The stable isotope ratio of non-exchangeable hydrogen (δ2Hn) emerged as a promising new tool for source attribution in aquatic ecology, which can better discriminate between the organic matter sources. However, determining the absolute isotopic values is problematic due to the functional groups with hydrogen (H) that can easily exchange with the ambient water. This can lead to significant uncertainties in the absolute isotopic values, which eventually translates into errors in source attribution. However, controlled H exchange experiments with dual water equilibrations can alleviate this problem. However, current methods report significant variation in the absolute values, likely originating in partial H exchange, uncertainty in fractionation factors between exchangeable H and ambient water, and residual moisture. Here I used two methods for H exchange based on steam and liquid water using novel equipment for sample preparation called the Isobox. I evaluated the exchangeable H fraction in materials commonly analysed in ecology. Furthermore, I have investigated how these methods and associated analytical uncertainties can influence the mathematical mixing models used to resolve the source attribution using known sample mixtures made with soils and algae. The results show that 1) H exchange experiments using liquid water equilibration provide a higher exchangeable H fraction than the steam-based method, which was approximately three times higher. 2) The two-source mixing model proved to effectively determine the source attribution with known soil and algae mixtures, as evidenced by both water and steam equilibration. However, prior exposure to isotopically divergent waters can lead to source attribution errors, particularly with steam-based methods that provide low exchangeable H fractions. 3) When labile H is fully exchanged, source attribution does not depend on absolute δ2Hn determination, and simple one-water equilibration is sufficient. 4) Additional uncertainties in source attribution could originate from fractionation factors and δ2H measurement variability. The findings of this study conclude that the variations in fractionation factors did not significantly alter the mixing model as the error was below 5%. 5) Based on these experiments, I recommend keeping the analytical uncertainty of δ2H below ±5‰, which amounts to about a 6% error factor in source attribution. Finally, these experiments and analyses show how the methods can generate reliable data, depending on the research questions and whether absolute or relative isotopic values are required. This study provides different analytical pathways.

<p>Methods for performing large-scale parallel Molecular Dynamics(MD) simulations are investigated. A perspective on the field of parallel MD simulations is given. Hardware and software aspects are characterized and the interplay between the two is briefly discussed. </p><p>A method for performing <i>ab initio </i>MD is described; the method essentially recomputes the interaction potential at each time-step. It has been tested on a system of liquid water by comparing results with other simulation methods and experimental results. Different strategies for parallelization are explored.</p><p>Furthermore, data-parallel methods for short-range and long-range interactions on massively parallel platforms are described and compared. </p><p>Next, a method for treating electrostatic interactions in MD simulations is developed. It combines the traditional Ewald summation technique with the nonuniform Fast Fourier transform---ENUF for short. The method scales as <i>N log N</i>, where <i>N </i>is the number of charges in the system. ENUF has a behavior very similar to Ewald summation and can be easily and efficiently implemented in existing simulation programs.</p><p>Finally, an outlook is given and some directions for further developments are suggested.</p>

Methods for performing large-scale parallel Molecular Dynamics(MD) simulations are investigated. A perspective on the field of parallel MD simulations is given. Hardware and software aspects are characterized and the interplay between the two is briefly discussed. A method for performing ab initio MD is described; the method essentially recomputes the interaction potential at each time-step. It has been tested on a system of liquid water by comparing results with other simulation methods and experimental results. Different strategies for parallelization are explored. Furthermore, data-parallel methods for short-range and long-range interactions on massively parallel platforms are described and compared. Next, a method for treating electrostatic interactions in MD simulations is developed. It combines the traditional Ewald summation technique with the nonuniform Fast Fourier transform---ENUF for short. The method scales as N log N, where N is the number of charges in the system. ENUF has a behavior very similar to Ewald summation and can be easily and efficiently implemented in existing simulation programs. Finally, an outlook is given and some directions for further developments are suggested.

A core level spectroscopy study of ice and water is presented in this thesis. Combining a number of experiments and spectrum calculations based on density functional theory, changes in the local valence electronic structure are shown to be sensitive to the local H-bonding configurations. Exploiting this sensitivity, we are able to approach important scientific problems for a number of aggregation states; liquid water, the water-metal interface, bulk and surface of hexagonal ice. For the H-bonded model system hexagonal ice, we have probed the occupied valence electronic structure by x-ray emission and x-ray photoelectron spectroscopy. Stepwise inclusion of different types of interactions within density functional theory, together with a local valence electron population analysis, show that it is essential to include intermolecular charge transfer together with internal s-p rehybridizations in order to describe the changes in electronic structure seen in the experiment. The attractive electrostatic interaction between water molecules is enhanced by a decrease in Pauli repulsion. A simple electrostatic model due to charge induction from the surrounding water is unable to explain the electronic structure changes. By varying the probing depth in x-ray absorption the structure of the bulk, subsurface and surface regions is probed in a thin ice film. A pronounced continuum for fully coordinated species in the bulk is in sharp contrast to the spectrum associated with a broken symmetry at the surface. In particular molecular arrangements of water with one uncoordinated OH group have unoccupied electronic states below the conduction band that are responsible for a strong anisotropic pre-edge intensity in the x-ray absorption spectrum. The topmost layer is dominated by an almost isotropic distribution of these species, which is inconsistent with an unrelaxed surface structure. For liquid water the x-ray absorption spectrum resembles that of the ice surface, indicating a domination of species with broken hydrogen bond configurations. The sensitivity to the local hydrogen bond configuration, in particular the sensitivity to broken bonds on the donor side, allows for a detailed analysis of the liquid water spectrum. Most molecules in liquid water are found in two-hydrogen-bonded configurations with one strong donor and one strong acceptor hydrogen bond. The results, consistent with diffraction data, imply that most molecules are arranged in strongly H-bonded chains or rings embedded in a disordered cluster network. Molecular dynamics simulations are unable to describe the experimental data. The water overlayer on the close-packed platinum surface is studied using a combination of core-level spectroscopy and density functional theory. A new structure for water adsorption on close-packed transition metal surfaces is found, where a weakly corrugated non-dissociated overlayer interacts via alternating oxygen-metal and hydrogen-metal bonds. The latter results from a balance between metal-hydrogen bond formation and OH bond weakening. The ultrashort core-hole lifetime of oxygen provides a powerful probe of excited state dynamics via studies of the non-radiative or radiative decay following x-ray absorption. Electrons excited into the pre-edge state for single donor species at the ice surface remain localized long enough for early time solvation dynamics to occur and these species are suggested as strong pre-existing traps to the hydrated electron. Fully coordinated molecules in the bulk contribute to a strong conduction band with electron transfer times below 0.5 femtoseconds. Upon core-ionization, both protons are found to migrate substantial distances on a femtosecond timescale. This unusually fast proton dynamics for non-resonant excitation is captured both by theory and experiment with a measurable isotope effect.

In this thesis, we have presented a systematic analysis of the change of cloud properties due to variation in aerosol concentration over Indian region using satellite observations, and Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) simulations. The Tropical Rainfall Measurement Mission (TRMM) based Microwave Imager (TMI) estimates (2A12) have been used to compare and contrast the characteristics of cloud liquid water and ice over the Indian land region and the surrounding oceans, during the pre-monsoon (May) and monsoon (June–September) seasons. Based on the spatial homogeneity of rainfall, we have selected five regions for our study (three over ocean, two over land). In general, we find that the mean cloud liquid water and cloud ice content of land and oceanic regions are different, with the ocean regions showing higher amount of CLW. A comparison across the ocean regions suggests that the cloud liquid water over the or graphically influenced Arabian Sea (close to the Indian west coast) behaves differently from the cloud liquid water over a trapped ocean (Bay of Bengal) or an open ocean (Equatorial Indian Ocean). Specifically, the Arabian Sea region shows higher liquid water for a lower range of rainfall, whereas the Bay of Bengal and the Equatorial Indian Ocean show higher liquid water for a higher range of rainfall. Apart from geographic differences, we also documented seasonal differences by comparing cloud liquid water profiles between monsoon and pre-monsoon periods, as well as between early and peak phases of the monsoon. We find that the cloud liquid water during the lean periods of rainfall (May or June) is higher than during the peak and late monsoon season (July-September) for raining clouds over central India. However, this is not true over the ocean. As active and break phases are important signatures of the monsoon progression, we also analyzed the differences in cloud liquid water during various phases of the monsoon, namely, active, break, active-to-break (a2b) and break-to-active (b2a) transition phases. We find that the cloud liquid water content during the b2a transition phase is significantly higher than that during the a2b transition phase over central India. We speculate that this could be attributed to higher amount of aerosol loading over this region during the break phase. We lend credence to this aerosol-liquid water/rain association by comparing the central Indian cloud liquid water with Southeast Asia (where the aerosol loading is significantly smaller) and find that in the latter region, there are no significant differences in cloud liquid water during the different phases of their monsoon. The second part of our study involves evaluating the ability of the Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) to simulate the observed variation of cloud liquid water and rain efficiency. We have used no chemistry option, and the model was run with constant aerosol concentration. The model simulations (at 4.5 km resolution) are done for the month of June–July 2004 since this period was particularly favorable for the study of an active–break cycle of the monsoon. We first evaluate the sensitivity of the model to different parameterizations (microphysical, boundary layer, land surface) on the simulation of rain over central India and Bay of Bengal. This is done to identify an “optimal” combination of parameterizations which reproduces the best correlation with observed rain over these regions. In this default configuration (control run), where the aerosol concentration is kept constant throughout the simulation period, the model is not able to reproduce the observed variations of cloud liquid water during the different phases of an active-break cycle. To this end, we proceeded to modify the model by developing an aerosol-rain relation, using Aerosol Robotic Network (AERONET) and TRMM 3B42 data that realistically captures the variation of aerosol with rain. It is worth highlighting here that our goal was to primarily isolate the indirect effect of aerosols in determining the observed changes in cloud liquid water (CLW) during the active-break phases of the Indian monsoon, without getting into the complexity of a full chemistry model such as that incorporated in WRF-Chem. Moreover, the proposed modification (modified run) is necessitated by the lack of realistic emission estimates over the Indian region as well as the presence of inherent biases in monsoon simulation in WRF. The main differences we find between the modified and control simulations is in the mean as well as spatial variability of CLW. We find that the proposed modification (i.e., rate of change of aerosol concentration as a function of rain rate) leads to a realistic variation in the CLW during the active-break cycle of Indian monsoon. Specifically, the peak value of CLW in the b2a (a2b) phase is larger (smaller) in the modified as compared to the control run. These results indicate a stronger change in CLW amount in the upper levels between the two transition phases in the modified scheme as compared to the control simulation. More significantly, we also observe a change in sign at the lower levels of the atmosphere, i.e., from a strong positive difference in the control run to a negative difference in the modified simulation, similar to that observed. Additionally, we investigated the impact of the proposed modification, via CLW changes, on cloud coverage, size of clouds and their spatial variability. We find that the transformation of optically thin clouds to thick clouds during the break phase was associated with larger cloud size in modified compared to the control simulation. Moreover, the higher rate of decay of the spatial variability of CLW with grid resolution, using the modified scheme, suggests that clusters of larger clouds are more in the modified compared to control simulation. Taken together, the interactive aerosol loading proposed in this thesis yields model simulations that better mimic the observed CLW variability between the transition phases.

This research is directed toward the investigation of a low temperature direct propane fuel cell (DPFC). Modeling included a parametric study of a direct propane fuel cell using computational fluid dynamics (CFD), specifically FreeFem++ software. Polarization curves predicted by the CFD model were used to understand fuel cell performance. The predictions obtained from the computational fluid dynamics mathematical model for the fuel cell were compared with experimental results. The computational work identified some critical parameters (exchange current density, pressure, temperature) for improving the overall performance of the fuel cell. The model predictions clearly highlighted the role of catalysts in significantly enhancing the overall performance of a DPFC. Experiments were performed using commercial Nafion-Pt based membrane electrode assemblies (MEAs) to obtain a basis for comparison. It is the first report in the literature that a Pt-Ru (Platinum-Ruthenium) MEA was used in the investigation of a DPFC. Also, it was the first study that fed liquid water continuously to a DPFC by using interdigitated flow field (IDFF) at the anode to humidify the dry propane feed gas. During the experiments oscillations were observed at very low current densities i.e. in nA/cm2, which is a rare case and not reported in the literature to date. This observation has raised serious concerns about the existence of absolute open-circuit cell potential difference for a DPFC. The cycling behaviour observed with DPFC indicated the presence of a continuous degradation-regeneration process of the catalyst surface near open-circuit potential. The experimental work further evaluated the performance of fuel cell by measurement of polarization curves.

Parmi les nombreuses problématiques liées à la PEMFC, l'eau est un point crucial car elle est à la fois indispensable et indésirable dans le coeur de pile. En effet, les flux gazeux qui alimentent le système en réactifs sont humidifiés pour que la membrane soit convenablement hydratée afin de faciliter le transport des protons de l'anode vers la cathode. Mais à cet apport initial vient s'ajouter l'eau produite par la réaction électrochimique. Des gouttes d'eau liquide peuvent alors se former dans les pores des couches actives et peuvent grossir jusqu'à boucher les canaux des plaques d'alimentation en gaz. Ce travail de thèse est centré sur l'étude des écoulements gaz-liquide dans ces canaux, dont le diamètre hydraulique est de l'ordre du millimètre. Dans un premier temps, des micro-capteurs ont été mis au point pour détecter la présence d'eau liquide. Après une phase de tests en maquette froide, ces micro-capteurs ont été insérés dans une cellule de 25 cm2 de surface active, identique à celles étudiées au LRGP. Ceci a permis de montrer que dans une pile en fonctionnement, les fluctuations de tension sont liées à la présence d'eau liquide. Par ailleurs, des corrélations existantes ont été utilisées pour prédire les pertes de charge engendrées par la présence de deux phases dans les mini-canaux. Ces calculs ont été comparés aux mesures expérimentales, mettant en évidence l'influence de la couche de diffusion des gaz, située entre les canaux et la membrane, et l'importance des conditions opératoires.Ces méthodes originales viennent compléter les outils de diagnostic existants sans demander d'appareillage complexe et coûteux, ni nécessiter le développement de matériel spécifique, non optimisé pour une utilisation commerciale / Water management is a critical issue in the operation of proton exchange fuel cells (PEMFC). On one hand, the membrane must be sufficiently hydrated to allow the transport of protons from the anode side to the cathode side. But on the other hand, supersaturation of water vapour in the gas phase results in liquid water formation, which can be detrimental to the fuel cell operation. Liquid water can clog up the porous structure of the gas diffusion layer (GDL) and hinder the transport of gases in the catalyst layer. Liquid accumulation can also lead to the formation of water columns inside the gas flow channels, thus preventing the fuel gas from flowing into the reaction area.Micro-sensors have been designed to detect the presence of liquid water. Three of them were inserted inside the gas distribution channels of a 25 cm2 cell. The tests run with this equipped cell highlighted the link between the presence of liquid water and the variations of the cell voltage. Besides, existing correlations were used to calculate the pressure drop between the inlet and the outlet of the cathode channel due to two-phase flow during the cell operation. The results of this calculation were compared with experimental results. This part of the study highlighted the influence of the GDL and of the operating conditions on the flows inside the channels

Táto diplomová práca sa zaoberá štúdiom alfa-Fe2O3(012) vystaveného vodnému prostrediu. Súčasný stav poznania ohľadom oxidov železa s pozornosťou vkladanou do popisu alfa-Fe2O3 a jeho (012) povrchu je stručne zhrnutá. Experimentálná časť tejto práce začína s popisom unikátného zariadenia na depozíciu kvapalnej vody na povrchy monokryštalických vzoriek compatibilného s podmienkami ultra vysokého vákuua. Jednotlivé konštrukčné časti a detaily sú diskutované. Navrhnutý systém bol testovaný na vzorkách striebornej fólie a monokryštálu Fe3O4 s povrchovom v rovine [100]. Chemické zloženie a morfológia povrchu po experimente s kvapalnou vodou je diskutovaná. Navrhnuté zariadenie bolo použité na štúdium interakcie vody so známymi (1x1) a (2x1) povrchovými alfa-Fe2O3(012). Experimentálne dáta ukazujú, že voda sa viaže na obe reconštrukcie disociatívne s určitým množstvom molekulárnej vody naviazanej na adsorbované hydroxydi. (1x1) sa zdá javý stabilná po expozícii rôznym tlakom vodnej pary, zatial čo (2x1) vykazuje zmenu na (1x1) pri expozíciach vyšším tlakom vodnej pary alebo po niekolo minútovej expozíci electrónovému zväzku. Ďalej sú v tejto práci prezentované prvé výsledky z štúdie prechodu (1x1) rekonštrukcie na (2x1) pomocou mikroskpie nízkoenergiových elektrónov. Výsledky ukazujú, že táto premena na nižších teplotách je inciovaná na hranách atomárnych vrstiev a defektov na povrchu, ktorá potom postupuje smerom k stredu atomárnych terás. Meranie na vyšších teplotách vykazuje postupnú premenu povrchu naznačúju viaceru nukleačných centrech z ktorých sa (2x1) povrch širi ďalej.

Monte-Carlo calculations are used to simulate the stochastic effects of fast neutron-induced chemical changes in the radiolysis of the ferrous sulfate (Fricke) dosimeter. To study the dependence of the yield of ferric ions, G(Fe[superscript 3+]), on fast neutron energy, we have simulated, at 25 [degree centigrade], the oxidation of ferrous ions in aerated aqueous 0.4 M H[subscript 2]SO[subscript 4] (pH 0.46) solutions when subjected to ~0.5-10 MeV incident neutrons, as a function of time up to ~50 s. The radiation effects due to fast neutrons are estimated on the basis of track segment (or"escape") yields calculated for the first four recoil protons with appropriate weighting according to the energy deposited by each of these protons. For example, a 0.8-MeV neutron generates recoil protons of 0.505, 0.186, 0.069, and 0.025 MeV, with linear energy transfer (LET) values of ~41, 69, 82, and 62 keV/[micro]m, respectively. In doing so, we consider that further recoils make only a negligible contribution to radiation processes. Our results show that the radiolysis of dilute aqueous solutions by fast neutrons produces smaller radical yields and larger molecular yields (relative to the corresponding yields for the radiolysis of water by [superscript 60]Co [gamma]-rays or fast electrons) due to the high LET associated to fast neutrons. The effect of recoil ions of oxygen, which is also taken into account in the calculations, is shown to decrease G(Fe[superscript 3+]) by about 10%. Our calculated values of G(Fe[superscript 3+]) are found to increase slightly with increasing neutron energy over the energy range covered in this study, in good agreement with available experimental data. We have also simulated the effect of temperature on the G(Fe[superscript 3+]) values in the fast neutron radiolysis of the Fricke dosimeter from 25 to 300 [degree centigrade]. Our results show an increase of G(Fe[superscript 3+]) with increasing temperature, which is readily explained by an increase in the yields of free radicals and a decrease in those of molecular products. For 0.8-MeV incident neutrons (the only case for which experimental data are available in the literature), there is a ~23% increase in G(Fe[superscript 3+]) on going from 25 to 300 [degree centigrade]. Although these results are in reasonable agreement with experiment, more experimental data, in particular for different incident neutron energies, would be needed to test more rigorously our Fe[superscript 3+] ion yield results at elevated temperatures.

Résumé : Les ions hydronium (H3O + ) sont formés, à temps courts, dans les grappes ou le long des trajectoires de la radiolyse de l'eau par des rayonnements ionisants à faible transfert d’énergie linéaire (TEL) ou à TEL élevé. Cette formation in situ de H3O + rend la région des grappes/trajectoires du rayonnement temporairement plus acide que le milieu environnant. Bien que des preuves expérimentales de l’acidité d’une grappe aient déjà été signalées, il n'y a que des informations fragmentaires quant à son ampleur et sa dépendance en temps. Dans ce travail, nous déterminons les concentrations en H3O + et les valeurs de pH correspondantes en fonction du temps à partir des rendements de H3O + calculés à l’aide de simulations Monte Carlo de la chimie intervenant dans les trajectoires. Quatre ions incidents de différents TEL ont été sélectionnés et deux modèles de grappe/trajectoire ont été utilisés : 1) un modèle de grappe isolée "sphérique" (faible TEL) et 2) un modèle de trajectoire "cylindrique" (TEL élevé). Dans tous les cas étudiés, un effet de pH acide brusque transitoire, que nous appelons un effet de "pic acide", est observé immédiatement après l’irradiation. Cet effet ne semble pas avoir été exploré dans l'eau ou un milieu cellulaire soumis à un rayonnement ionisant, en particulier à haut TEL. À cet égard, ce travail soulève des questions sur les implications possibles de cet effet en radiobiologie, dont certaines sont évoquées brièvement. Nos calculs ont ensuite été étendus à l’étude de l'influence de la température, de 25 à 350 °C, sur la formation in situ d’ions H3O + et l’effet de pic acide qui intervient à temps courts lors de la radiolyse de l’eau à faible TEL. Les résultats montrent une augmentation marquée de la réponse de pic acide à hautes températures. Comme de nombreux processus intervenant dans le cœur d’un réacteur nucléaire refroidi à l'eau dépendent de façon critique du pH, la question ici est de savoir si ces fortes variations d’acidité, même si elles sont hautement localisées et transitoires, contribuent à la corrosion et l’endommagement des matériaux. / Abstract : Hydronium ions (H3O+) are formed within spurs or tracks of the low or high linear energy transfer (LET) radiolysis of pure, deaerated water at early times. The in situ radiolytic formation of H3O+ renders the spur and track regions temporarily more acid than the surrounding medium. Although experimental evidence for an acidic spur has already been reported, there is only fragmentary information on its magnitude and time dependence. In this work, spur or track H3O+ concentrations and the corresponding pH values are obtained from our calculated yields of H3O+ as a function of time, using Monte Carlo track chemistry simulations. We selected four impacting ions and we used two different spur and track models: 1) an isolated “spherical” spur model characteristic of low-LET radiation and 2) an axially homogeneous “cylindrical” track model for high-LET radiation. Very good agreement was found between our calculated time evolution of G(H3O+) in the radiolysis of pure, deaerated water by 300-MeV incident protons (which mimic 60Co gamma/fast electron irradiation) and the available experimental data at 25 °C. For all cases studied, an abrupt transient acid pH effect, which we call an “acid spike”, is observed during and shortly after the initial energy release. This acid-spike effect is virtually unexplored in water or in a cellular environment subject to the action of ionizing radiation, especially high-LET radiation. In this regard, this work raises a number of questions about the potential implications of this effect for radiobiology, some of which are briefly evoked. Our calculations were then extended to examine the effect of temperature from 25 to 350 °C on the yield of H3O+ ions that are formed in spurs of the low-LET radiolysis of water. The results showed an increasingly acidic spike response at higher temperatures. As many in-core processes in a water-cooled nuclear reactor critically depend on pH, the question here is whether these variations in acidity, even highly localized and transitory, contribute to material corrosion and damage.