L'ion nitrate (NO3-) présent dans les neiges Antarctiques est issus de l'oxydation des oxydes d'azote (NOx = NO + NO2) dans l'atmosphère. Aux sites de faible accumulation de neige tels que Vostok et Dôme C sur le plateau de l'Est de l'Antarctique, le nitrate n'est pas piégé de manière ultime dans la neige, ce qui limite fortement l'interprétation des enregistrements en nitrate dans les carottes de glace. Des mesures récentes de la composition isotopique en azote du nitrate (δ15N) montrent des valeurs extrêmement élevées (+339‰) dans les premiers décimètres de la neige de Dôme C. Ces valeurs ont été attribuées à la photolyse du nitrate et au recyclage important qui en résulte. Le nitrate possède, par ailleurs, une anomalie isotopique en oxygène (Δ17O) qui permet de tracer l'activité de l'ozone (O3) au cours de sa formation. Ce travail de thèse présente le premier enregistrement de la composition isotopique complète du nitrate (δ15N, Δ17O et δ18O) dans une carotte de glace : la carotte de glace de Vostok dont les 64 échantillons analysés couvrent une période de 150 000 ans. Ce jeu de données a été complété par 313 échantillons collectés entre 2007 et 2010 dans le continuum atmosphère/givre/neige au Dôme C ainsi que dans 21 puits de neige prélevés dans une zone couvrant l'essentiel de l'Est de l'Antarctique. L'analyse isotopique de ces échantillons modernes a permis de contraindre le modèle conceptuel TRANSITS développé au cours de cette thèse et dont le but est de représenter le recyclage du nitrate à l'interface entre l'atmosphère et la neige ainsi que son impact sur la composition isotopique du nitrate archivé. Les valeurs positives et élevées du δ15N du nitrate piégé dans la carotte de glace de Vostok montrent que le recyclage du nitrate a toujours eu lieu sur le plateau Antarctique au cours de la période étudiée. Les variations du flux primaire de nitrate reçu au site de Vostok estimées à l'aide du modèle TRANSITS montrent, en périodes glaciaires, un flux primaire plus important qui pourrait être lié à une dénitrification stratosphérique plus conséquente. Les valeurs de Δ17O du nitrate montrent que l'incursion d'ozone d'origine stratosphérique dans la troposphère était plus fréquente en périodes glaciaires. Nous proposons enfin que les résultats acquis dans le cadre de cette thèse pourraient permettre de mieux contraindre le cycle de l'azote sur la côte Antarctique et d'apporter des éléments d'interprétation des enregistrements en nitrate dans les carottes de glace de sites de plus forte accumulation de neige (au Groenland par exemple). / Nitrate ions (NO3-) found in Antarctic snows stem from the degradation of nitrogen oxydes (NOx = NO + NO2) in the atmosphere. At sites with low snow accumulation rates such as Vostok or Dome C (East Antarctic plateau), nitrate deposition to the snow is not irreversible and this strongly hampers the interpretation of nitrate concentration records in ice cores. Nitrogen stable isotopic (δ15N) as high as +339‰ were measured in nitrate in the upper firn at Dome C and have been attributed to nitrate photolysis initiating a strong recycling at the snow surface. The oxygen isotopic anomaly (Δ17O) reflects the activity of ozone (O3) in nitrate formation. We present the first comprehensive isotopic analysis of nitrate (δ15N, Δ17O and δ18O) in a deep ice core. 64 samples of nitrate from the Vostok ice core have been analyzed and cover the last 150 000 years. This dataset has been completed with 313 samples recently collected in the atmosphere/surface hoar/snow continuum at Dome C as well as in several snowpits from various sites covering most of the East Antarctica. Those present-day samples are used to evaluate a conceptual model (named TRANSITS) developped during this PhD and which aims at representing nitrate recycling at the snow/atmosphere interface and at modelling its impact on the isotopic composition of the archived nitrate. High positive δ15N values measured in the Vostok ice core reveal that nitrate recycling has always occurred at the surface of the Antarctic plateau over this period. Past variations of the primary flux of nitrate to the Vostok site have been estimated using the TRANSITS model. They show that glacials are characterized by higher inputs which may be linked to a greater stratospheric denitrification. The Δ17O values indicate that intrusions of stratospheric air masses to the troposphere may have been more frequent in glacials thus incorporating significant amounts of stratospheric ozone to the lower atmosphere. Last, we suggest that this study may have some relevance to the coastal nitrogen budget in Antarctica and to the interpretation of ice cores retrieved from high accumulation sites (e.g. in Greenland).

Le nitrate, produit de la fin de chaîne de réaction des oxydes d’azotes de l’atmosphère (NOx = NO +NO2), est l’un des ions le plus abondant de la neige et de la glace polaire. Ses rapports isotopiques stables (δ18O, δ15N et Δ17O) ont été abondamment utilisés pour contraindre ses sources et les chemins réactionnels. De plus, le nitrate archivé dans les carottes de glace profondes peut apporter de nouvelles contraintes sur les conditions climatiques passées. Cependant, le dépôt de nitrate dans les régions polaires à faible accumulation est réversible en raison des processus post-dépôts, compliquant l’interprétation des enregistrements. Actuellement, il existe des enregistrements de nitrate issus de carottes de glace profonds couvrant de l’information climatique sur plusieurs milliers d’années dont leur interprétation dépend d’une quantification précise ces phénomènes post-dépôts. Nous avons étudié expérimentalement le transfert d’excès-17O de l’ozone durant la réaction en phase gaz de NO2 + O3  NO3 + O2, qui est une réaction importante de la chimie nocturne de formation du nitrate. De cette étude nous avons déterminé la fonction de transfert du 17O donnée par : ∆17O(O3*) = (1.23 ± 0.19) × ∆17O(O3)bulk + (9.02 ± 0.99). Nous avons aussi évalué la distribution intramoléculaire des isotopes de l’oxygène de l’ozone et observé que l’excès d’enrichissement résidait de manière prépondérante sur les atomes terminaux de l’ozone. Ces résultats auront une implication importante sur la compréhension de la formation du nitrate via les mécanismes d’oxydation des précurseurs NOx. L’impact de la photolyse sur les concentrations et les compositions isotopiques stables du nitrate est étudié dans ce travail de thèse sur la base d’étude de laboratoire et de terrain. Une étude de laboratoire a été conduite en irradiant de la neige naturelle de Dôme C avec une lampe UV à xénon et en utilisant différents filtres UV (280 nm, 305 nm et 320 nm). Sur la base des mesures des rapports isotopiques de l’oxygène et de l’azote, la dépendance aux longueurs d’onde des fractionnements isotopiques a été déterminée. En conséquence, en présence de lumière UV de haute énergie, le fractionnement isotopique est décalé vers des valeurs moins négatives et vice versa. Sur la base des fractionnements isotopiques obtenus en laboratoire, nous avons dérivé un décalage apparent de la valeur du zéro point d’énergie (ZPE) qui apporte une meilleure contrainte sur la section efficace d’absorption du 15NO3-. Ce décalage apparent est obtenu en minimisant les écarts entre les observations et les fractionnements isotopiques calculés basés sur un modèle de décalage ZPE, modèle qui inclut outre le décalage ZPE, le changement des largeurs, de l’asymétrie et de l’amplitude des sections efficaces d’absorption lors de la substitution isotopique. Nous avons validé le nouveau ZPE apparent en conduisant une étude de terrain à Dôme C, Antarctique. Dans cette étude, un dispositif expérimental a été construit sur le site et l’effet du rayonnement solaire UV sur la photolyse du nitrate de la neige investigué. Cette étude était basée sur la comparaison de deux puits remplis par de la neige soufflée homogénéisée dont l’un des deux puits n’était pas soumis aux rayonnements UV. Le fractionnement isotopique de 15N pour la neige exposée aux UV (-67.9 ± 12 ‰) est en bon accord avec le modèle de décalage ZPE estimé au cours de ce travail de thèse (-55.4 ‰). Ces valeurs sont aussi dans la gamme des fractionnements isotopiques apparents observée précédemment au Dôme C. Nous pensons que l’inclusion des ces nouvelles connaissances dans un modèle prédisant l’enrichissement du 15N dans les carottes de glace permettra une interprétation quantitative de l’information préservée dans la glace. / Nitrate, the end product of oxidation of atmospheric NOX (= NO + NO2), is one of the most abundant anions present in polar snow and ice. Its stable isotope ratios (δ18O, δ15N and Δ17O) have been widely used to constrain its sources and oxidation pathways. In addition, the nitrate archived in deep ice cores may be an important metric to constrain past climatic conditions. However, deposition of nitrate in polar regions with low snow accumulation is reversible due to post-depositional processes, and interpretation of this record is complicated. Currently, there exist deep ice core records of nitrate encompassing climatic information of millennial time scales, and their interpretation relies on careful quantification of post-depositional effects. We have experimentally studied the 17O-excess transfer from ozone during the gas phase NO2 + O3 → NO3 + O2 reaction, which is an important nighttime nitrate formation pathway. From this study, we have determined the ∆17O transfer function given by: ∆17O(O3*) = (1.23 ± 0.19) × ∆17O(O3)bulk + (9.02 ± 0.99). We have also evaluated the intramolecular oxygen isotope distribution of ozone and have observed the excess enrichment resides predominantly on the terminal oxygen atoms of ozone. The findings from this study will have an important implication for understanding nitrate formation pathways via different NOX oxidation mechanisms. The impact of photolysis on the amount and stable isotope enrichments of nitrate is investigated in this PhD study based on laboratory and field experiments. A laboratory study was conducted by irradiating a natural snow from Dome C with a Xe UV lamp and a selection of UV-filters (280 nm, 305 nm and 320 nm). Based on the oxygen and nitrogen isotope ratio measurements, wavelength dependent isotopic fractionations were determined. Accordingly, in the presence of high-energy UV light, isotopic fractionation is shifted towards less negative values and the reverse for lower energy UV photons. Based the isotopic fractionations obtained in the laboratory study, we derived an apparent ZPE-shift value, which better constrains the absorption cross-section of 15NO3-. This apparent shift is derived from the best fit between the experimental observations and calculated fractionations based on existing ZPE-shift model and it includes actual ZPE-shift and changes in width, asymmetry and amplitude in absorption cross-section during isotopic substitution. We have validated the newly derived apparent ZPE-shift by conducting a field study at Dome C, Antarctica. In this study, an experimental setup was built on-site and the effect of solar UV photolysis on snow nitrate was investigated. This study was based on a comparison of two snow pits filled with locally drifted snow and by allowing/blocking the solar UV. The 15N fractionation for the UV exposed samples (-67.9 ± 12 ‰) was in fairly good agreement with the ZPE-shift model estimate from this study (-55.4 ‰). These values are also within the range of apparent isotopic fractionation observed at Dome C in previous studies. Further calculations to better constrain the absorption cross-section of 15NO3- with the ZPE-shift are underway, and we propose that the newly derived apparent ZPE-shift value should be used in future studies. We believe that incorporating these new findings in models predicting the enrichments of 15N nitrate in ice cores will allow a quantitative interpretation of the information preserved in ice.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-09T20:44:52Z No. of bitstreams: 1 FRANCISCO RUBENS MACEDO DE QUEIROZ - TESE PPGEQ 2017..pdf: 6491313 bytes, checksum: 6c4f94936ecedff528d64322072a5f31 (MD5) / Made available in DSpace on 2018-03-09T20:44:52Z (GMT). No. of bitstreams: 1 FRANCISCO RUBENS MACEDO DE QUEIROZ - TESE PPGEQ 2017..pdf: 6491313 bytes, checksum: 6c4f94936ecedff528d64322072a5f31 (MD5) Previous issue date: 2016-12-09 / Capes / Um dos grandes desafios da atualidade vem sendo a conservação e manutenção dos corpos de águas do mundo, devido as suas contaminações em função das atividades humana. A diversidade das substâncias toxicas de diferentes naturezas são veiculadas como fontes de doenças de alto risco para todos os seres e vegetações do planeta. Um dos pontos preliminares é o acesso ao saneamento básico que a maioria das cidades brasileiras não possuem e que carreiam seus resíduos para mananciais superficiais e subterrâneas, deixando-os com altos índices de bactérias, inclusive com o aumento da concentração de nitrato nas águas subterrâneas. O presente trabalho visa estudar o desempenho de dois sistemas de membranas para reduzir a concentração de nitrato presente em águas de poços doces e salobros, contendo índices de nitrato acima dos padrões de potabilidade da legislação brasileira. Os desempenhos dos sistemas de membranas de microfiltração/nanofiltração e ultrafiltração/osmose inversa, foram estudados em função de seus limites de pressões de operações para diferentes níveis de concentrações de nitrato presentes nos meios aquosos. Os níveis das pressões de operações para todas as águas estudadas foram obtidos com auxílio de um simulador de processos de membranas (Reverse Osmose System Analysis), o qual contribui para realizar o planejamento experimental em função das pressões de operações versus concentrações nitrato. A primeira fase do trabalho os dois sistemas operaram com uma solução de nitrato na faixa de 0,67 mg.L-1 ≤ [N-N03-] ≤ 23,3 mg.L-1 visando explorar os níveis das taxas rejeição do nitrato em função de suas pressões de operações. Os desempenhos dos dois sistemas de membranas foram estudados com água doce de poço contaminada com nitrato, água de abastecimento da rede do LABDES e água de poço salobra, ambas com adição de 20,8 mg.L-1 de nitrato. Os resultados das taxas de rejeição de nitrato para os dois sistemas foram comparados em função do tipo de água de alimentação e seus níveis de concentrações de nitrato. Observou-se que o sistema de membranas de ultrafiltração/osmose inversa apresentou uma remoção de nitrato superior para todos os casos estudados, quando comparados com os obtidos pelo sistema de microfiltração/nanofiltração. Comparando os resultados para uma pressão de operação comum para os dois sistemas de membranas estudados de 3,2 bar o sistema de membrana de microfiltração/nanofiltração conseguiu uma taxa de remoção de 54,50% e o sistema de ultrafiltração/osmose inversa foi de 86,10% para uma concentração de 20,8 mg.L-1 de nitrato na água doce de poço. Observou-se que uma redução de nitrato e dos sólidos totais dissolvidos em águas doces para os padrões de potabilidade foram significativas para o sistema de ultrafiltração/osmose inversa do que a do sistema de microfiltração/nanofiltração, em função da pressão de operação. Com auxilio do MINITAB Versão 17.0 os modelos foram validados a partir das curvas dos dados experimentais para os dois sistemas de membranas estudados. / One of the great challenges of the present time has been the conservation and maintenance of the bodies of water of the world, due to its contaminations due to human activities. The diversity of toxic substances of different natures are conveyed as sources of high risk diseases for all beings and vegetations of the planet. One of the preliminary points is access to basic sanitation that most Brazilian cities do not have and that carry their waste to surface and underground springs, leaving them with high rates of bacteria, including with increasing nitrate concentration in groundwater. The present work aims to study the performance of two membrane systems to reduce the concentration of nitrate present in waters of sweet and brackish wells, containing nitrate indices above the potability standards of Brazilian legislation. The performances of the microfiltration/nanofiltration and ultrafiltration/reverse osmosis membranes systems were studied as a function of their operating pressure limits for different levels of nitrate concentrations present in the aqueous media. The operating pressure levels for all studied waters were obtained using a Reverse Osmose System Analysis, which contributes to perform the experimental planning as a function of the operating pressures versus nitrate concentrations. In the first phase of the work the two systems operated with a nitrate solution in the range of 0,67 mg.L-1 ≤ [N-N03-] ≤ 23,3 mg.L-1 to explore the levels of nitrate rejection rates as a function of their pressures Operations. The performances of the two membrane systems were studied with fresh water from well contaminated with nitrate, LABDES network water supply and brackish water, both with addition of 20,8 mg.L-1 of nitrate. The results of the nitrate rejection rates for the two systems were compared according to the type of feed water and their levels of nitrate concentrations. It was observed that the ultrafiltration / reverse osmosis membrane system showed superior nitrate removal for all the studied cases when compared to those obtained by the microfiltration / nanofiltration system. Comparing the results to a common operating pressure for the two 3,2 bar membrane systems studied, the microfiltration/nanofiltration membrane system achieved a removal rate of 54,50% and the ultrafiltration/reverse osmosis system was 86,10% for a concentration of 20,8 mg.L-1 nitrate in freshwater well. It was observed that a reduction of nitrate and total solids dissolved in fresh water to the potability standards were significant for the ultrafiltration / reverse osmosis system than that of the microfiltration/nanofiltration system as a function of the operating pressure. With the help of MINITAB Version 17.0 the models were validated from the curves of the experimental data for the two systems of membranes studied.

Os ritmos circadianos coordenam grande parte dos mecanismos fisiológicos, principalmente no metabolismo do nitrogênio, inclusive a assimilação do nitrato, que é a forma de nitrogênio mais incorporada pelos organismos fotossintéticos marinhos. Sua assimilação é feita pela enzima nitrato redutase (NR) que é regulada de forma sistêmica e em vários níveis: transcricional, pós-transcricional e pós-traducional. Tal modulação é exercida por diversos fatores como nitrato, luz, glutamato, quinases e por fatores de transcrição centrais do ritmo circadiano. A fotossíntese fornece os esqueletos de carbono e poder redutor para a incorporação do nitrogênio na síntese de glutamato. Gracilaria birdiae é uma macroalga endêmica do litoral brasileiro e ainda precisa de mais estudos em fisiologia, apesar da sua grande importância econômica. Este estudo desenvolveu um novo protocolo para o ensaio em larga escala da atividade enzimática da NR e analisou a oscilação do desempenho fotossintético ao longo do dia em G. birdiae. A alga, proveniente do Rio Grande do Norte, foi isolada a nível unialgal e apresentou uma taxa de crescimento relativo diário de 6,5% em laboratório. O novo protocolo descrito propõe as seguintes adaptações: amostragem de 20 mg de biomassa algal em vez de 100 mg, extrato bruto com 100 µL em vez de 1 mL, ensaio enzimático de 50 µL e parada da reação com sulfanilamida em vez de EtOH/ZnSO4. Estas modificações permitem o ensaio enzimático da NR semi-purificada de 8 testes com réplicas experimentais e biológicas e controle negativo (96 ensaios no total) em 3 horas. A caracterização enzimática demonstrou os seguintes parâmetros ótimos para atividade máxima: tampão fosfato pH 8, temperatura 25°C, 60 minutos de incubação, 1,25 mMol de nitrato e 50 µMol de NADH. A atividade máxima de 5,4 ± 0,7 nMol.min-1.mg-1 de proteínas e o KM 6 ± 2,2 µMol.L-1 para NADH e de 109 ± 11 µMol.L-1 para o nitrato. A enzima não apresentou atividade na presença de NADPH e demonstrou atividade 48 vezes maior que no protocolo inicial. Descrevemos um método preciso e reprodutível para análise em larga escala da atividade da NR que pode ser utilizado em estudos comparativos de cinética enzimática da NR de diferentes espécies ou em estudos de ritmos biológicos. A análise do desempenho fotossintético, feita em coletas de 15 mg de alga, foi caracterizada pela fluorescência da clorofila, demonstrando os seguintes parâmetros máximos: taxa de transporte de elétrons relativa (rETR) de 15,29 µMol elétrons.m-2.s-1, eficiência fotossintética (alfa) de 0,37 fótons/elétrons, irradiância de saturação (IK) foi de 41,32 µE.m-2.s-1 e houve fotoinibição a partir de 300 µE.m-2.s-1. Apenas o parâmetro alfa apresentou oscilação significativa em claro constante e manteve o período de 24 horas, apesar de ter diminuído sua amplitude em 50%. Isso pode ser devido a um controle pelo mecanismo central dos ritmos circadianos sobre proteínas ou pigmentos ligados ao fotossistema II, influenciando na capacidade de transformação de fótons em elétrons. Paralelamente, a aclimatação da alga à luz constante pode ter levado a uma queda na produção de pigmentos e fotoxidação, justificando a queda nos valores médios de alfa. G. birdiae é uma alga com grande importância econômica e ecológica e este estudo, ligado a outros trabalhos de fisiologia, confirma seu grande potencial para estabelecimento como organismo modelo para estudos fisiologia e fotossíntese / Circadian rhythms control most of physiological processes, including nitrate assimilation. This nutrient is the most incorporated form of nitrogen by marine plants and its assimilation is made by the nitrate reductase enzyme (NR) that is highly regulated in all levels expression, since mRNA transcription until protein degradation. Many factors coordinate this regulation, including the nitrate itself, light glutamate, kinases and by transcription factors of the central oscillator of the circadian rhythms. Photosynthesis also plays an especial role in NR regulation through carbon skeleton and NADPH synthesis that allows the last step of nitrate assimilation: glutamate synthesis. Gracilaria birdiae is an endemic marine rhodophyte from Brazil that still lacks physiological and molecular studies despite its extensively exploitation for agar-agar extraction. This study aimed the development of a large scale enzymatic assay of NR (NRA) and the analysis of daily oscillation of photosynthesis performance for G. birdiae. The algae, collected ant Rio Grande do Norte state, was isolated to a unialgal level and presented an average of relative daily growth rate of 6.5% in laboratory. The new protocol here described proposes the following adaptations for NRA: sampling of 20 mg instead of 100 mg, 100 µL of crude extract rather than 1 mL, NRA in 50 µL in place of 1 mL and reaction stop with sulphanilamide instead of an EtOH/ZnSO4 system. These changes allow the assay of the semi-purified NR of 24 samples all with its experimental and biological triplicates and negative control in 3 hours. Phosphate buffer at pH 8, 25°C, 60 minutes of incubation, 1.25 mMol of nitrate and 50 µMol of NADH. The maximum activity was 5.4 ± 0.7 nMol.min-1.mg-1 of protein and a KM of 6 ± 2.2 µMol.L-1 for NADH and of 109 ± 11 µMol.L-1 for nitrate. NR didn\'t show any activity in the presence of only NADPH as the electron donor and showed and 48 times greater activity in the new protocol, compared to the old one. We describe here an accurate and reproducible method for large scale NRA that can be used in comparative studies of NR kinetics or in biological rhythms of NR. The analysis of photosynthetic performance, made in 15 mg sampling of algal biomass, was characterized through chlorophyll fluorescence, revealing the maximum values of these parameters: relative electrons transfer rate (rETR) of 15,29 µMol elétrons.m-2.s-1, photosynthetic efficiency (the alpha parameter) of 0,37 photons/electrons, the saturating irradiance (IK) was 41.32 µE.m-2.s-1 and there was photoinhibition below the irradiance of 300 µE.m-2.s-1. The only variable that oscillated during the continuous light experiment and maintained the 24-hour period was the Alfa parameter, besides its 50% lower amplitude. This oscillation can be due to an endogenous control of the central circadian oscillator into proteins or pigments bound to the photosystem II, influencing the capacity of photon-electron transformation. At the same time, the acclimation to constant light could have driven the algae to a damping of pigment production and photoxidation, what explains the fall of alpha average values. G. birdiae is an alga with great economic and ecological relevance and this study confirms the potential for its establishment as a model organism.

De nombreuses substances chimiques sont susceptibles de mener à des phénomènes d'incompatibilité, lors de leur mise en contact avec d'autres produits ou matériaux. Pour maîtriser ces risques, une identification rapide et précise de ces incompatibilités est nécessaire. Elle est réalisée, jusqu’à présent, par des outils expérimentaux qui malgré leur incontestable importance, ne fournissent que des informations limitées. Pour les compléter et améliorer la compréhension des processus d'incompatibilité, ce travail de thèse, vise à étudier la réactivité du nitrate d'ammonium, produit très utilisé dans l'industrie, connu pour sa longue liste d'incompatibilités et impliqué dans des nombreux accidents majeurs (Toulouse 2001), à l'aide de la modélisation moléculaire. Une étude théorique approfondie, basée sur des calculs DFT, destinée à identifier les chemins réactionnels, les produits formés ainsi que la chaleur dégagée par les réactions a été menée.Après avoir caractérisé le mécanisme radicalaire de décomposition du nitrate d’ammonium pur en phase gaz, une étude détaillée de la réactivité du mélange du nitrate d’ammonium et du dichloroisocyanurate de sodium (DCCNa), a été réalisée. Un chemin réactionnel a été caractérisé, il s'agit de la réaction directe entre le nitrate d'ammonium et le DCCNa, en présence d'une molécule d'eau. Ensuite, ces méthodes théoriques ont été appliquées à d'autres systèmes d'incompatibilités chimiques avec le nitrate d'ammonium (NaNO2, substances chlorées) en focalisant sur les étapes limitantes des mécanismes afin de tester leur pertinence et potentiel en tant qu'outil de prédiction a priori du phénomène d'incompatibilité. Ce travail, pionnier dans l'étude microscopique des incompatibilités chimiques du nitrate d'ammonium, a permis de clarifier les mécanismes réactionnels lors de la décomposition du produit pur et en contact avec des contaminants. / Numerous chemical reactants tend to lead to undesired phenomena of incompatibility. In order to prevent the happening of those phenomena, a rapid and accurate identification of the incompatibilities is needed. Until now, experimental studies, which provide insightful, but limited information, were the only possible approach used for the study of incompatibilities. In this work a molecular modeling approach was used in order to complete and improve experimental results of incompatibility processes for the reactivity of ammonium nitrate. Ammonium nitrate is a widely used compound in the chemical industry, known for its long list of incompatibilities and often involved in major accidents (Toulouse, 2001).This theoretical work, based on Density Functional Theory (DFT) calculations, is intended to provide insights into the possible reaction pathways, enthalpies and products formed by incompatibility reaction between ammonium nitrate and other compounds. In this thesis the mechanism of the decomposition of pure ammonium nitrate in the gas phase was firstly characterized and then the reactivity of the mixture of ammonium nitrate – sodium dichloroisocyanurate (DCCNa) was considered. The results obtained suggest the existence of a reaction path, involving a direct reaction between the ammonium nitrate and DCCNa in the presence of a molecule of water.Furthermore, the theoretical approach was employed focusing on the study of the limiting steps of other chemical incompatibilities for ammonium nitrate systems (NaNO2, chlorinated substances). Those results were employed to understand the potentiality of the theoretical approach as a priori predicting tool for the incompatibility processes.In summary this work, pioneer in the microscopic study of chemical incompatibilities of ammonium nitrate, has clarified the reaction mechanisms involved in the decomposition of pure compounds, as well as in contact with other contaminants.

In the United States, many private wells are used as the only source of potable water. These wells, under current federal and state regulations, are neither monitored nor checked for water purity. The purpose of qualitative case study was to gain an understanding about how the documented nitrate contamination problem in the Lower Yakima Valley River Valley is perceived by members of the community and to measure their willingness to engage in collective action for social change. Purposive samples of 6 participants were interviewed using 10 questions derived from the drinking water disparities framework by Balazs and Ray. Additional historical information and data were reviewed. While analyzing interview responses, observations, and documents to understand how the documented nitrate contamination problem, themes and patters emerged and were identified. According to the study results, the community was not actively engaged in any communication regarding the nitrate contamination. Private well owners hold beliefs about the safety of their individual water supply but had no knowledge of the water quality being used by their friends, neighbors, and families This community, if engaged in a collective action to deal with the nitrate contamination problem, could be successful in influencing larger organizations, such as state and federal governmental entities, to work toward nitrate contamination source identification and remediation.

L’accroissement des dépôts de nitrate atmosphérique (NO3-atm) sur les bassins versants d’altitude, limités en ressources, entraîne des changements nets de disponibilité d’azote. Ces apports modifient la diversité biologique (végétation, plantes), les processus des sols liés à l’azote et conduisent à l’eutrophisation des cours d’eau. A terme, l’impact sur les populations humaines se traduira par la perte d’importants services fournis par ces écosystèmes (alimentation en eau, qualité du fourrage, contrôle de l’érosion, biodiversité). Si les effets des dépôts de NO3-atm sur les bassins versants pauvres en azote sont maintenant bien documentés, il n’en reste pas moins à comprendre les processus régissant la rétention de NO3-atm dans les écosystèmes de montagne. Pour ce faire, la variabilité spatio-temporelle de la répartition du NO3-atm dans tous les compartiments subalpins est ici étudiée en utilisant un traceur multi-isotopique (17O, 18O, 15N) du NO3-. L’importante proportion de NO3-atm dans les cours d’eau de montagne, tout au long de l’année et plus particulièrement à la fonte des neiges, laisse à penser que les bassins versants sont cinétiquement saturés en azote. La composition isotopique du NO3- dans les eaux de surface illustre la transformation rapide de l’ammonium de la neige et confirme que la fonte des neiges est une période cruciale du cycle de l’azote dans les montagnes enneigées. La proportion de NO3-atm dans les sols varie, quant à elle, en fonction du type d’occupation des sols et des propriétés biotiques et abiotiques afférentes. Le suivi de la végétation a montré une forte teneur en NO3-atm dans les tissus, par assimilation racinaire et foliaire. Ces avancées scientifiques permettront, à terme, de mieux comprendre comment les dépôts de NO3-atm affectent l’environnement. / Increasing rates of atmospheric nitrate (NO3-atm) deposition in nutrients poor mountainous regions have led to critical changes in nitrogen (N) availability, with consequences on biodiversity (plants, microbes), soils N turnover, and water nutrients status. This will ultimately affect human populations through the loss of critical ecosystem services (e.g., provision of clean freshwater, erosion control, biodiversity). If the impacts of NO3-atm deposition to N-limited basins are now well documented, little is known about the processes driving NO3-atm retention in subalpine ecosystems. In this context, new tools are necessary to better understand the fate of NO3-atm in mountains and to predict the mid and long-term ecological consequences of increasing NO3-atm deposition. This work uses a high-resolution multi-isotopic technique combining 17O, 18O and 15N signatures of NO3- in the different subalpine compartments to understand the temporal and spatial evolution of NO3-atm partitioning in a subalpine watershed of the French Alps. Subalpine streams elevated year-round exports of NO3-atm suggest that the watersheds are kinetically N saturated, especially after snowmelt. The isotopic composition of NO3- in freshwaters also points at the rapid processing of snow ammonium, confirming that snowmelt is “hot moment” for the N cycle in seasonally snow-covered catchments. The monitoring of soils reveals varying NO3-atm proportions depending on the land management treatments and implied biotic and abiotic characteristics. Two dominant subalpine plants showed high proportions of NO3-atm in organs acquired by both root and foliar uptake. These scientific breakthroughs will ultimately lead to a better understanding of how NO3-atm deposition affects the environment.

La connaissance des dynamiques hydrologiques et du transport chimique associé est indispensable à la mise en place de stratégies de gestion de l’eau et du territoire, mais elle est difficile à consolider pour tous les exutoires de bassins versants porteurs d’enjeux car ils sont souvent « non-jaugés ». A partir d’un hydrogramme observé à l’exutoire d’un bassin jaugé, l'inversion d’un modèle hydrologique à base géomorphologique rend accessible la variable pluie nette en pied de versant. Cette variable indépendante d'échelle est ensuite transposée vers un bassin non-jaugé similaire et reconvoluée en hydrogramme à son exutoire. Cette méthode de "transposition d'hydrogramme", est appliquée pour la première fois en régime pluvio-nival dans 21 bassins Québécois. Le succès de la simulation pour le couple de bassins « jaugé » et « non-jaugé » est conditionné par la similarité hydrologique, soit l’ensemble des caractéristiques assurant un fonctionnement proche entre bassins versants. Nous testons si la composition chimique de l’eau est susceptible de révéler cette similarité à l’aide d’une analyse de type spectral développée sur l’ouest de la France, à l’échelle synoptique. Des groupes de bassins versants se démarquent par une homogénéité / hétérogénéité spatiale des faciès de concentrations, et de l’aire à partir de laquelle est observée la stabilisation de ce faciès. Ceci suggère que la composition chimique des rivières est informative d’un fonctionnement hydrologique similaire. Cette hypothèse est ensuite validée grâce à la transposition avec succès sur six bassins de méso-échelle des hydrogrammes et des relations concentrationdébit (CQ), les meilleurs résultats étant obtenus lorsque le couple respecte une similarité hydrochimique. Enfin, le couplage des hydrogrammes et des relations CQ a permis de prédire efficacement, grâce au principe de similarité, les flux en bassin versant non-jaugé, au pas de temps de 15 minutes. / The knowledge of hydrological and hydrochemical dynamics is essential for policy makers to develop appropriate policies of remediation, but this goal is hard to achieve in « ungauged catchments ». Through the inversion of a geomorphology-based hydrological modelling, the net rainfall entering the stream network is assessed from a gauged catchment. This net rainfall is scale independant and can be convoluted in another (ungauged) catchment. This method is applied for the first time in a pluvio-nival context on 21 catchments from Québec. Success of the simulation depends of the hydrological similarity between gauged and ungauged catchments, which is defined as the ensemble of caracteristics insuring a close functionning. We test how riverwater chemical composition reveals this similarity through a synoptic spectral analysis developped on western France. Groups of catchments are identified by their spatial homogeneity/heterogeneoty of the hydrochemical facies, and the area at which hydrochemical stabilisation occurs. This result suggest that riverwater chemical composition is informative of a hydrological similarity. This hypothesis is successfully tested on six mesoscale catchments, by transposing hydrographs and concentration discharge relatioships (CQ), best transpositions are associated to similar catchments. Finally, the coupling of hydrological simulation to CQ curves allowed the prediction of hydrochemical fluxes in ungauged catchments with a 15 minutes timestep.

As harmful algal blooms begin to appear in unexpected places such as rivers in predominantly forested systems, a better understanding of the nutrient processes within these contributing watersheds is necessary. However, these systems remain understudied. Utilization of high-resolution water quality data applied to deterministic numerical modeling has shown that a 0.42% watershed area backwater riparian wetland along the Ohio River floodplain can attenuate 18.1% of nitrate discharged from local mixed-use watersheds and improves in performance during high loading times due to coinciding increased hydrological connectivity and residence times of water in these wetlands. Loading from the Fourpole Creek watershed was typical for mixed-use systems at 3.3 kgN/ha/yr. The high-resolution data were used to improve boundary condition parameterization, elucidate shortcomings in the model structure, and reduce posterior solution uncertainty. Using high resolution data to explicitly inform the modeling process is infrequently applied in the literature. Use of these data significantly improves the modeling process, parameterization, and reduces uncertainty in a way that would not have been possible with a traditional grab sampling approach.

Le domaine de l'agriculture produit une part importante des gaz à effet de serre (GES) au Canada (8%) soit 8% des 747 Mt eq. CO[indice inférieur 2] émis chaque année. L'industrie porcine, un secteur clé de l'industrie agroalimentaire est en forte croissance au Canada depuis le milieu des années 80. L'entreposage du lisier préalablement séparé compte pour la plus grande partie du méthane (CH[indice inférieur 4]) émis, un GES au pouvoir de réchauffement global 25 fois celui du dioxyde de carbone (CO[indice inférieur 2]). Pour traiter le CH[indice inférieur 4], la biofiltration a déjà fait ses preuves pour le traitement des émissions de CH[indice inférieur 4] provenant des lieux d'enfouissement sanitaires (LES) et des mines. Ce procédé peut être également appliqué au CH[indice inférieur 4] issu de l'industrie porcine. Lors de la biofiltration du CH[indice inférieur 4], plusieurs facteurs clé peuvent améliorer la performance du système de traitement biologique comme, par exemple, la température, le pH, la nature du milieu filtrant, le taux d'humidité du lit et les nutriments. En particulier, l'apport en nutriments est un facteur déterminant pour la croissance et le maintien des microorganismes traitant le CH[indice inférieur 4]. Plusieurs nutriments doivent être fournis pour assurer le bon fonctionnement d'un biofiltre : carbone, oxygène, azote, phosphore, potassium et autres. D'un autre côté, certaines substances peuvent inhiber l'oxydation du CH[indice inférieur 4] dans un biofiltre et influencer la flore microbienne : un inhibiteur ayant fait l'objet de nombreuses études sur des supports de terre est l'ammonium (NH[indice inférieur 4][indice supérieur +]). Les expériences en laboratoire devaient déterminer l'impact du NH[indice inférieur 4][indice supérieur +] dans la solution nutritive contenant du nitrate sur un biofiltre rempli d'un garnissage inorganique traitant le CH[indice inférieur 4]. Dans les conditions expérimentales considérées (Débit d'air : 0,18 m[indice supérieur 3] h[indice supérieur -1] ; Concentration de CH[indice inférieur 4] à l'entrée : 3000 ppmv ; Débit de solution nutritive : 1,5 L j[indice supérieur -1]), l'ajout de NH[indice inférieur 4][indice supérieur +] dans la solution nutritive a eu un impact sur la performance du biofiltre, faisant diminuer la conversion du CH[indice inférieur 4] de 70 à 13% entre 0,05 et 0,5 gN-NH[indice inférieur 4][indice supérieur +] L[indice supérieur -1]. Les résultats de cette étude ont aussi démontré que l'augmentation progressive du NH[indice inférieur 4][indice supérieur +] réduit l'effet inhibiteur de celui-ci sur la performance du biofiltre.