux. We demonstrate that the new method is significantly more sensitive to the presence of large-scale structure in the Ly alpha forest than a two-point correlation function analysis. We apply this method to 2 A resolution spectra of ten QSOs which cover the redshift range 2.2 < z < 3.4. The QSOs form a closely spaced group on the sky and are concentrated within a 1-deg^2 field. We find evidence for large-scale structure in the distribution of Ly alpha forest absorption at the > 99 per cent confidence level. Along the line of sight we find overdense Ly alpha absorption on scales of up to 1200 km s^-1. There is also strong evidence for correlated absorption across line of sight pairs separated by < 3 h^-1 Mpc. For larger separations the cross-correlation signal becomes progressively less significant. Using the same technique and dataset we confirm the existence of the proximity effect. We derive a value for the mean intensity of the extragalactic background radiation at the Lyman limit of J = (3.6^+3.5_-1.3) x 10^-22 ergs s^-1 cm^-2 Hz^-1 sr^-1. This value assumes that QSO redshifts measured from high ionization lines differ from the true systemic redshifts by Delta v = 800 km s^-1. Allowing for known QSO variability we find evidence at a level of 2.1 sigma that the significance of the proximity effect is correlated with QSO Lyman limit luminosity. From the complete sample we find no evidence for the existence of a foreground proximity effect, implying either that J > 20 x 10^-22 ergs s^-1 cm^-2 Hz^-1 sr^-1 or that QSOs emit at least a factor of 1.4 less ionizing radiation in the plane of the sky than along the line of sight to Earth. We do, however, find one counter-example where a foreground QSO apparently depletes the absorbing gas in four surrounding lines of sight. We discuss the feasibility of pre-selecting absorption systems from low resolution data for a measurement of the primordial deuterium abundance. We present a new, low resolution spectroscopic survey of 101 high redshift QSOs aimed at identifying candidate D/H systems. We further present an echelle spectrum of a Lyman limit system at z = 2.917. We find that this system is most likely heavily contaminated and does not yield an interesting limit on D/H.
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Etude du plasma secondaire créé dans le neutraliseur d'ITER pour la formation de neutres rapidesDuré, Franck 21 December 2011 (has links) (PDF)
Pour réaliser les conditions des réactions de fusion thermonucléaire dans le tokamak ITER, des moyens additionnels de chauffage sont requis. L'une des principales méthodes pour chauffer les ions du plasma de coeur sera l'injection de neutres D0 énergétiques. Le neutraliseur est l'étape de l'injecteur de neutres d'ITER où le faisceau de deutérium prend ses propriétés en termes de taux de neutres D0 et de direction de propagation. L'interaction entre le faisceau à 1MeV et le gaz D2 neutralisant (~0.1Pa) crée un plasma secondaire. Les phénomènes physiques en jeu sont présentés à travers l'analyse des résultats du code OBI-2. OBI-2 est un code PIC-MCC (Particle In Cell Monte Carlo Collision) en géométrie cylindrique (2D3V) développé au LPGP qui permet de suivre la propagation du faisceau et les particules du plasma le long du neutraliseur.L'injection de lithium comme cible neutralisante a été étudiée et comparée au deutérium. Une étude paramétrique sur le neutraliseur basé sur le lithium a été réalisée dans la mesure où la longueur et/ou la densité de Li injectée peuvent être modifiées. Le profil de densité de Li a été estimé par le code Monte-Carlo 3D MC-OLIJET développé au LPGP. Le profil résultatnt a été implémenté en entrée du code PIC-MCC. Les résultats montrent la faisabilité du neutraliseur basé sur le lithium, gardant la convergence correcte du faisceau et avec de meilleures performances en termes de durée de vie des cryompompes avant régénération, de neutralisation du faisceau, d'effet de rétrodiffusion des ions positifs.
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Monitoring climate and plant physiology using deuterium isotopomers of carbohydratesAugusti, Angela January 2007 (has links)
Climate is changing and it is certain that this change is due to human activities. Atmospheric greenhouse gases have been rising in an unprecedented way during the last two centuries, although the land biosphere has dampened their increase by absorbing CO2 emitted by anthropogenic activities. However, it is unclear if this will continue in the future. This uncertainty makes it difficult to predict future climate changes and to determine how much greenhouse gas emissions must be reduced to protect climate. To understand the future role of plants in limiting the atmospheric CO2 level, the effect of increasing CO2 on plant photosynthesis and productivity has been studied. However, studies on trees showed contradictory results, which depended on the duration of the experiment. This revealed that an initial strong CO2 fertilization may be a transient response that disappears after a few years. Because climate changes over centuries, we must explore the response of vegetation to increasing CO2 on this time scale. Studying tree rings is a good alternative to impractical decade-long experiments, because trees have experienced the CO2 increase during the last 200 years and may already have responded to it. This thesis shows that the intramolecular distribution of the stable hydrogen isotope deuterium (deuterium isotopomer distribution, DID) of tree rings is a reliable tool to study long-term plant-climate adaptations. The premise for this is that the deuterium abundance in tree rings depends on environmental as well as physiological factors. Using newly developed methodology for DID measurements, the influences of both factors can be separated. Applied to tree rings, separating both factors opens a strategy for simultaneous reconstruction of climate and of physiological responses. The results presented show that DIDs are influenced by kinetic isotope effects of enzymes, allowing studies of metabolic regulation. We show that the abundances of specific D isotopomers in tree-ring cellulose indeed allow identifying environmental and physiological factors. For example, the D2 isotopomer is mostly influenced by environment, its abundance should allow better reconstruction of past temperature. On the other hand, the abundance ratio of two isotopomers (D6R and D6S) depends on atmospheric CO2, and might serve as a measure of the efficiency of photosynthesis (ratio of photorespiration to assimilation). The presence of this dependence in all species tested and in tree-ring cellulose allows studying adaptations of plants to increasing CO2 on long time scales, using tree-ring series or other remnant plant material. / Klimatet förändras och det är numera allmänt vedertaget att detta beror på människans aktiviteter. Halten av växthusgaser har stigit onormalt mycket under de senaste två århundradena och detta beror i största del på människans användning av fossila bränslen. Landbiosfären har hittills haft en buffrande effekt på klimatförändringen eftersom den tar upp och lagrar mycket av växthusgasen CO2. Det är dock osäkert om, och i så fall hur länge, denna effekt kvarstår. Detta gör det mycket svårt att förutsäga framtida klimatförändringar, och därmed hur mycket utsläppen av växthusgaser måste reduceras för att skydda klimatet. För att förstå växternas framtida förmåga att begränsa halten atmosfäriskt CO2 har man studerat effekten av förhöjda halter av CO2 på växters fotosyntes och produktivitet. Resultaten av dessa försök varierar i stor omfattning. Studier på träd odlade under höga halter CO2 indikerar att den initiala ökningen av en trädets produktivitet kan vara en temporär effekt som försvinner redan efter några år. Eftersom klimatförändringen sker under århundraden, måste även växternas anpassningar på förhöjd CO2 halt utforskas på denna tidsskala, men experiment som skulle ta tiotals år är opraktiska att utföra. Trädringar är ett bra sätt att studera sådana anpassningar, eftersom träd redan har upplevt de senaste två hundra årens ökning av koldioxid och dess trädringar därför kan innehålla information om en respons som redan skett. Denna avhandling visar att den intramolekylära fördelningen av den stabila väteisotopen deuterium i trädringar är en tillförlitlig metod för att studera växters anpassningsförmåga till långsiktiga klimatförändringar. Antagandet bakom denna strategi är att isotopfördelningen i trädringar beror på faktorer både från miljön och växtens fysiologi. Om båda faktorerna skulle kunna utvinnas från trädringar, skulle detta öppna en helt ny väg för parallell rekonstruktion av klimatet och växters anpassning till det. Avhandlingen presenterar den första tekniken för att mäta isotopfördelningen av deuterium i växtglukos. Resultaten visar att deuteriumfördelningen hos växtglukos påverkas av enzymers isotopeffekter, vilket möjliggör att regleringen av växternas metabolism kan kartläggas. I avhandlingen bevisas att halten deuterium i skilda intramolekylära positioner (isotopomerer) av glukos från trädringcellulosa bestäms av miljöfaktorer respektive trädets fysiologi. T.ex. påverkas deuteriumhalten i position 2 (D2 isotopomer) av glukosmolekylen huvudsakligen av miljön, vilket kan användas för att förbättra temperaturrekonstruktioner från trädringar. Å andra sidan är kvoten deuterium mellan två andra positioner (D6R och D6S) relaterat till halten atmosfäriskt koldioxid, och kvoten skulle kunna användas som mått för fotosyntesens effektivitet, dvs. förhållandet mellan fotorespiration och fotosyntes. Närvaron av denna relation i trädringar och annat växtmaterial i alla de växter vi hittills studerat, öppnar en helt ny möjlighet att studera växters anpassning till den ökande mängden CO2 i atmosfären under århundraden.
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Deuterium isotopomers as a tool in environmental researchBetson, Tatiana January 2006 (has links)
This thesis describes the development and the use of quantitative deuterium Nuclear Magnetic Resonance spectroscopy (NMR) as a tool in two areas of environmental research: the study of long term climate-plant interactions and the source tracking of persistent organic pollutant. Long-term interactions between plants and climate will influence climate change during this century and beyond, but cannot be studied in manipulative experiments. We propose that long tree rings series can serve as records for tracking such interactions during past centuries. The abundance of the stable hydrogen isotope deuterium (D) is influenced by physical and biochemical isotope fractionations. Because the overlapping effects of these fractionations are not understood, studies of the D abundance of tree rings led to conflicting results. We hypothesized that both types of fractionations can be separated if the D abundance of individual C-H groups of metabolites can be measured, that is if individual D isotopomers are quantified. The first paper describes a technique for quantification of D isotopomers in tree-ring cellulose by NMR. The technique showed that the D isotopomers distribution (DID) was non-random. Therefore, the abundance of each isotopomer potentially contains individual information which suggests an explanation for the conflicting results obtained by measuring the overall D abundance (dD). In the second paper, this technique was used to study hydrogen isotope exchange during cellulose synthesis in tree rings. This revealed that some C-H positions exchange strongly with xylem water, while others do not. This means that the exchanging C-H positions should acquire the D abundance of source water, which is determined by physical fractionations, while non-exchanging C-H positions of tree-ring cellulose should retain biochemical fractionations from the leaf level. Therefore, the abundance of the corresponding D isotopomers should contain information about climate and physiology. When analysing tree-ring series, the DIDs should reflect information about temperature, transpiration and regulation of photosynthesis. In the third paper, we showed that CO2 concentration during photosynthesis determines a specific abundance ratio of D isotopomers. This dependence was found in metabolites of annual plants, and in tree-ring cellulose. This result shows that D isotopomers of tree-ring series may be used to detect long-term CO2 fertilisation effects. This information is essential to forecast adaptations of plants to increasing CO2 concentrations on time scales of centuries. In the fourth paper, the source of persistent organic pollutants in the environment was tracked using DID measurements. The dD values of two compounds of related structures were not enough to show indisputably that they did not originate from the same source. However, the DIDs of the common part between the two compounds proved that they did not originate from the same source. These results underline the superior discriminatory power of DIDs, compared to dD measurements. The versatility of DID measurements makes them a precious tool in addressing questions that can not be answered by dD measurements. / Betson, Tatiana R
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Approximate quantum dynamics methods for time correlation functionsSmith, Kyle Kurt Gabriel 03 July 2014 (has links)
The dynamic structure factor of liquid para-hydrogen and ortho-deuterium in corresponding thermodynamic states, (T = 20.0 K, n = 21.24 nm⁻³) and (T = 23.0 K, n = 24.61 nm⁻³) respectively, has been computed by both the Feynman-Kleinert linearized path-integral (FK-LPI) and Ring-Polymer Molecular Dynamics (RPMD) methods and compared with Inelastic X-ray Scattering spectra. The combined use of computational and experimental methods enables a reduction in experimental uncertainties for the determination of the true sample spectrum. Furthermore, the refined experimental spectrum of para-hydrogen and ortho-deuterium is consistently reproduced by both FK-LPI and RPMD at momentum transfers lower than 12.8nm⁻¹. At larger momentum transfers the F K - LP I results agree with experiment much better for ortho-deuterium than for para-hydrogen. More specifically we found that for k ~ 20.0 nm⁻¹ para-hydrogen provides a test case for improved approximations to quantum dynamics. We meet this demand for an improved approximate quantum dynamics method by developing two classes of quasi-classical dynamics that are shown to conserve the initial quantum ensemble when used in conjunction with the Feynman-Kleinert approximation of the density operator. As shown, both classes of dynamics are able to recover the exact classical and high temperature limits of the quantum time correlation function, while a subset is able to recover the exact harmonic limit. A comparison of the approximate quantum time correlation functions obtained from both classes of dynamics are made with the exact results for the challenging model problems of the quartic and double-well potentials. It is found that this new Feynman-Kleinert Quasi-Classical Wigner (FK-QCW) method provides a great improvement over the Feynman-Kleinert implementation of the classical Wigner approximation, also known as FK-LPI, in which purely classical dynamics are used. Furthermore, it is shown that the first class of dynamics reduces to Centroid Molecular Dynamics (CMD) when used within the framework of the classical Wigner approximation for the Kubo transformed time correlation function. Finally, we apply the Feynman-Kleinert Quasi-Classical Wigner (FK- QCW) method to the same liquid para-hydrogen and ortho-deuterium system, previously studied using FK-LPI and RPMD. When applied to this challenging system, it is shown that this new FK-QCW method consistently reproduces the experimental dynamic structure factor for all momentum transfers considered. This shows that FK-QCW provides a great improvement over FK-LPI for not only model problems, but also realistic systems. Furthermore, for small momentum transfers, where RPMD is applicable, it is shown that FK-QCW provides nearly the same results as RPMD, thus suggesting that FK-QCW provides a potentially more appealing algorithm than RPMD since one is not limited to correlation functions involving linear operators. This then suggests that the FK-QCW method is a top contender in the realm of approximate quantum dynamics methods which allow for the practical evaluation of time correlation functions. / text
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Influence of surface passivation on the photoluminescence from silicon nanocrystalsSalivati, Navneethakrishnan 07 January 2011 (has links)
Although silicon (Si) nanostructures exhibit size dependent light emission, which can be attributed to quantum confinement, the role of surface passivation is not yet fully understood. This understanding is central to the development of nanocrystal-based detectors. This study investigated the growth, surface chemistry, passivation with deuterium (D2), ammonia (ND3) and diborane (B2D6) and the resulting optical properties of Si nanostructures.
Si nanocrystals less than 6 nm in diameter are grown on SiO2 surfaces in an ultra high vacuum chamber using hot-wire chemical vapor deposition and the as grown surfaces are exposed to atomic deuterium. Temperature programmed desorption (TPD) spectra show that that the nanocrystals surfaces are covered by a mix of monodeuteride, dideuteride and trideuteride species. The manner of filling of the deuteride states on nanocrystals differs from that for extended surfaces as the formation of the dideuteride and trideuteride species is facilitated by the curvature of the nanocrystal. No photoluminescence (PL) is observed from the as grown unpassivated nanocrystals. As the deuterium dose is increased, the PL intensity also begins to increase. This can be associated with increasing amounts of mono-, di- and trideuteride species on the nanocrystal surface, which results in better passivation of the dangling bonds and relaxing of the reconstructed surface. At high deuterium doses, the surface structure breaks down and amorphization of the top layer of the nanocrystal takes place. Amorphization reduces the PL intensity. Finally, as the nanocrystal size is varied, the PL peak shifts, which is characteristic of quantum confinement.
The dangling bonds and the reconstructed bonds at the NC surface are also passivated and transformed with D and NDx by using deuterated ammonia (ND3), which is predissociated over a hot tungsten filament prior to adsorption. At low hot wire ND3 doses PL emission is observed at 1000 nm corresponding to reconstructed surface bonds capped by predominantly monodeuteride and Si-ND2 species. As the hot wire ND3 dose is increased, di- and trideuteride species form and intense PL is observed around 800 nm that does not shift with NC size and is associated with defect levels resulting from NDx insertion into the strained Si-Si bonds forming Si2=ND. The PL intensity at 800 nm increases as the ND3 dose is increased and the intensity increase is correlated to increasing concentrations of deuterides. At extremely high ND3 doses PL intensity decreases due to amorphization of the NC surface. In separate experiments, Si NCs were subjected to dissociative (thermal) exposures of ammonia followed by exposures to atomic deuterium. These NCs exhibited size dependent PL and this can be attributed to the prevention of the formation of Si2=ND species.
Finally, deuterium-passivated Si NCs are exposed to BDx radicals formed by dissociating deuterated diborane (B2D6) over a hot tungsten filament and photoluminescence quenching is observed. Temperature programmed desorption spectra reveal the presence of low temperature peaks, which can be attributed to deuterium desorption from surface Si atoms bonded to subsurface boron atoms. The subsurface boron likely enhances nonradiative Auger recombination. / text
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RAMAN SPECTROSCOPIC STUDIES OF HYDROGEN CLATHRATE HYDRATESStrobel, Timothy A., Koh, Carolyn A., Sloan, E. Dendy 07 1900 (has links)
Raman spectroscopic measurements of various hydrogen bearing clathrate hydrates have been performed under high (< 1cm-1) and low resolution (>2 cm-1) conditions. Raman bands for hydrogen in most common clathrate hydrate cavities have been assigned. Unlike most clathrate hydrate guests, the general observation is no longer valid that the larger the clathrate cavity in which a guest resides, the lower the vibrational frequency. This is rationalized by the multiple hydrogen occupancies in larger clathrate cavities. Both the roton and vibron bands for hydrogen clathrates illuminate interesting quantum dynamics of the enclathrated hydrogen molecules. At 77K, the progression from ortho to para H2 occurs over a relatively slow time period (days). The para contribution to the roton region of the spectrum exhibits the triplet splitting also observed in solid para H2. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature and with isotopic substitution by deuterium. Raman spectra from H2 and D2 hydrates suggest that the occupancy patterns between the two hydrates are analogous. The Raman measurements demonstrate that this is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.
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