Submitted by Marco Antônio de Ramos Chagas (mchagas@ufv.br) on 2017-07-20T13:35:31Z No. of bitstreams: 1 texto completo.PDF: 286988 bytes, checksum: d9f6fc5b932ecff9285c6e82130b932f (MD5) / Made available in DSpace on 2017-07-20T13:35:31Z (GMT). No. of bitstreams: 1 texto completo.PDF: 286988 bytes, checksum: d9f6fc5b932ecff9285c6e82130b932f (MD5) Previous issue date: 2001-03-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho teve como objetivo analisar alguns aspectos da tolerância ao Al em dois cultivares de arroz: Maravilha (sensível: CNA-6843-1) e Fernandes (tolerante: CNA-1158), em solução nutritiva. Num primeiro experimento, plantas dos dois cultivares foram expostas ao Al em soluções nutritivas com diferentes proporções de NO 3- :NH 4+ e avaliados os efeitos do Al sobre o crescimento das plantas e sobre a liberação de H + para a solução nutritiva. Independente da proporção NO 3- :NH 4+ , tanto o comprimento quanto a produção de matéria seca de raízes e parte aérea diminuíram na presença de Al, nos dois cultivares, principalmente no sensível. O cultivar tolerante mostrou-se mais eficiente no consumo de H + quando o N disponível estava exclusivamente na forma nítrica. O sensível, entretanto, mostrou-se mais eficiente na liberação de H + para a solução nutritiva quando o N foi fornecido sob duas formas ou exclusivamente na forma amoniacal. Num segundo experimento, as plantas dos dois cultivares foram expostas a duas concentrações de Al e avaliados seus efeitos sobre os teores, as taxas de absorção líquida e os índices de eficiência de utilização de alguns elementos minerais, nas duas partes das plantas. Na presença de Al as plantas apresentaram teores mais elevados deste elemento nas duas partes da planta, principalmente nas raízes. O cultivar tolerante mostrou-se mais eficiente na retenção deste elemento nas raízes. Na presença de Al, observou-se redução nos teores de todos os elementos minerais estudados, tanto nas raízes como na parte aérea, exceto no de Ca nas raízes e no de K na parte aérea, do cultivar tolerante. De modo geral, as reduções nos teores destes elementos minerais foram mais intensas no cultivar sensível, nas duas partes das plantas. As taxas de absorção líquida, sofreram reduções crescentes com os níveis de Al na solução nutritiva, tendo o cultivar tolerante apresentado, de modo geral, taxas mais elevadas para todos os elementos minerais estudados. O efeito do Al sobre os índices de eficiência de utilização dos elementos minerais estudados foi variado. No cultivar tolerante, observou-se aumento nos índices de eficiência de utilização de P, Ca e Mg, permanecendo inalterado o de K. No cultivar sensível, os índices de eficiência de utilização de P e K diminuíram, o de Ca permaneceu inalterado e o de Mg aumentou. Na ausência de Al os cultivares não diferiram entre si quanto a estes índices, mas na presença deste elemento, seus valores foram, de modo geral, mais elevados no cultivar tolerante. / The objective of this work was to study some aspects of Al tolerance in two rice cultivars: Maravilha (sensitive: CNA-6843-1) and Fernandes (tolerant: CNA:1158), grown in nutrient solution. In a first experiment, plants of the two cultivars were exposed to Al in nutrient solutions with different NO 3- :NH 4+ proportions and the Al effects on plant growth and on H + exsudation to the nutrient solution were evaluated. Independent of the NO 3- :NH 4+ proportion, both the length and dry matter yield of roots and shoots decreased in Al presence, in both cultivars, mainly in the sensitive. The tolerant cultivar showed higher efficiency in the H + consumption in nutrient solution with the nitric form. The sensitive, however, showed higher the N exclusively in efficiency in the exudation of H + to the nutrient solution, when N was supplied in both N forms or exclusively in the ammonium form. In a second experiment, plants of both cultivars were exposed to two Al concentrations and its effects on the contents, on the net absorption rates and on the use efficiency indices of some mineral elements, were evaluated in both parts of the plants. In Al presence the plants exhibited increased contents of these element in both parts of the plant, mainly in the roots. The tolerant cultivar was more efficient in the Al retention in the roots than the sensitive one. In Al presence, the contents of all mineral elements decreased in both roots and shoots, except the content of Ca in the roots and of K in the shoots, of the tolerant cultivar. In general, the reductions in the mineral contents were stronger in the sensitive cultivar, in both parts of the plants. The net absorption rates reductions increased with Al levels in the nutrient solution. The tolerant cultivar, in general, exhibited higher absorption rates of all mineral elements studied. Aluminum effect on the use efficiency indices was quite variable. In the tolerant cultivar, the use efficiency indices of P, Ca and Mg increased and of K remained unaffected. In the sensitive cultivar, the use efficiency indices of P and K decreased, of Ca remained unaffected and of Mg increased. In Al absence there was no difference between cultivars with respect to these indices, but in the presence of this element, the tolerant cultivar showed higher values. / Dissertação importada do Alexandria

Le présent travail a pour but d'évaluer les potentialités électrocatalytiques du cuivre sous différentes formes pour les réactions de réduction du dioxyde de carbone et de réduction de l'ion nitrate. Dans la première partie du travail, nous avons comparé, à l’aide de la voltampérométrie, d’électrolyses à potentiel contrôlé et d’analyses chromatographiques, l'activité d'électrodes polycristalline et monocristallines de Cu et d'alliages AuxCuy de différentes orientations cristallines pour l'électroréduction de CO2. Nous avons pu établir une étroite corrélation entre l'activité de l'électrode de Cu et l'arrangement atomique de sa surface. L'activité et la sélectivité pour CH4 de Cu décroissent selon la séquence : Cu (111) > Cu (100) > Cu (poly). La réduction du CO2 et la formation de CH4 sont favorisées sur les surfaces lisses et denses à l'échelle atomique. La sélectivité des alliages AuxCuy est considérablement orientée vers CO quand la fraction superficielle de Au augmente. L'alliage de composition 50-50 conduit à la formation exclusive de CO. La seconde partie de la thèse est consacrée à l'étude de l'activité d'électrodes massives de Cu polycristallin et monocristallin d’orientation (111) et de dispersions de Cu pour la réduction électrochimique de NO3-. Nous avons mis en évidence l'importance des conditions de pH pour le déroulement des processus à l'électrode de cuivre. En milieu acide, NO3- est directement réduit en NH4+ alors qu’en milieu neutre, les réactions de réduction de NO3- en NO2- et de NO2- en NH4+ s’observent successivement en fonction du potentiel. L'activité des dispersions de Cu dans un film de polyaniline dépend fortement des conditions de dépôt. Le cuivre incorporé au film sous sa forme réduite est plus actif que le cuivre incorporé au film initialement oxydé. Par ailleurs, nous avons montré que la concentration de H+ dans le polymère est limitée. En conséquence, le processus de réduction de NO3- sur le cuivre dispersé dans un film de polyaniline est modifié en milieu acide. L’utilisation d’un film de poly-3,4-éthylènedioxythiophène déposé sur une surface de Pt s'est quant à elle révélée inadéquate comme support pour l'incorporation de Cu dans le cadre de l'étude de la réduction de NO3- en milieu acide.

The focus of this dissertation is to decipher the previously unknown reaction dynamics of NO3 photodissociation. Although the NO + O2 products are known to catalyze atmospheric ozone destruction, the mechanism by which these products are formed has remained a mystery, and no energetically accessible transition state has ever been calculated. Using velocity map ion imaging experiments to carefully study the stereochemistry of the product fragments combined with theoretical calculations performed by Drs. Xiao, Maeda, and Morokuma at Kyoto University, we have determined that the reaction proceeds exclusively via the unusual "roaming mechanism," with no evidence of a competing traditional transition state pathway. Within, the significance of this discovery is discussed in regards to both the NO3 system and roaming dynamics in general, for which this system has provided new insight.

The aim of this study was to investigate the reaction behaviors of nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the electrokinectic (EK) process for remediation of NO3− and Cr6+ in saturated soil. To assure the above-mentioned nanomaterials were capable of reductively adsorbing inorganic pollutants (e.g., NO3− and Cr6+) in the acidic environment in the anode reservoir of the ek remediation system, an investigation on transformation of the concerned nanomaterials in different aqueous solutions (de-ionized water and simulated groundwater ) of different initial pHs (2 and 3.5) was conducted. Due to a high dose of nanoscale Fe3O4 and a resulting serious agglomeration while adsorbing NO3− and Cr6+, the characteristic peaks of the X-ray diffraction (XRD) analysis for nanoscale Fe3O4 remained the same after adsorption experiments. But the situations were quite different in the case of nanoscale H1/10-[Fe3O4]MgO, the characteristic peaks of £\-Fe2O3 in the XRD pattern were detected, confirming that this nanomaterial could reductively adsorb NO3− and Cr6+ in the acidic environment. The effectiveness of using polyacrylic acid (PAA) and soluble starch (SS) to stabilize nanoscale Fe3O4 and H1/10-[Fe3O4]MgO in different aqueous solutions containing humic acid was compared. It was found the former yielded a better stability. Therefore, PAA was chosen to prepare the slurries of target nanomaterials. Then slurry injection coupled with the EK process was tested for remediation of NO3- and Cr6+ in saturated soil. The results showed that the removal efficiency of NO3− was more than 90%, and the NO3− concentration in the anode reservoir was below Taiwan¡¦s Pollution Control Standards of type¢¹Groundwater for NO3−-N. Under the same test conditions, however, the removal efficiency of Cr6+ was unsatisfactory. This might be ascribed to acidification of soil near the anode resulting in high adsorption of Cr2O72− by soil. Thus, a solution to solve this problem has to seeked. The solution lies in how to enhance the contact of the above-mentioned nanomaterials with Cr6+ in the anode reservoir. One possibility is to use the nature of SS would hydrolyze in the acidic environment. Therefore, SS-stabilized nanomaterials in the acidic environment would hydrolyze resulting in the exposure of the soil nanomaterials therein. To this end, SS was used to replace PAA for nanomaterial slurry preparation for remediation of Cr6+. In addition, polarity reversal was practiced in the EK system to maintain a neutral ph of soil and increase the mobility of Cr6+ in soil. Finally, the result showed that nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the polarity reversal electrokinetic system could really enhance the removal efficiency of Cr6+ in the saturated soil. In summary, nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the EK process has been proven to be capable of remedying NO3− and Cr6+ in saturated soil. Meanwhile, the concept of reductive adsorption was realized in this work as well.

This study was to investigate the reaction behavior of laboratory-prepared nanoscale adsorbents (Fe3O4 and H-[Fe3O4]MgO) and inorganic pollutants (NO3-, Cd2+and Cr6+) in simulated groundwater. First, Fe3O4 and the composites of nanoscale Fe3O4 and MgO were prepared using chemical co-precipitation method. Then they were characterized and verified by various apparatuses and methods including X-ray diffractometry, scanning electron microscopy, Zetasizer, and specific surface area measurements. Second, the nanoscale adsorbents were used to adsorb inorganic pollutants in simulated groundwater of different conditions. The relevant reaction behavior and mechanisms were also investigated. Results of this research showed that Fe3O4 and H-[Fe3O4]MgO had the greater adsorption amount when the initial concentration of inorganic pollutants was higher than lower. The adsorption rate of inorganic pollutants at 28¢J was greater than that of at 18¢J. The experimental results also showed that at a higher pH environment or the existence of humic acid in simulated groundwater would increase the removal efficiency of Cd2+, but decrease the removal efficiency of NO3- and Cr6+. Analysis of inorganic pollutants adsorption on nanoscale adsorbents in simulated groundwater indicated that a Langmuir-type of chemical adsorption and pseudo-second-order reaction kinetic equation would have better fit. In this study, it was also found that nanoscale adsorbents not only adsorbed inorganic pollutants but also reduced NO3- and Cr6+ to NO2-, NH4+, and Cr3+ at pH=3, respectively. Thus, the nanoscale adsorbents (Fe3O4 and H-[Fe3O4]MgO) prepared and were capable of reductively adsorbing inorganic pollutants (e.g., NO3- and Cr6+) for environmental remediation.

Atmospheric deposition of nitrogen has been implicated in the destruction of seagrass beds and in the decline of water quality of Tampa Bay, Florida. The objective of this research was to determine the tendency for air masses of different origins to wet-deposit nitrate and ammonium species to the bay. Precipitation chemistry data was obtained via the NADP AIRMoN Gandy Bridge monitoring site for the period of 1 August 1996 through 31 December 2000. Rainfall events were classified by using the NOAA HYSPLIT trajectory model, precipitation chemistry data, and tropical storm history data. Average nitrate and ammonium concentrations and nitrogen fluxes were calculated based upon the chosen categories. The average annual nitrogen flux for nitrate and ammonium were 2.1 kg/ha/yr and 1.4 kg/ha/yr, respectively. For trajectory-classified data, the lowest nitrate and ammonium nitrogen fluxes were observed with air masses from the west and south, over the Gulf of Mexico. The highest ammonium nitrogen flux was seen from trajectories from the east, while local trajectories demonstrated the highest average nitrate nitrogen flux. For chemically-classified data, the highest nitrate and ammonium fluxes were associated with the local combustion classification. Rainfall from tropical weather systems deposited lower average nitrate nitrogen fluxes than non-tropical events, but ammonium nitrogen fluxes were the same between tropical and non-tropical precipitation. Even the events representing the cleanest air masses contributing precipitation to Tampa Bay had nitrate and ammonium concentrations more than two times the background concentrations associated with the northern hemisphere.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2016-10-06T18:31:14Z No. of bitstreams: 1 2011 - Ana Maria Silva de Araujo.pdf: 2356633 bytes, checksum: ddb45ffd88bc508180544f6f9a4cb0a3 (MD5) / Made available in DSpace on 2016-10-06T18:31:14Z (GMT). No. of bitstreams: 1 2011 - Ana Maria Silva de Araujo.pdf: 2356633 bytes, checksum: ddb45ffd88bc508180544f6f9a4cb0a3 (MD5) Previous issue date: 2011-02-24 / CAPES / CNPq / The wet tropical climate, characteristic of great part of the Northeast, Midwest and part of the Southeast regions of Brazil, present markedly a rainy season and a dry one. During the dry season, the evapotranspiration provides capillary movements of water in soil coincidently with the superficial accumulation of NO3 -. The amount of nitrate in the soil may vary with the seasonality of environmental variables, such as the temperature and precipitation, thus influencing the assimilation process, the consumption and the storage of that ion by the plants. This way, in the beginning of the rainy period there is a great availability of NO3 - in the soil. This phenomenon has being identified as nitrate flush. The objective of the study was to evaluate the possibility of occurrence of synchronism among N-NO3 - flush and absorption of N by two rice varieties dissimilar in the storage capacity and remobilization of N in field conditions. Two experiments were installed in two consecutive years in the town of S?o Luis and in Miranda do Norte, Maranh?o State. The areas had three different management systems: alley cropping, slash-and-burn agriculture (cutting down and burning), and conventional system. The legume trees used were: Leucaena leucocephala (Leucena); Clitoria fairchildiana (Philippine pigeonwings); and Acacia mangium (acacia). They were combined among themselves, in the following treatments: Philippine pigeonwings + Leucena (S + L); Acacia + Leucena (A + L), and a reference plot, without legume trees. The experimental design was of random blocks in sub-subdivided plots with four repetitions. The appraised parameters were: nitrate reductase (NR) activity, the plant N metabolism, the mineralization of N in soil, the seasonal flow of NO3 - in soil, biomass production, and the rice productivity. According to the results, the addition of biomass from legume trees did not cause great alterations in the soil characteristics, in S?o Luis and in the Miranda do Norte areas. In the soil the largest changes were observed for the burnt area and the one with conventional system. The Acacia + Leucena alley cropping influenced significantly most of evaluated variables, and in most of the time they showed superior to Sombreiro + Leucena alley and the testimony. In general, the activity of the nitrate reductase was low, for all systems. However, a variation was verified in the enzyme activity according to sampling period. The results showed the largest reductions in NO3 - in the hems, indicating this is the preferential plant part for N remobilization in rice. The traditional variety always presented lower values of NR activity, and it accumulated more NO3 - compared with the improved variety. There were seasonal variations in the levels of NO3 - and NH4 + in the soil; however the largest accumulations of NH4 + occurred in the superficial layer and in the beginning of the rainy season. The rice productivity was low; however it differed significantly among the management systems. / O clima tropical ?mido, caracter?stico de grande parte do Nordeste, Centro-Oeste e parte do Sudeste do Brasil, apresenta de forma marcante uma esta??o chuvosa e outra seca. Durante a esta??o seca, a evapotranspira??o proporciona movimentos capilares de ?gua no solo coincidentes com o ac?mulo superficial de NO3 -. Esse conte?do de nitrato no solo pode variar com a sazonalidade de vari?veis ambientais, tais como a temperatura e a precipita??o, assim influenciando o processo de assimila??o, o consumo e o armazenamento desse ?on pelas plantas. Portanto, no in?cio do per?odo chuvoso ocorre grande disponibilidade de NO3 - no solo e este fen?meno tem sido denominado como ?flush? de nitrato. O objetivo do estudo foi o de avaliar a possibilidade de ocorr?ncia do sincronismo entre esse ?flush? de N-NO3 - e a absor??o de N por duas variedades de arroz diferentes quanto ? capacidade de armazenamento e remobiliza??o de N em condi??es de campo. Para tal, foram instalados dois experimentos por dois anos consecutivos nos munic?pios de S?o Luis e Miranda do Norte, Estado do Maranh?o em tr?s diferentes sistemas de manejo: cultivo em al?ias, ro?a no toco (derrubada e queima) e sistema convencional. As esp?cies de leguminosas utilizadas foram: Leucaena leucocephala (leucena); a Clitoria fairchildiana (sombreiro) e a Acacia mangium (ac?cia), combinadas entre si, nos seguintes tratamentos: Sombreiro + Leucena (S + L); Ac?cia + Leucena (A+ L) e Testemunha, sem leguminosas. Em todos os sistemas de manejo adotou-se o delineamento experimental de blocos casualizados em parcelas sub-subdivididas com quatro repeti??es. Os par?metros avaliados foram ? atividade da nitrato redutase, o metabolismo do N na planta, o fluxo sazonal de NO3 - no solo, produ??o de biomassa e a produtividade do arroz. De acordo com resultados, a adi??o de biomassa das leguminosas n?o causou grandes altera??es nas caracter?sticas do solo tanto em S?o Luis quanto no munic?pio de Miranda do Norte. No solo as maiores altera??es foram observadas para o a ?rea queimada e a ?rea mantida em sistema convencional. As al?ias de Ac?cia + Leucena influenciaram de forma significativa a maioria das vari?veis avaliadas apresentando-se na maioria das vezes superiores as al?ias de Sombreiro + Leucena e a testemunha. No geral, a atividade da nitrato redutase foi baixa em todos os sistemas de manejo. No entanto, constatou-se varia??o na atividade da enzima em fun??o ?poca de amostragem. Os resultados mostraram que as maiores redu??es nos teores de NO3 - foram observados nas bainhas, indicando ser este o local preferencial para a remobiliza??o de N em arroz. A variedade tradicional apresentou sempre valores mais baixos de atividade da NR e acumulou mais NO3 - comparada com a variedade melhorada. Houve varia??es sazonais no teor de NO3 - e NH4 + no solo, por?m os maiores ac?mulos de NH4 + ocorreram na camada superficial e in?cio da esta??o chuvosa. A produtividade do arroz foi baixa, por?m diferiu de forma significativa entre os sistemas de manejo.

L'acide nitrique est largement utilisé dans le procédé de retraitement du combustible nucléaire usé, le procédé PUREX (Plutonium and Uranium Refining by EXtration). Ce procédé est fondé sur l'extraction liquide-liquide de l'uranium et du plutonium aux degrés d'oxydation (+VI) et (+IV) respectivement. Le plutonium est ensuite désextrait, et ainsi séparé de l'uranium par ajout d'uranium (+IV) stabilisé en milieu acide nitrique par des ions hydrazinium (N2H5+). Or, la radiolyse de l'acide nitrique, inhérente à la présence d'émetteurs α dans ces solutions, génère des espèces radicalaires et moléculaires susceptible de modifier, d'une part, le comportement redox des actinides et, d'autre part, de réagir avec les ions hydrazinium. Le but de ce travail est de mieux maîtriser les paramètres chimiques et physico-chimiques susceptibles de modifier les degrés d'oxydation de l'uranium et du plutonium dans les solutions d'acide nitrique. Parmi ces paramètres, le rôle de l'acide nitreux et du peroxyde d'hydrogène, générés par radiolyse de l'acide nitrique, est primordial. L'objectif est de repréciser les cinétiques de formation du peroxyde d'hydrogène et de l'acide nitreux par radiolyse alpha des milieux acide nitrique / nitrate de sodium en fonction des paramètres : acidité, concentration des ions nitrate et transfert d'énergie linéique du rayonnement ionisant.Il a été montré que la formation de peroxyde d'hydrogène diminue avec l'augmentation de la concentration des ions nitrate et augmente fortement avec l'acidité de la solution, jusqu'à atteindre une valeur stationnaire pour une acidité proche de 0,2 mol L-1. Pour sa part, la formation de l'acide nitreux est favorisée par l'augmentation de la concentration des ions nitrate. Il a été observé que G(HNO2) évolue selon deux tendance distincte, la première dans les solutions diluées d'ions nitrate et la seconde dans les solutions concentrées d‘ions nitrate. Ces deux variations traduisent des phénomènes radiolytiques directs et indirects modifiant les mécanismes de formation de HNO2. L'étude de l'acidité des solutions irradié a montré que la formation de H2O2 et de HNO2 est favorisé avec l'augmentation de la concentration des ions hydronium, jusqu'à atteindre une valeur stationnaire pour une acidité proche de 0,2 - 0,5 mol L-1.Par ailleurs, les effets induits par la nature du rayonnement ionisants (,,,…), sur les rendements de formation de H2O2 et HNO2, ont été étudiés. Il a été montré que le transfert d'énergie linéique (TEL), compris entre 0,2 keV µm-1 (caractéristique d'un rayonnement gamma) et 130 keV µm-1 (caractéristique d'un rayonnement alpha émis par la décroissance radioactive d'un actinide), a une influence significative sur les rendements de formation de H2O2 et de HNO2. Il a été observé que l'impact des ions nitrate sur le rendement de formation de H2O2 devient plus marqué, lorsque le TEL augmente. A contrario, l'impact des ions nitrate favorisant le rendement de formation de HNO2, diminue lorsque le TEL augmente. Sur la base des résultats acquis durant cette étude et des données présentes dans la littérature, deux équations paramétriques ont été développées. L'intérêt de cette paramétrisation des effets est de prédire les rendements radiolytiques de formation de H2O2 et de HNO2 selon les conditions chimique du milieu ([NO3-] ≤ 4 mol L-1 et 10-5 mol L-1 ≤ [H+] ≤ 4 mol L-1) et selon la nature du faisceau (TEL compris entre 0,2 – 130 keV µm-1).La finalité de cette étude serait de prédire les quantités de H2O2 et de HNO2 formés par radiolyse de HNO3/NaNO3 dans les étapes du procédé de retraitement des combustibles nucléaires. / Nitric acid is widely used in spent nuclear fuel reprocessing, especially in PUREX process (Plutonium and Uranium Refining by Extraction). This process is based on liquid-liquid extraction of Uranium (+VI) and Plutonium (+IV). Plutonium is separated from Uranium by addition of Uranium (+IV) in nitric acid, stabilized by hydrazinium ion (N2H5+). However, the radiolysis of nitric acid, result of the presence of alpha emitting radionuclides, generates in solutions free radicals and molecular species. These species are capable of modifying the redox state of actinides and reacting with hydrazinium ions.The aim of this work is to reveal the chemical and physical-chemical parameters that may modify the oxidation states of Uranium and Plutonium in nitric acid solutions. Among these parameters, the role of nitrous acid and hydrogen peroxide, generated by radiolysis of the nitric acid, is very important. The objective is to redefine the kinetics of formation of hydrogen peroxide and nitrous acid during alpha radiolysis of nitric acid / sodium nitrate, as a function of three parameters: acidity, nitrate concentration and the linear energy transfer of ionizing radiation.It was shown that the formation of hydrogen peroxide decreases with increasing nitrate ions concentration and increases greatly with the acidity of the solution (until it reaches a stationary value for an acidity of 0.2 mol L-1). The formation of nitrous acid is promoted by the increase the nitrate ions concentration. It was observed that G(HNO2) varies according to two trends. The first one in dilute nitrate solutions and the second in concentrated nitrate solutions. These two trends reflect the direct and indirect radiolytic phenomena, modifying the mechanisms of formation of HNO2. The study of acidity has showed that the formation of H2O2 and HNO2 is promoted by increasing the concentration of hydronium ions, until it reaches a steady state value for an acidity close to 0.2-0.5 mol L-1.Furthermore, the effects induced by ionizing radiation (,,,…) on formation yields of H2O2 and HNO2 were studied. It has been shown that the linear energy transfer (LET), between 0.2 keV µm-1 (characteristic of a gamma radiation) and 130 keV µm-1 (characteristic of the alpha radiation emitted by radioactive decay of actinides), has a significant influence on formation yield of H2O2 and HNO2. It was observed that the impact of nitrate ions on the formation yield of H2O2 becomes more pronounced when the LET increases. Conversely, the impact of nitrate ions which promote the formation of HNO2, decreases when the LET increases.Based on these results, two parametric equations were developed. The advantage of this parameterization is to predict the radiolytic yields formation of H2O2 and HNO2 according to chemical conditions ([NO3-] ≤ 4 mol L-1 and 10-5 mol L-1 ≤ [H+] ≤ 4 mol L-1) and the nature of the beam (LET between 0.2 to 130 keV µm-1).The purpose of this study is to predict the quantity of H2O2 and HNO2 formed by radiolysis of HNO3/NaNO3, during the different steps of the nuclear fuel reprocessing.

La composition isotopique (¹³C/¹²C) du CO₂ respiré par les feuilles et les racines dans l'obscurité et celle des substrats respiratoires putatifs, y compris les sucres solubles et les acides organiques (malate et citrate), l'activité de la PEPc ainsi que les échanges gazeux des feuilles ont été déterminés sur le haricot (Phaseolus vulgaris L.) et l’épinards (Spinacia oleracea L.) cultivés dans du sable avec différents rapports NH₄⁺: NO₃⁻ dans N fourni. Le CO₂ respiré par les feuilles était enrichi en ¹³C sous NO₃⁻ s’appauvrissant progressivement avec l’augmentation de la fraction de NH₄⁺ dans le N fourni, tandis que la composition isotopique du CO₂ issu de la respiration des racines restait inchangée quel que soit le rapport NH₄⁺: NO₃⁻. Nous avons suggéré qu'une plus grande quantité de pools enrichis en ¹³C fixés par la PEPc via la voie anaplérotique contribuait à la respiration foliaire sous NO₃⁻. Cependant, un effet similaire dans les racines attendu sous NH₄⁺ a été masqué en raison d'une refixation (par la PEPc) du CO₂ respiré (appauvrie en ¹³C). De manière inattendue, les modifications de la composition isotopique du C des métabolites individuels, leurs quantités, ainsi que l'activité de l’enzyme PEPc, présentaient des profils différents entre les deux espèces étudiées. Des expériences de double marquage (¹³C et ¹⁵N) sont nécessaires pour mieux comprendre l’impact de la plasticité métabolique du TCA sur l’écart isotopique entre le malate et le citrate et sur la composition isotopique du CO₂ respiré chez différentes espèces sous différentes formes d’azote. / C-isotope composition of leaf- and root-respired CO₂ in the dark and that of putative respiratory substrates including soluble sugars and organic acids (malate and citrate), PEPc activity, as well as leaf gas exchanges were determined on bean (Phaseolus vulgaris L.) and spinach (Spinacia oleracea L.) plants grown in sand with varying ratios of NH₄⁺: NO₃⁻ in supplied N. Leaf-respired CO₂ was ¹³C enriched under NO₃⁻ nutrition and became progressively ¹³C depleted with increasing amount of NH₄⁺ in supplied N, while C-isotope composition of root-respired CO₂ remained unchanged across N-type gradient. We suggested that a higher amount of ¹³C enriched C-pools fixed by PEPc through anaplerotic pathway contributed to respired CO₂ in leaves under NO₃⁻ nutrition. However, a similar effect in roots expected under NH4+ nutrition was masked because of a rather ¹³C depleted C source (respired CO₂) refixation by PEPc. Unexpectedly, the changes in C-isotope composition of individual metabolites and their amounts as well as PEPc activity exhibited different patterns between the two species. Double labelling experiments (¹³C and ¹⁵N) are needed for better understanding the impact of metabolic plasticity of TCA on isotopic gap between malate and citrate and on C-isotope composition of respired CO₂ in different species under varying N-type nutrition.

Afin de réduire la consommation en énergie fossile et ainsi limiter les émissions de gaz à effet de serre, l’un des objectif du Grenelle de l’Environnement est de porter à 23% la part des énergies renouvelables dans la consommation d’énergie finale en France en 2020. Le bois-énergie représente une alternative à l’utilisation des énergies fossiles, mais c’est également une source de polluants dans l’atmosphère et il est essentiel de déterminer sa contribution potentielle à la dégradation de la qualité de l’air intérieur et extérieur. Au cours de cette thèse, mes travaux de recherche se sont focalisés sur l’étude en chambres de simulation de la dégradation atmosphérique de composés émis par la combustion du bois : les méthoxyphénols. Au Laboratoire de Physico-Chimie de l’Atmosphère (LPCA) de l’Université du Littoral Côte d’Opale (ULCO), des tests ont tout d’abord été réalisés afin de s’assurer que les parois de la chambre, en PMMA (PolyMéthacrylate de Méthyle), n’induisaient pas d’artéfacts lors de son irradiation et des réactions chimiques réalisées avec l’ozone, les radicaux hydroxyles et les radicaux nitrates. La constante de réaction du syringol avec les radicaux OH a été déterminée à (294 ± 3) K. La valeur obtenue (9,65x10⁻¹¹ cm³.molécule⁻¹.s⁻¹) conduit à une durée de vie atmosphérique du syringol d’environ 2 heures pendant la journée. L’oxydation du guaiacol et du syringol par les radicaux hydroxyles a permis d’observer la formation d’aérosols organiques secondaires (AOS) avec des rendements de 0,003 - 0,87 et 0,10 - 0,36, respectivement. L’étude des produits d’oxydation gazeux et particulaires de la réaction du guaiacol avec les radicaux OH a mis en évidence principalement la présence de nitroguaiacols dans la phase gazeuse et nous avons suggéré d’utiliser ces composés comme traceurs de la combustion du bois du fait de leur faible réactivité atmosphérique.Les études cinétiques des réactions des radicaux nitrates avec le guaiacol, le 3-méthoxyphénol et le syringol réalisées à (294 ± 3) K ont permis de déterminer les constantes de réactions correspondantes. Celles-ci se trouvent dans la gamme (1,15 – 21,7) × 10⁻¹¹ cm³.molécule⁻¹.s⁻¹ et les durées de vie associées sont d’environ 2 minutes pendant la nuit. À la Bergische Universität Wuppertal (en Allemagne), la réaction d’une série de composés aromatiques méthoxylés (anisole, 2-méthylanisole, guaiacol, 3-méthoxyphénol, 4-méthoxyphénol, 2-méthoxy-4-méthylphénol, syringol et 2,3-diméthoxyphénol) avec les radicaux hydroxyles a été étudiée. Les constantes des méthoxybenzènes et méthoxyphénols obtenues sont comprises entre (2,12 – 4,64) x 10⁻¹¹ cm³.molécule⁻¹.s⁻¹ et (5,75 - 8,10) x 10⁻¹¹ cm³.molécule⁻¹.s⁻¹, respectivement, ce qui conduit à des durées de vie de 4-8 et 3-2 heures. Pour ces mêmes composés, nous avons également déterminé, les constantes pour leur réaction avec les atomes de chlore qui sont dans la gamme (1,07 – 1,20) x 10⁻¹⁰ cm³.molécule⁻¹.s⁻¹, pour les méthoxybenzènes et (2,71 – 4,73) x 10⁻¹⁰ cm³.molécule⁻¹.s⁻¹ pour les méthoxyphénols. Leurs durées de vie vis-à-vis de cette réaction sont respectivement de 46-52 heures et 12-21 heures. Cette étude sur l’oxydation troposphérique des méthoxyphénols est à notre connaissance la première qui ait été réalisée. Elle a permis de mettre en évidence une réactivité élevée diurne et nocturne de ces composés ainsi que leur contribution à la formation d’AOS. Le bois-énergie est donc à la fois une source d’aérosols primaires mais également secondaires et son utilisation a donc des effets sur l’homme (santé) et l’environnement. / One of the objectives of the Grenelle Environment Forum is to increase the quantity of the renewable energy up to 23% in the final energy consumption in France in 2020, to reduce fossil fuel consumption and thus restrict the level of greenhouse gas emissions. The wood-energy represents an alternative to fossil fuel, but it also a source of atmospheric pollutants. It is necessary to determine its potential contribution to the degradation of air quality (indoor and outdoor). During this PhD, my works focused on the study, in simulation chambers, of the atmospheric degradation of compounds emitted by wood combustion : the methoxyphenols. In the Laboratory of Physical Chemistry of the Atmosphere (LPCA) of the Universite of Littoral-Côte d’Opale (ULCO), tests were carried out to be sure that the walls of the chamber (in PMMA PolyMethacrylate of Methyl) are not a source of artifacts during its irradiation and chemical reactions with ozone, hydroxyl radicals and nitrate radicals. The rate coefficient of the reaction of syringol with OH radicals was determinate at (294 ± 2) K and is 9,65 x 10−¹¹ cm³ molecule−¹ s−¹. Then the atmospheric lifetime was calculated : it is about 2 hours during the day. During the oxidation of guaiacol and syringol, we observed the formation of Secondary Organic Aerosol (SOA) with yields ranging from of 0.003 to 0.87 and from 0.10 to 0.36, respectively. Oxidation products study in the gas- and particle- phases for the reaction of guaiacol with OH radicals showed principally the presence of nitroguaiacols in the gas phase, which may be potential wood combustion tracers due to their low atmospheric reactivity. The kinetic studied of NO₃ radicals with guaiacol, 3-methoxyphenol and syringol were realized at (294 ± 3) K. They were leaded to rate coefficients in the range of (1,15 – 21,7) x 10−¹¹ cm³ molecule−¹ s−¹ and so associated atmospheric lifetimes about 2 minutes, overnight. At the Bergische Universität Wuppertal (Germany), the reaction of a series of methoxylated aromatic compounds (anisole, 2-methylanisole, guaiacol, 3-methoxyphenol, 4-methoxyphenol, 2-methoxy-4-methylphenol, syringol and 2,3-dimethoxyphenol) with hydroxyl radicals were studied leading to the following rate coefficients for methoxybenzenes and metoxyphenols, (2,12 -4,64) x 10−¹¹ cm³ molecule−¹ s−¹ and (5,75 -8,10) x 10−¹¹ cm³ molecule−¹ s−¹, respectively. The estimated atmospheric lifetimes are in the range from 4 to 8 hours and from 2 to 3 hours, for methoxybenzenes and methoxyphenols, respectively. For these compounds, we also determined, the rate coefficients for their reaction with chlorineatoms, which are between (1,07 – 1,20) x 10−¹¹ cm³ molecule−¹ s−¹, for methoxybenzenes, and (2,71 – 4,73) x 10−¹¹ cm³ molecule−¹ s−¹, for methoxyphenols. Thus, their respective atmospheric lifetimes are 46-52 hours and 12-21 hours. This study of tropospheric oxidation of methoxyphenols is to our knowledge the first one. It allows underlining a high reactivity of these compounds during the day and overnight and also their contribution to SOA formation. The wood-energy is thus both a source of primary and secondary aerosols. Its use therefore impacts human health and the environment.