Thèses sur le sujet « Ammoniac (NH3) »

Nous avons étudié les transferts inélastiques rotationnels induits par collisions dans l'ammoniac perturbé par H₂et He, systèmes d’intérêt astrophysique et fondamental (test du potentiel intermoléculaire). Nous avons mené cette étude par deux méthodes différentes : - Profil de raies d'absorption infrarouge - Double résonance infrarouge-infrarouge résolue dans le temps. La première nous a permis de déterminer les sections efficaces d'élargissement par pression et de couplage intradoublet (très sensible au potentiel intermoléculaire) en fonction du nombre quantique de rotation j et de la température dans la bande v₄et l'état vibrationnel fondamental. Afin de comprendre, d'une part, la différence entre les résultats obtenus en micro-onde et ceux de la bande v₄, et d'autre part pour effectuer une meilleure comparaison entre l'expérience et la théorie, nous avons mesuré des sections efficaces d'élargissement par pression dans l'état vibrationnel fondamental. Les résultats expérimentaux ainsi que les calculs théoriques semi-classiques effectués en collaboration avec G. Billing ont permis d'aboutir aux conclusions suivantes : - Différence entre la collision NH₃- He et NH₃- H₂para. -Mise en évidence d'un effet vibrationnel dans la collision NH₃- H₂ -Rôle de l'excitation rotationnelle de H₂lors de la collision. - Désaccord entre les valeurs expérimentales et théoriques du coefficient de couplage dans la collision NH₃- He. La deuxième méthode consiste à créer une perturbation de populations d'un niveau rotationnel sélectionné à l'aide d'un pulse laser (laser à C0₂TEHP), puis à détecter l'absorption transitoire avec un laser continu (diode laser). Cette étude permet de déterminer les sections efficaces collisionnelles niveau par niveau. En sondant les niveaux voisins du niveau pompé, on pourra déterminer les règles de sélection collisionnelles
We have studied rotational transfer induced by inelastic collision in NH₃perturbed by Hz and He. Their systems have astrophysical and fundamental interests. We have undertaken this study by using two methods: 1) Absorption line-profiles in the infrared. 2) Time resolved infrared-infrared double resonance. The first one allowed to determine pressure broadening (PB) cross sections and intradoublet cross relaxation (CR) cross sections caused by molecular inversion. These last ones are very sensitive to the detail of intermolecular potential. These measurements were done as a function of the rotational quantum number j and the temperature in both range of the v₄ band and of the vibrational ground state. Because of the difference between results obtained in the v₄ band and in the microwave, and in order to obtain a better comparison between measurements and calculations, we have studied the absorption line-profiles in the vibrational ground state. The main results lead to the following conclusions: - PB cross section increases with the vibrational quantum number the NH₃ - He one. - PB cross section for NH₃- H₂ para system are larger than the NH₃ - He one. - It is necessary to take the rotational excitation of H₂ into account. - Good agreement has been obtained between calculated (using a semi-classical method) and measurements for NH₃ - H₂ system. The only remaining discrepancy between theory and experience is then intradoublet CR cross section for the NH₃ - He system; we think that this could be caused by inaccuracies in the NH₃ - He potential. The second method, which is a very sensitive mean to study rotational transfer induced by inelastic collision, consist of pumping the v₂ band of NH₃ with an infrared pulse TEHP C0₂ laser in order to create a non-equilibrium population in specific rotational quantum state. This state as well as others subsequently populated by collision induced transition is monitored by diode laser tuned on the v₄ band. This study permit to determine the inelastic cross-section for every level and the collisional selection rules

L’ammoniac (NH3) est un polluant atmosphérique émis à 80 % par l’agriculture, qui contribue à l’eutrophisation et l’acidification des milieux naturels. C’est aussi un précurseur de particules fines (PM2.5) nocives pour la santé. Malgré ce rôle scientifique et sociétal majeur, nos connaissances sur l’ammoniac atmosphérique restent très limitées. La mesure du profil vertical de NH3 constitue l’une des clés permettant d’approfondir ces connaissances. C’est pourquoi, l’objectif principal de cette thèse est de développer un instrument de mesure de l’ammoniac embarquable dans un ballon captif afin de mesurer ces profils verticaux. Un état de l’art de la mesure de NH3 a d’abord été réalisé à travers l’analyse des données de la campagne AMICA (Analyse Multi-Instrumentale des Concentrations d’Ammoniac) à l'automne 2021. Il a montré la nécessité de concevoir un instrument sans système de prélèvement pour éviter les biais liés à l’adsorption de NH3. Afin de tester et valider les techniques de spectroscopie infrarouge (DAS et WMS) envisagées pour la mesure de NH3, un premier instrument pour la mesure du CO2 (premier gaz à effet de serre d'origine anthropique) a été développé et a permis de réaliser des mesures de profils verticaux. NH3 étant bien plus difficile à détecter que le CO2, une cellule optique à grande longueur de parcours a été conçue afin d’améliorer la sensibilité de l’instrument. Plus généralement, les outils conçus et mis en place au cours de cette thèse peuvent s’appliquer à la mesure de toutes les espèces atmosphériques d’intérêt et en particulier à celles présentes à l’état de traces
Ammonia (NH3) is an atmospheric pollutant, emitted at 80 % by agriculture, which contributes to the eutrophication and acidification of natural environments. It is also a precursor of fine particles (PM2.5) that are harmful to human health. Despite this major scientific and societal role, our knowledge about atmospheric ammonia is still very limited. Measuring the vertical profile of NH3 is one of the keys to improving this knowledge. For this reason, the main objective of this thesis is to develop an ammonia measurement instrument that can be embedded in a tethered balloon to measure these vertical profiles. To begin, a state of the art of NH3 measurement was carried out through the data analysis of the AMICA campaign (Multi-Instrumental Analysis of Ammonia Concentrations) in autumn 2021. It highlighted the need to design an instrument without a sampling system to avoid bias due to NH3 adsorption. To assess the infrared spectroscopy techniques (DAS and WMS) intended for NH3 detection, a first instrument aimed at atmospheric CO2 measurements (main anthropogenic greenhouse gas) was developed and used to carry out vertical profiles. As NH3 is much more difficult to detect than CO2 , a long-path optical cell was designed to improve the instrument’s sensitivity. On a more general level, the tools developed and implemented during this thesis can be applied to the measurement of all the atmospheric species of interest, and in particular those that exist in trace quantities

Ce travail avait pour but de déterminer les paramètres des raies d’absorption de la molécule d’ammoniac en vue d’applications atmosphériques. A ce sujet, nous avons mesuré, à température ambiante, les intensités et les coefficients d’élargissement et de déplacement collisionnels des raies des bandes v1, v3, 2v4, et 4v2 dans la région spectrale 3050-3600 cm-1 de NH3 auto-perturbé. Ces mesures ont été effectuées dans un grand nombre de branches de ces bandes avec une très grande précision à l’aide d’un spectromètre infrarouge à transformée de Fourier à haute résolution (0.008 cm-1). Ces paramètres spectroscopiques ont été déterminés à l’aide d’une technique d’ajustement multi-pression utilisant deux profils différents : un profil de Voigt et un profil de Rosenkranz. Le manuscrit comporte cinq parties. La première partie concerne les propriétés spectroscopiques de l’ammoniac. La deuxième partie est dédiée à l’appareillage, avec la description du spectromètre IRTF Bruker IFS125HR. Dans la troisième partie, nous exposons les résultats des intensités et des auto-élargissements de raies isolées, qui sont extrait à partir des spectres enregistré, des bandes v1, v3,2v4 et 4v2 de NH3. La quatrième partie présente les résultats obtenus sur les déplacements de raies et les effets d’interférence entre les composantes des doublets des bandes v1 et v3 de NH3.Pour interpréter les résultats des mesures de largeurs de raies du système collisionnel NH3 auto-perturbé, nous allons présenter dans le chapitre 5 le formalisme adopté pour le calcul de ces largeurs. Une comparaison entre les largeurs calculées et mesurées permet de tester la validité du formalisme utilisé
The aim of this work was to determine the parameters of the absorption lines of the ammonia molecule for atmospheric applications. In this regard, we measured, at room temperature, the intensities, the broadening and the shift coefficients of the lines of the bands v1, v3, 2v4, and 4v2 in the spectral region 3050-3600 cm-1 of self-disturbed NH3. These measurements were carried out in a large number of branches of these bands with very high precision using a high resolution Fourier transform infrared spectrometer (0.008 cm-1).These spectroscopic parameters were determined using a multi-pressure fitting technique using two different profiles: a Voigt profile and a Rosenkranz profile.The manuscript consists of five parts. The first part concerns the spectroscopic properties of ammonia. The second part is dedicated to the apparatus, with the description of the Bruker IFS125HR IRTF spectrometer. In the third part, we expose the results of the line intensities and self-broadenings of isolated lines, which are extracted from the recorded spectra, bands v1, v3, 2v4 and 4v2 of NH3. The fourth part presents the results obtained on line shifts and the interference effects between the components of the doublets of the v1 and v3 bands of NH3.To interpret the results of the line width measurements of the self-disturbed NH3 collisional system, we will present in chapter 5 the formalism adopted for the calculation of these widths. A comparison between the calculated and measured widths makes it possible to test the validity of the formalism used

Les moteurs Diesels connaissent un intérêt récent tout particulier car ils rejettent moins de CO2 que les moteurs essences à puissance égale, du fait qu’ils travaillent en mélange pauvre (en excès d’oxygène). Récemment, des catalyseurs de réduction catalytique sélective (SCR) déposés sur des filtres à particules diesel (FAP) ont été développés pour les applications automobiles en raison de leur capacité à réduire simultanément les émissions de NOx et de particules. Une telle mise en œuvre nécessite une résistance thermique améliorée du catalyseur SCR du fait des exothermes liés à la régénération périodique du FAP. Le but de ce travail est de proposer un catalyseur pour la réduction des NOx par NH3 actif après vieillissement à haute température. La première partie de ce manuscrit détaille les modifications du catalyseur CeV0.95W0.05O4 en ajoutant des éléments de terres rares (Pr3+, Gd3+, Tb3+, Er3+). Le catalyseur le plus prometteur obtenu par la substitution partielle du cérium par des terres rares était finalement le catalyseur Ce0.5Er0.5V0.95W0.05O4. Une substitution partielle du cérium par de l’erbium permet d’obtenir un gain d’activité après vieillissement à 600 et 850°C attribué à la capacité de l'erbium à favoriser la stabilité thermique des catalyseurs contenant du vanadium. Ce comportement pourrait également être corrélé aux caractéristiques de la liaison Er3+_O_V5+ et à leur capacité à modifier les caractéristiques de la liaison V_O et les propriétés acide/base de surface. Le catalyseur Ce0.5Er0.5V0.95W0.05O4, la formulation optimisée, permet d’obtenir une conversion de NOx supérieure à 80% entre 250 et 400°C en condition Fast-SCR après un vieillissement à 850°C
Diesel engines have been extensively implemented because they emit lesser CO2 than gasoline engine of equivalent power, since they work in lean condition, i.e. in excess of oxygen. Recently, Selective Catalytic Reduction (SCR) catalysts coated on Diesel Particulate Filters (DPF) have been introduced for automotive applications due to capability of reducing NOx and PM simultaneously. However, such implementation requires improved thermal resistance of the SCR catalyst due to the exotherms related to the periodic regeneration of DPF. The point of this manuscript is to propose a catalyst active in NOx reduction by NH3 after aging at high temperature. The first part of this manuscript details the modifications of CeV0.95W0.05O4 catalyst by adding of rare earths elements (Pr3+, Gd3+, Tb3+, and Er3+). The most promising catalyst obtained by the partial substitution of cerium by rare earths was finally Ce0.5Er0.5V0.95W0.05O4 catalyst. A partial substitution of the cerium by the erbium allows obtaining an increase of the activity after an aging at 600°C and 850°C attributed to the ability of erbium to promote thermal stability of the vanadium-containing catalysts. This behaviour might be also correlated with the characteristics of Er3+_O_V5+ bond and to their ability to alter the characteristics of the V_O bond and the acid/base surface properties. Ce0.5Er0.5V0.95W0.05O4 catalyst, an optimized formulation, is able to get a NOx conversion superior to 80% between 250 and 400°C in Fast-SCR condition after an aging at 850°C

Les moteurs Diesels connaissent un intérêt récent tout particulier car ils rejettent moins de CO2 que les moteurs essences à puissance égale, du fait qu’ils travaillent en mélange pauvre (en excès d’oxygène). Récemment, des catalyseurs de réduction catalytique sélective (SCR) déposés sur des filtres à particules diesel (FAP) ont été développés pour les applications automobiles en raison de leur capacité à réduire simultanément les émissions de NOx et de particules. Une telle mise en œuvre nécessite une résistance thermique améliorée du catalyseur SCR du fait des exothermes liés à la régénération périodique du FAP. Le but de ce travail est de proposer un catalyseur pour la réduction des NOx par NH3 actif après vieillissement à haute température. La première partie de ce manuscrit détaille les modifications du catalyseur CeV0.95W0.05O4 en ajoutant des éléments de terres rares (Pr3+, Gd3+, Tb3+, Er3+). Le catalyseur le plus prometteur obtenu par la substitution partielle du cérium par des terres rares était finalement le catalyseur Ce0.5Er0.5V0.95W0.05O4. Une substitution partielle du cérium par de l’erbium permet d’obtenir un gain d’activité après vieillissement à 600 et 850°C attribué à la capacité de l'erbium à favoriser la stabilité thermique des catalyseurs contenant du vanadium. Ce comportement pourrait également être corrélé aux caractéristiques de la liaison Er3+_O_V5+ et à leur capacité à modifier les caractéristiques de la liaison V_O et les propriétés acide/base de surface. Le catalyseur Ce0.5Er0.5V0.95W0.05O4, la formulation optimisée, permet d’obtenir une conversion de NOx supérieure à 80% entre 250 et 400°C en condition Fast-SCR après un vieillissement à 850°C
Diesel engines have been extensively implemented because they emit lesser CO2 than gasoline engine of equivalent power, since they work in lean condition, i.e. in excess of oxygen. Recently, Selective Catalytic Reduction (SCR) catalysts coated on Diesel Particulate Filters (DPF) have been introduced for automotive applications due to capability of reducing NOx and PM simultaneously. However, such implementation requires improved thermal resistance of the SCR catalyst due to the exotherms related to the periodic regeneration of DPF. The point of this manuscript is to propose a catalyst active in NOx reduction by NH3 after aging at high temperature. The first part of this manuscript details the modifications of CeV0.95W0.05O4 catalyst by adding of rare earths elements (Pr3+, Gd3+, Tb3+, and Er3+). The most promising catalyst obtained by the partial substitution of cerium by rare earths was finally Ce0.5Er0.5V0.95W0.05O4 catalyst. A partial substitution of the cerium by the erbium allows obtaining an increase of the activity after an aging at 600°C and 850°C attributed to the ability of erbium to promote thermal stability of the vanadium-containing catalysts. This behaviour might be also correlated with the characteristics of Er3+_O_V5+ bond and to their ability to alter the characteristics of the V_O bond and the acid/base surface properties. Ce0.5Er0.5V0.95W0.05O4 catalyst, an optimized formulation, is able to get a NOx conversion superior to 80% between 250 and 400°C in Fast-SCR condition after an aging at 850°C

Conception d'un dispositif experimental dans le but d'etudier les proprietes physiques et cinetiques des systemes bacl::(2)/nh::(3) et cacl::(2)/nh::(3). Mesures de vitesses de desorption et d'absorption. Modele d'optimisation des processus et experimentation d'un prototype de refrigeration a capteur solaire plan

La Reduction Catalytique Sélective (SCR) par l’ammoniac est un procédé qui est commercialement utilisé pour l’élimination des oxydes d’azote (NOx) issus des moteurs Diesel afin de répondre aux exigences des normes européennes concernant les émissions. Pour pouvoir mieux traiter les NOx, surtout à froid, la combinaison du catalyseur SCR à base de zéolithe échangée au Cu (Cu-Zéolithe) et le filtre à particules (SCRF) représente un avantage à son rapprochement du moteur. Néanmoins, la combinaison peut avoir aussi des inconvénients, lors de la régénération en continue du filtre à particules, le catalyseur SCRF sera soumis à de multiples occurrences thermiques et à de possible empoisonnement par le carburant et l’huile moteur durant toute la vie du système de post-traitement en véhicule. Etant donné que la législation européenne exige que le système de post-traitement soit opérationnel et efficace jusqu’à 160.000km, il est donc important de comprendre les phénomènes engendrés par le vieillissement hydrothermal du SCRF afin de pouvoir l’améliorer. Dans le cadre de ce travail, des simulations du vieillissement hydrothermal dans un four de laboratoire et en parallèle un vieillissement réel d’environ 120.000km d’une ligne de post-traitement comprenant le SCRF ont été réalisés. Les différents résultats ont permis de comprendre le mécanisme de dégradation de la performance du catalyseur à base de Cu-Zéolithe lié au traitement hydrothermal et de pouvoir corréler un vieillissement réel en véhicule à un vieillissement accéléré au four. De plus, des techniques rapides de caractérisation permettant de détecter l’état de vieillissement d’un catalyseur SCRF ont été sélectionnées. Finalement, un modèle mathématique basé sur les résultats expérimentaux a permis de décrire la dégradation de la capacité de stockage de l’ammoniac du catalyseur SCRF avec le traitement hydrothermal
The selective catalytic reduction (SCR) by urea or ammonia is a well-known method to meet the European emission regulation requirements concerning the reduction of nitrogen oxides (NOx) emissions from Diesel engines. In order to optimize the NOx reduction activity at all temperature range, a copper-exchanged zeolite (Cu-Zeolite) SCR catalyst is combined to a Diesel Particulate Filter (SCRF). However, during the continuous regeneration of the particulate filter, the SCRF catalyst will go through numerous constraints such as variable high temperature, poisoning compounds from Diesel fuel and engine oil, during the entire vehicle life of the after-treatment line. Moreover, the European legislation requires a durability of the after-treatment line for about 160,000km. Understanding the degradation of the SCRF catalyst by the hydrothermal ageing is of interest to apprehend the deactivation mechanism in order to develop a stable material. In the present work, accelerated hydrothermal ageing in laboratory oven and also a real driving ageing of an SCRF catalyst, included in an after-treatment line for about 120,000km, were performed. The different results obtained help to apprehend the degradation mechanism of a Cu-Zeolite SCRF catalyst performance and also to find a correlation between a 120,000km real driving ageing and an equivalence oven aged SCRF catalysts. Moreover, rapid characterization methods, to detect the hydrothermal ageing status of an SCRF catalyst, have been selected. Finally, a mathematical model, based on experimental results, has allowed to describe the degradation of the ammonia storage capacity of the SCRF catalyst with the hydrothermal ageing

ENGLISH:

The natural nitrogen cycle has been and is significantly perturbed by anthropogenic emissions of reactive nitrogen (Nr) compounds into the atmosphere, resulting from our production of energy and food. In the last century global ammonia (NH3) emissions have doubled and represent nowadays more than half of total the Nr emissions. NH3 is also the principal atmospheric base in the atmosphere and rapidly forms aerosols by reaction with acids. It is therefore a species of high relevance for the Earth's environment, climate and human health (Chapter 1). As a short-lived species, NH3 is highly variable in time and space, and while ground based measurements are possible, they are sparse and their spatial coverage is largely heterogeneous. Consequently, global spatial and temporal patterns of NH3 emissions are poorly understood and account for the largest uncertainties in the nitrogen cycle. The aim of this work is to assess distributions and saptiotemporal variability of NH3 using satellite measurements to improve our understanding of its contribution to the global nitrogen cycle and its related effects.

Recently, satellite instruments have demonstrated their abilities to measure NH3 and to supplement the sparse surface measuring network by providing global total columns daily. The Infrared Atmospheric Sounding Interferometer (IASI), on board MetOp platforms, is measuring NH3 at a high spatiotemporal resolution. IASI circles the Earth in a polar Sun-synchronous orbit, covering the globe twice a day with a circular pixel size of 12km diameter at nadir and with overpass times at 9:30 and 21:30 (local solar time when crossing the equator). An improved retrieval scheme based on the calculation of Hyperspectral Range Index (HRI) is detailed in Chapter 2 and compared with previous retrieval methods. This approach fully exploits the hyperspectral nature of IASI by using a broader spectral range (800-1200 cm-1) where NH3 is optically active. It allows retrieving total columns from IASI spectra globally and twice a day without large computational resources and with an improved detection limit. More specifically the retrieval procedure involves two steps: the calculation of a dimensionless spectral index (HRI) and the conversion of this index into NH3 total columns using look-up tables (LUTs) built from forward radiative transfer simulations under various atmospheric conditions. The retrieval also includes an error characterization of the retrieved column, which is of utmost importance for further analysis and comparisons. Global distributions using five years of data (1 November 2007 to 31 October 2012) from IASI/MetOp-A are presented and analyzed separately for the morning and evening overpasses. The advantage of the HRI-based retrieval scheme over other methods, in particular to identify smaller emission sources and transport patterns over the oceans is shown. The benefit of the high spatial sampling and resolution of IASI is highlighted with the regional distribution over China and the first four-year time series are briefly discussed.

We evaluate four years (1 January 2008 to 31 December 2011) of IASI-NH3 columns from the morning observations and of LOTOS-EUROS model simulations over Europe and Western Russia. We describe the methodology applied to account for the variable retrieval sensitivity of IASI measurements in Chapter 3. The four year mean distributions highlight three main agricultural hotspots in Europe: The Po Valley, the continental part of Northwestern Europe, and the Ebro Valley. A general good agreement between IASI and LOTOS-EUROS is shown, not only over source regions but also over remote areas and over seas when transport is observed. The yearly analyses reveal that, on average, the measured NH3 columns are higher than the modeled ones. Large discrepancies are observed over industrial areas in Eastern Europe and Russia pointing to underestimated if not missing emissions in the underlying inventories. For the three hotspots areas, we show that the seasonality between IASI and LOTOS-EUROS matches when the sensitivity of the satellite measurements is taken into account. The best agreement is found in the Netherlands, both in magnitude and timing, most likely as the fixed emission timing pattern was determined from experimental data sets from this country. Moreover, comparisons of the daily time series indicate that although the dynamic of the model is in reasonable agreement with the measurements, the model may suffer from a possible misrepresentation of emission timing and magnitude. Overall, the distinct temporal patterns observed for the three sites underline the need for improved timing of emissions. Finally, the study of the Russian fires event of 2010 shows that NH3 modeled plumes are not enough dispersed, which is confirmed with a comparison using in situ measurements.

Chapter 4 describes the comparisons of IASI-NH3 measurements with several independent ground-based and airborne data sets. Even though the in situ data are sparse, we show that the yearly distributions are broadly consistent. For the monthly analyzes we use ground-based measurements in Europe, China and Africa. Overall, IASI-derived concentrations are in fair agreement but are also characterized by less variability. Statistically significant correlations are found for several sites, but low slopes and high intercepts are calculated in all cases. At least three reasons can explain this: (1) the lack of representativity of the point surface measurement for the large IASI pixel, (2) the use of a single profile shape in the retrieval scheme over land, which does therefore not account for a varying boundary layer height, (3) the impact of the averaging procedure applied to satellite measurements to obtain a consistent quantity to compare with the in situ monthly data. The use of hourly surface measurements and of airborne data sets allows assessing IASI individual observations. Much higher correlation coefficients are found in particular when comparing IASI-derived volume mixing ratio with vertically resolved measurements performed from the NOAA WP-3D airplane during CalNex campaign in 2010. The results demonstrate the need, for validation of the satellite columns, of measurements performed at various altitudes and covering a large part of the satellite footprint.

The six-year of IASI observations available at the end of this thesis are used to analyze regional time series for the first time (Chapter 5). More precisely, we use the IASI measurements over that period (1 January 2008 to 31 December 2013) to identify seasonal patterns and inter-annual variability at subcontinental scale. This is achieved by looking at global composite seasonal means and monthly time series over 12 regions around the world (Europe, Eastern Russia and Northern Asia, Australia, Mexico, South America, 2 sub-regions for Northern America and South Asia, 3 sub-regions for Africa), considering separately but simultaneously measurements from IASI morning and evening overpasses. The seasonal cycle is inferred for the majority of these regions. The relations between the NH3 atmospheric abundance and emission processes is emphasized at smaller regional scale by extracting at high spatial resolution the global climatology of the month of maxima columns. In some region, the predominance of a single source appears clearly (e.g. agriculture in Europe and North America, fires in central South Africa and South America), while in others a composite of source processes on small scale is demonstrated (e.g. Northern Central Africa and Southwestern Asia).

Chapter 6 presents the achievements of this thesis, as well as ongoing activities and future perspectives.

FRANCAIS:

Le cycle naturel de l'azote est fortement perturbé suite aux émissions atmosphériques de composés azotés réactifs (Nr) résultant de nos besoins accrus en énergie et en nourriture. Les émissions d'ammoniac (NH3) ont doublé au cours du siècle dernier, représentant aujourd'hui plus de la moitié des émissions totales de Nr. De plus, le NH3 étant le principal composé basique de notre atmosphère, il réagit rapidement avec les composés acides pour former des aérosols. C'est dès lors un constituant prépondérant pour l'environnement, le climat et la santé publique. Les problématiques environnementales y étant liées sont décrites au Chapitre 1. En tant que gaz en trace le NH3 se caractérise par une importante variabilité spatiale et temporelle. Bien que des mesures in situ soient possibles, elles sont souvent rares et couvrent le globe de façon hétérogène. Il en résulte un manque de connaissance sur l'évolution temporelle et la variabilité spatiale des émissions, ainsi que de leurs amplitudes, qui représentent les plus grandes incertitudes pour le cycle de l'azote (également décrites au Chapitre 1).

Récemment, les sondeurs spatiaux opérant dans l'infrarouge ont démontré leurs capacités à mesurer le NH3 et par là à compléter le réseau d'observations de surface. Particulièrement, l'Interféromètre Atmosphérique de Sondage Infrarouge (IASI), à bord de la plateforme MetOp, mesure le NH3 à une relativement haute résolution spatiotemporelle. Il couvre le globe deux fois par jour, grâce à son orbite polaire et son balayage autour du nadir, avec un temps de passage à 9h30 et à 21h30 (temps solaire local quand il croise l'équateur). Une nouvelle méthode de restitution des concentrations basée sur le calcul d'un index hyperspectral sans dimension (HRI) est détaillée et comparée aux méthodes précédentes au Chapitre 2. Cette méthode permet d'exploiter de manière plus approfondie le caractère hyperspectral de IASI en se basant sur une bande spectrale plus étendue (800-1200 cm-1) au sein de laquelle le NH3 est optiquement actif. Nous décrivons comment restituer ces concentrations deux fois par jour sans nécessiter de grandes ressources informatiques et avec un meilleur seuil de détection. Plus spécifiquement, la procédure de restitution des concentrations consiste en deux étapes: le HRI est calculé dans un premier temps pour chaque spectre puis est ensuite converti en une colonne totale de NH3 à l'aide de tables de conversions. Ces tables ont été construites sur base de simulations de transfert radiatif effectuées pour différentes conditions atmosphériques. Le processus de restitution des concentrations comprend également le calcul d'une erreur sur la colonne mesurée. Des distributions globales moyennées sur cinq ans (du 1 novembre 2007 au 31 Octobre 2012) sont présentées et analysées séparément pour le passage diurne et nocturne de IASI. L'avantage de ce nouvel algorithme par rapport aux autres méthodes, permettant l'identification de sources plus faibles de NH3 ainsi que du transport depuis les sources terrestres au-dessus des océans, est démontré. Le bénéfice de la haute couverture spatiale et temporelle de IASI est mis en exergue par une description régionale au-dessus de la Chine ainsi que par l'analyse de premières séries temporelles hémisphériques sur quatre ans.

Au Chapitre 3, nous évaluons quatre ans (du 1 janvier 2008 au 31 décembre 2011) de mesures matinales de IASI ainsi que de simulations du modèle LOTOS-EUROS, effectuées au-dessus de l'Europe et de l'ouest de la Russie. Nous décrivons une méthodologie pour prendre en compte, dans la comparaison avec le modèle, la sensibilité variable de l'instrument IASI pour le NH3. Les comparaisons montrent alors une bonne concordance générale entre les mesures et les simulations. Les distributions pointent trois régions sources: la vallée du Pô, le nord-ouest de l'Europe continentale et la vallée de l'Ebre. L'analyse des distributions annuelles montre qu'en moyenne, les colonnes de NH3 mesurées sont plus élevées que celles simulées, à part pour quelques cas spécifiques. Des différences importantes ont été identifiées au-dessus de zones industrielles en Europe de l'est et en Russie, ce qui tend à incriminer une sub-estimation voire une absence de ces sources dans les inventaires d'émissions utilisés en entrée du modèle. Nous avons également montré que la saisonnalité est bien reproduite une fois la sensibilité des mesures satellites prise en compte. La meilleure concordance entre le modèle et IASI est observée pour les Pays-Bas, ce qui est certainement dû au fait que le profil temporel des émissions utilisé pour les simulations LOTOS-EUROS est basé sur des études expérimentales réalisées dans ce pays. L'étude des séries temporelles journalières indique que la dynamique du modèle est raisonnablement en accord avec les mesures mais pointe néanmoins une possible mauvaise représentation du profil temporel ainsi que de l'ampleur des émissions. Finalement, l'étude des importants feux ayant eu cours en Russie à l'été 2010 a montré que les panaches modélisés sont moins étendus que ceux observés, ce qui a été confirmé grâce à une comparaison avec des mesures sols.

Le chapitre 4 est dédié à la confrontation des mesures IASI avec différents jeux de données indépendants acquis depuis le sol et par avion. Les distributions globales annuelles sont concordantes, bien que la couverture spatiale des mesures sols soit limitée. Des mesures effectuées à la surface en Europe, en Chine et en Afrique sont utilisées pour les comparaisons mensuelles. Ces dernières révèlent une bonne concordance générale, bien que les mesures satellites montrent une plus faible amplitude de variations de concentrations. Des corrélations statistiquement significatives ont été calculées pour de nombreux sites, mais les régressions linéaires sont caractérisées par des pentes faibles et des ordonnées à l'origine élevées dans tous les cas. Au minimum, trois raisons contribuent à expliquer cela: (1) le manque de représentativité des mesures ponctuelles pour l'étendue des pixels IASI, (2) l'utilisation d'une seule forme de profil vertical pour la restitution des concentrations, qui ne prend dès lors pas en compte la hauteur de la couche limite, (3) l'impact de la procédure utilisée pour moyenner les observations satellites afin d'obtenir des quantités comparables aux mesures sols mensuelles. La prise en compte de mesures en surface effectuées à plus haute résolution temporelle ainsi que de mesures faites depuis un avion permet d'évaluer les observations IASI individuelles. Les coefficients de corrélation calculés sont bien plus élevés, en particulier pour la comparaison avec les mesures effectuées depuis l'avion NOAA WP-3D pendant la campagne CalNex en 2010. Ces résultats démontrent la nécessité de ce type d'observations, effectuées à différentes altitudes et couvrant une plus grande surface du pixel, pour valider les colonnes IASI-NH3.

Les six ans de données IASI disponibles à la fin de cette thèse sont utilisées pour tracer les premières séries temporelles sub-continentales (Chapitre 5). Plus spécifiquement, nous explorons les mesures IASI durant cette période (du 1 janvier 2008 jusqu'au 31 décembre 2013) pour identifier des structures saisonnières ainsi que la variabilité inter-annuelle à l'échelle sous-continentale. Pour arriver à cela, des moyennes saisonnières composites ont été produites ainsi que des séries temporelles mensuelles au-dessus de 12 régions du globe (Europe, est de la Russie et nord de l'Asie, Australie, Mexique, Amérique du Sud, 2 sous-régions en Amérique du nord et en Asie du sud et 3 sous-régions en Afrique), considérant séparément mais simultanément les mesures matinales et nocturnes de IASI. Le cycle saisonnier est raisonnablement bien décrit pour la plupart des régions. La relation entre la quantité de NH3 atmosphérique et ses sources d'émission est mise en exergue à l'échelle plus régionale par l'extraction à haute résolution spatiale d'une climatologie des mois de colonnes maximales. Dans certaines régions, la prédominance d'un processus source apparait clairement (par exemple l'agriculture en Europe et en Amérique du nord, les feux en Afrique du Sud et en Amérique du Sud), alors que, pour d'autres, la diversité des sources d'émissions est démontrée (par exemple pour le nord de l'Afrique centrale et l'Asie du sud-ouest).

Le Chapitre 6 reprend brièvement les principaux aboutissements de cette thèse et présente les différentes recherches en cours et les perspectives associées.

Doctorat en Sciences agronomiques et ingénierie biologique
info:eu-repo/semantics/nonPublished

La prise de conscience de l'importance de la gestion des déchets et de la préservation des ressources a conduit de plus en plus d'acteurs du monde agricole à s'intéresser au compostage comme mode de traitement d'effluents d'élevage ou de boues de stations d'épuration. Les filières d'utilisation de ces substrats, épandage, compostage ou autre, doivent donc être comparées. On sait en effet que l'agriculture est responsable d'une part importante des émissions d'ammoniac (NH3) et de protoxyde d'azote (N2O) et ainsi, indirectement ou directement, de l'augmentation de la concentration de N2O dans l'atmosphère. Trois séries d'expérimentations ont été menées respectivement sur des mélanges d'écorces de peuplier et de fientes de poules pondeuses, sur du fumier de poulet sans ou avec additifs et sur un mélange de paille et de boues de station d'épuration rurale, en parallèle avec un nouveau mélange d'écorces et de fientes. La première a permis de mesurer les émissions de gaz azotés d'un andain (25 m3) en cours de compostage. Elles étaient de 50% environ de l'azote initial sous forme N- NH3 et de moins de 1% sous forme N-N2O. La production de N2O était associée à des activités de nitrification/dénitrification et avait principalement lieu en phase de maturation. La seconde a révélé, pour du compostage de courte durée (1,5 mois) et en taille expérimentale (2 m3), les conditions dans lesquelles les émissions de NH3 et de N2O étaient les plus fortes ou les plus faibles et lesquelles favorisaient l'activité de dénitrification des micro-organismes. L'augmentation du rapport carbone/azote et l'addition de composés ou microorganismes adéquats font passer les pertes en NNH3 de 55 à 7% de l'azote initial. Leur effet sur la libération de N2O (0,2-0,9%) dépend de nombreux facteurs. La troisième a montré que les andains de compostage (10 et 25 m3) devaient être considérés comme des écosystèmes à part entière composés de différents compartiments (grossièrement entrée, fond, sortie et croûte) où les populations microbiennes s'organisent différemment, l'entrée étant productrice de N2O, le fond et la sortie, producteurs, en équilibre ou consommateurs suivant les moments. La taille de l'andain en expérimentation est donc une donnée capitale pour considérer les résultats comme représentatifs de la réalité.

Introduction Nitrogen [13N] NH3 is a liquid radioisotope, produced by medical cyclotrons for nuclear medicine application and widely applied for evaluation of myocardial perfusion in clinical assessments [1,2]. Owing to its short half-life (10 minutes), the unloading procedure of the radio-active solution of [13N]NH3 from the target is crucial in saving the activity produced for patient. Therefore, an efficient technique in un-loading the radioactive solution from the target body was developed using COMSOL Multiphysics. The new design of the target with improved unloading technique resulted in 30% increase of the available 13N activity. In our experiments, 13N was produced by the 16O(p,α)13N reaction. The energy of proton beam was 16.5 MeV. Material and Methods A 2D model was developed using COMSOL Multiphysics to simulate the inner geometry of [13N] Ammonia target. In the 2D model, water and aluminum were used as materials for the inner body and outer boundary (walls), respectively. The physical equations used to solve the problem of allocating proper place for the loading/unloading opening is turbulent, k-ε Module being extracted from fluid flow module. FIGURE 1 shows the result of simulating water flow on the target water channels. The entrance of the pushing solution (for unloading) was designed to create a turbulent flow inside the target body and, hence, to collect most of the activity inside the target. FIGURE 2 shows the setup for 13N production. A peristaltic pump is used to push the solution after irradiation to the hotcell at 6 ml/min flowrate. The distance from the target to the hotcell is approximately 30 meters. Results and Conclusion FIGURE 3 presents activity produced in milicurie (mCi) for several patient runs. The activity obtained in some experiments reached up to 330 mCi when we irradiated the target with 25 μA for 15 min. This was satisfactory for delivery to the patient at the nuclear medicine department. Moreover, purity of [13N] purity was above 95 % what meets the standard regulation for administration to a patient.

One of the most crucial issues nowadays is the protection of the environment and the replacement of fossil fuels, which are abundantly used around the world, with more efficient and renewable sources. The highest portion of global energy demands today is used in heating and cooling purposes. One way of alleviating the fossil-based thermal energy uses is to harvest excess thermal energy using thermochemical storage materials (TCMs) for use at heating/cooling demands at different times and locations. Along this, in this master’s thesis, a bench-scale thermochemical heat storage (TCS) system is numerically designed, as a part of a collaborative project: Neutrons for Heat Storage (NHS), funded by Nordforsk. The TCS system that is designed herein employs the reversible chemical reaction of ammonia with a metal halide (MeX) for a heat storage capacity of 0.5 kWh, respectively releasing and storing heat during absorption and desorption of ammonia into and from the MeX. This system is designed for low temperature heat applications, around 40-80 °C. SrCl2 is chosen as the metal halide to be used, based on the research outcomes in determining the most suitable materials conducted by NHS project partners. In the ammonia-SrCl2 system, only the absorption and desorption between SrCl2∙NH3 and SrCl2∙8NH3 are considered. The main reason is because absorption/desorption between the last ammine and SrCl2 undergoes at a significantly higher/lower reaction pressure (for a given temperature), with a significant volume change compared to the rest of the ammines, and therefore is practically less cost effective. This thesis also includes a detailed discussion of four different thermochemical storage designs from literature, found as the most relevant to the present TCS system study, which use the reaction between ammonia and metal halides. The first system that was examined is a TCS system built by the NHS project partners at Technical University of Denmark (DTU), owing to its similarities with the desired project, regarding the design and parameters the system uses. This system works in batch mode, only allowing either absorption (i.e. heat release) or desorption (i.e. heat storage) at a given cycle. Thus, upgrading the design of this TCS system at DTU is considered as a most-likely solution to the research objectives of this current thesis project. Moreover, the TCS system at DTU uses storage conditions and desorption temperature similar to the current project’s desired low temperature range of 40-80 °C. The second system discussed herein from literature uses two reactors for cold and heat generation, which means that both charging and discharging processes occur simultaneously. This simultaneous operability is the main reason that this particular system was examined in this thesis. The next discussed system from literature also uses two reactors, for absorption and desorption processes, which work reversibly when each process is completed, like in the desired concept of this project. These two systems (i.e., the secondly and the thirdly discussed systems) use the reversible solid-gas reaction for absorption and desorption between SrCl2∙NH3 and SrCl2∙8NH3, however, the conditions of pressure and temperature between them differ. The second system from literature operates at desorption and absorption at respective conditions of 96 °C, 15 bar and 87 °C, 11 bar while the third system discussed operates at 103 °C, 16 bar and 59 °C, 3 bar during desorption and absorption respectively. The last system from literature that is discussed herein provides the same desorption temperature of 80 °C. Inaddition this particular study suggests that the reaction of solid with gaseous NH3 is better (than the solid with liquid NH3 reaction) based on results derived from several different low-pressure experiments of the reactions. The main differences between all these discussed systems from literature, as opposed to the desired TCS system design in this thesis project, concern the systems’ operating mode and the pressure and temperature-conditions. The first difference is that only one of the examined systems pumps the solid VIII powder salt around the system in contrast to the others that keep the salt static inside the reactors and pumped only the ammonia around the system, as chosen in the current system. The second difference concerns the operating conditions during absorption and desorption reactions, where these different systems operate at a widely different pressure and temperature conditions as compared to the current system expectations. Thus, there are four main lessons that were learnt via this literature analysis, to improve the TCS system at DTU to the desired new system in this work. The first lesson is related to the reactants’ transportation mechanism that should be used in this system. Regarding this, it was decided to maintain the solid salt (metal halide) stationary inside each reactor (but not pumping it instead of ammonia), similar to the majority of designs discussed from literature. According to the second and third lessons, the solid-gas reaction is the most suitable solution and only the reactions of absorption and desorption between SrCl2∙NH3 and SrCl2∙8NH3 are considered, following the experience from literature (for the reasons explained earlier). The last lesson regards the system’s suitable operating conditions and more specifically the TCS system’s temperatures that should match the district heating temperatures. Thus, the temperature point that was chosen as a priority was 80 °C, from the range 40- 80 °C set in the partner project NHS. To maintain this condition, therefore, the most suitable condition of pressure of both reactions (according to the equilibrium pressure vs temperature curve) was chosen to be at around 8 bar. This same pressure was chosen for both reactions, since the pressure difference between these reactors and the storage of ammonia (i.e. from 8 to 10 bar) should be as small as possible due to the high costs that can arise in the case of a higher pressure difference (i.e. requiring more compressors and heat exchangers). Inspired by these literature cases, firstly a conceptually suitable TCS system was proposed in this project and after that the final desired system was designed and was implemented and evaluated numerically. The numerical design and optimization of the chosen TCS system was performed herein by using the software Aspen Plus (version 9), which contains both fluids and solids in a simulation environment, using consistent physical properties. This TCS system is designed to store and release heat at around 80 °C and 8 bar through absorption and desorption by using two identical reactors respectively. Each reactor includes the amount of around 1 kg (more specifically 0.985 kg) strontium chloride salt reacting with 1.7 kg of ammonia. A verification system is also modelled in Aspen, using available experimental data from literature. Here, the modelled novel system design was adapted to this chosen other system layout from literature which uses the same reaction pair, yet at different operating conditions. This adapted system design in Aspen was then used to verify the chosen configuration and the reliability of the constructed system for the NHS project. Good agreements between the modelled results in Aspen against the available experimental data of this verification model are obtained. A sensitivity analysis is also conducted herein on the proposed novel TCS system to identify the optimum operating conditions and the behaviour of the chosen most important parameters of the system. The designed system provides an energy storage capacity of 0.5 kWh for the specific amounts (in volumetric flow rates) of ammonia and monoammine of strontium chloride, that comes from the analysis, of 1.08696 e-05 kmol/s and 1.5528 e-06 kmol/s respectively. For these specific values of the HTF, the analysis showed that the volumetric flow rates of the heat and cold external sources must be 1.56 l/min (which is decreasing with the increase of the inlet HTF temperature) and 0.42 l/min (which is increasing with the increase of the inlet HTF temperature) respectively. In conclusion, this study presents an ammonia-SrCl2 TCS benchscale system design that allows continuous heat storage and release, in an easy-to-scale up design, also suggesting optimum operating conditions.
En av de mest avgörande frågorna i dag är skyddet av miljön och utfasningen av fossila bränslen som används allmänt över hela världen för mer effektiva och förnybara resurser. Den största delen av den globala energibehovet idag avser uppvärmnings- och kylapplikationer. Ett sätt att minska fossilbaserad termiskenergianvändning är att lagra överskottsvärmeenergi genom termokemiska lagringsmaterial (TCM) och använda den för värme- och kylbehov vid olika tidpunkter och platser. I samband med detta är ett termokemiskt värmelagringssystem numeriskt utformat i detta mastersexamensprojekt, som en del av ett samarbetsprojekt Neutrons for Heat Storage (NHS) finansierat av Nordforsk. Det termokemiska lagringssystemet (TCS) som är konstruerat utnyttjar den reversibla kemiska reaktionen av ammoniak med en metallhalogenid (MeX) för en värmelagringskapacitet på 0.5 kWh, och frigör och lagrar värme respektive under absorption och desorption av ammoniak till och från MeX. Systemet är designat för lågtemperaturuppvärmningstillämpningar runt 40-80 °C. SrCl2 väljs som det mest lämpliga metallhalogeniden för systemet, baserat på studier som utförts av NHS-projektpartnerna. I ammoniak SrCl2-systemet beaktas endast absorption och desorption mellan SrCl2NH3 och SrCl28NH3. De huvudsakliga orsakerna till detta är att absorptionen/desorptionen mellan den sista aminen och SrCl2 kräver ett betydligt högre/lägre reaktionstryck (för en given temperatur), och resulterar i en betydande volymförändring jämfört med resten av aminerna, och är därför praktiskt taget mindre kostnadseffektivt. Detta mastersexamensprojekt inkluderar en detaljerad genomgång av fyra olika TCS-system från litteratur som använder reaktionen mellan ammoniak och metallhalogenider. Dessa väljs här eftersom dessa anses vara de mest relevanta (från litteratur) jämfört med det valda systemet i denna studie. Det första undersökta systemet är ett system byggt av NHS-projektpartnerna vid Danmarks Tekniska Universitet (DTU). Detta har valts på grund av likheterna med det önskade systemet i det aktuella mastersexamensprojektet, vad gäller systemdesign och parametrar. Detta system fungerar i batch-läge, vilket endast tillåter antingen absorption (dvs värmeavgivning) eller desorption (dvs värmelagring) under en specifik cykel. Således kan en uppgraderad design av detta TCS-system vid DTU möjligen vara en lämplig lösning på forskningsmålen för detta mastersexamensprojekt. Dessutom använder detta TCS-system från DTU ganska liknande driftsförhållanden (temperaturer och tryck) i nivå med det aktuella projektets önskade lågtemperaturintervall på 40-80 °C. Det andra systemet från den litteratur som diskuterats använder två reaktorer för kyla och värmeproduktion, vilket innebär att både laddningsoch urladdningsprocesser sker samtidigt. Denna samtidiga operation är främst anledningen till att systemet undersöktes, eftersom detta är en önskad funktion att uppnå i det aktuella projektet. Nästa system från den litteratur som diskuteras häri använder också två reaktorer för absorptions- och desorptionsprocesser, som fungerar reversibelt när varje process är klar, precis som önskat i detta projekt. Dessa två system (dvs det andra och det tredje diskuterade systemen) använder den reversibla fastgasreaktionen för absorption och desorption mellan SrCl2NH3 och SrCl28NH3, dock vid olika tryck- och temperaturförhållanden. Det andra systemet arbetar nämligen under kombinationer av absorption och desorption av 96 °C, 15 bar och 87 °C, 11 bar, medan det tredje systemet arbetar vid 103 °C, 16 bar respektive 59 °C, 3 bar. Det sista systemet som diskuterats från litteraturen arbetar vid samma temperatur som det önskade systemet gör (dvs. 80 ° C) och genom olika lågtrycksexperiment visar att den fasta salt-gasreaktionen är ett bättre val än reaktionen av det fasta saltet med flytande gasreaktion. De viktigaste skillnaderna mellan alla dessa diskuterade system från litteratur i motsats till det önskade TCS-system i detta mastersexamensprojekt, avser systemdriftläge samt deras tryck och X temperaturförhållanden. Den första skillnaden är att endast ett av alla undersökta system pumpar saltet i fast pulverform, till skillnad från de andra som håller saltet stillastående i reaktorerna och endast pumpar ammoniak. Den andra skillnaden gäller driftsförhållandena under absorptions- och desorptionsreaktioner där dessa system arbetar vid mycket olika tryck- och temperaturförhållanden jämfört med det nuvarande systemet. Således, från översynen av alla system, finns det fyra huvudsakliga lärdomar för att förbättra TCS-systemet vid DTU till det önskade nya systemet. Den första är relaterad till reaktanttransportmekanismen som bör användas i detta system. I detta avseende har det beslutats att hålla det fasta saltet (metallhalogenid) stillastående i varje reaktor (men inte pumpa det istället för ammoniak), till skillnad från de flesta system i litteraturen. Enligt dem andra och tredje lektionerna är den fasta gasreaktionen den mest lämpliga lösningen och endast reaktionerna på absorption och desorption mellan SrCl2∙NH3 och SrCl2∙8NH3 bör övervägas enligt erfarenheten från litteraturen (av de skäl som förklarats tidigare). Den sista lärdomen avser systemets lämpliga driftsförhållanden och mer specifikt TCS-systemets temperaturer för att matcha fjärrvärmetemperaturerna. Den temperaturpunkten valts som prioritet, från området 40-80 °C inställt av moderprojektet NHS, sattes till 80 °C. För att bibehålla detta tillstånd var det lämpligaste tryckvillkoret för båda reaktionerna (enligt jämviktstrycket kontra temperaturkurva) valdes att ligga på cirka 8 bar. Samma tryck valdes för båda reaktionerna, eftersom tryckskillnaden mellan dessa reaktorer och lagring av ammoniak (dvs. från 8 till 10 bar) borde vara så liten som möjligt på grund av de höga kostnaderna som kan uppstå vid högre tryckskillnad (dvs. fler kompressorer krävs och värmeväxlare). Inspirerad av denna litteratur föreslogs för det första ett konceptuellt lämpligt TCS-system i detta mastersexamensprojekt, varefter det slutliga systemet implementerades och utvärderades numeriskt för de önskade förhållandena. Den numeriska utformningen och optimeringen av det valda TCS-systemet utfördes här med hjälp av programvaran Aspen Plus (version 9), som innehåller både vätskor och fasta ämnen i en simuleringsmiljö, med konstant fysiska egenskaper. Detta TCS-system är utformat för att lagra och släppa värme vid cirka 80 °C och 8 bar genom absorption och desorption med användning av två identiska reaktorer respektive. Varje reaktor innefattar cirka 1 kg (närmare bestämt 0.985 kg) strontiumkloridsalt reagerande med 1.7 kg ammoniak. Ett verifieringssystem modelleras också i Aspen med hjälp av tillgängliga experimentella data från litteraturen. I detta anpassades den modellerade nya systemdesignen till denna valda andra verifieringssystemlayout från litteratur, som använder samma reaktionspar, men under olika driftsförhållanden. Denna anpassade systemdesign i Aspen användes sedan för att verifiera den valda konfigurationen och tillförlitligheten för det designade systemet för NHS-projektet. Här erhålls ett bra avtal för denna verifieringssystemdesign mellan Aspenmodellresultaten och experimentdata. Här utförs också en känslighetsanalys för det utformade TCSsystemet i det aktuella projektet för att identifiera de optimala driftsförhållandena och beteendet för de valda viktigaste parametrarna i systemet. Det konstruerade systemet ger en energilagringskapacitet på 0.5 kWh för de specifika mängderna (i volymflöde) av ammoniak och monoamin av strontiumklorid, som kommer från analysen, av 1.08696 e-05 kmol/s och 1.5528 e-06 kmol/s respektive. För dessa specifika värden på värmeöverföringsvätskan visade analysen att de volymetriska flödeshastigheterna för värme och kalla yttre källor måste vara 1.56 l/min (vilket minskar när temperaturen på värmeöverföringsvätskan ökar) och 0.42 l/min (som ökar när temperaturen på värmeöverföringsvätskan ökar). Sammanfattningsvis presenterar denna studie ett ammoniak-SrCl2 TCS-bänkskålsystem som möjliggör kontinuerlig värmelagring och frigöring, har en design som är lätt att anpassa och föreslår också optimala driftsförhållanden.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior
A amÃnia à um composto tÃxico para os organismos aquÃticos e em elevadas concentraÃÃes na Ãgua pode causar diversas alteraÃÃes no animal. Dessa forma, torna-se importante determinar o limite de tolerÃncia dos animais aquÃticos cultivados à essa substÃncia. Sendo assim, o objetivo do trabalho foi determinar a concentraÃÃo letal mÃdia (CL50-96h) da amÃnia nÃo ionizada (NH3) em alevinos de tambacu (Colossoma macropomum x Piaractus mesopotamicus), em teste de toxicidade aguda e avaliar os efeitos de concentraÃÃes subletais atravÃs da anÃlise de parÃmetros hematÃlogicos. No teste de toxicidade aguda, os alevinos foram expostos à amÃnia, nas concentraÃÃes de: 0,09 (controle); 0,54; 1,23; 2,52; 3,44 e 3,66 mg L-1 NH3, que foram obtidas a partir da aplicaÃÃo de NH4Cl. O teste teve duraÃÃo de 96h e as mortalidades foram registradas ao longo desse perÃodo. A CL50 foi determinada pelo mÃtodo estatÃstico Trimmed Spearman Karber. No teste de exposiÃÃo subletal à amÃnia, utilizou-se as concentraÃÃes: 0,04 (controle), 0,19 e 0,35 mg L-1 NH3. Para anÃlise dos parÃmetros hematolÃgicos, foram realizadas coletas de sangue antes da adiÃÃo de NH4Cl (tempo zero) e apÃs 96h de exposiÃÃo. Os parÃmetros hematolÃgicos analisados foram: hematÃcrito (Ht), taxa de hemoglobina (Hb), nÃmero de eritrÃcitos (RBC), volume corpuscular mÃdio (VCM), hemoglobina corpuscular mÃdia (HCM) e concentraÃÃo de hemoglobina corpuscular mÃdia (CHCM). Os dados dos parÃmetros hematolÃgicos foram submetidos à anÃlise de variÃncia (ANOVA) e quando houve diferenÃa significativa entre os tratamentos, as mÃdias foram comparadas duas a duas atravÃs do teste de Tukey (α=0,05). A CL50-96h da amÃnia nÃo ionizada (NH3) para alevinos do hÃbrido tambacu foi 1,63 mg L-1. ApÃs exposiÃÃo de 96h a 0,35 mg L-1 NH3, os peixes apresentaram reduÃÃes significativas no Ht e VCM e aumento significativo na CHCM. Jà Hb, RBC e HCM nÃo diferiram significativamente entre os tratamentos e o tempo 0. A exposiÃÃo de alevinos de tambacu por curto perÃodo de tempo a 0,19 mg L-1 de amÃnia nÃo ionizada (NH3) nÃo causa alteraÃÃes significativas nos parÃmetros hematolÃgicos desses peixes.
Ammonia is a toxic compound to aquatic organisms and at high concentrations in the water can cause various changes in the animal. Therefore, it becomes important to determine the tolerance of farmed aquatic animals for that substance. Thus, the aim of this study was to determine the median lethal concentration (LC50-96h) of un-ionized ammonia (NH3) in fingerlings tambacu (Colossoma macropomum x Piaractus mesopotamicus) in acute toxicity test and evaluate the effects of concentrations sublethal through the analysis of hematological parameters. In the acute toxicity test, the fingerl ings were exposed to ammonia at concentrations of: 0,09 (control); 0,54; 1,23; 2,52; 3 ,44 and 3,66 mg L-1NH3, which were obtained from the application of NH4Cl. The test lasted 96 hours and mortalities were recorded over that period. The LC50 was determin ed by statistical method Trimmed Spearman Karber . In sublethal exposure to ammonia test concentrations used were : 0,04 (control), 0,19 and 0,35mg L-1NH3.For analysis of hematological parameters, blood samples were collected before the addition of NH4Cl(timezero) and after 96 hours of exposure.The hematological parameters analyzed were: hematocrit ( Ht), hemoglobin(Hb), red blood cell count(RBC) mean corpuscular volume (MCV), mean corpuscular hemoglobin (MCH) and mean corpuscular hemoglobin concentration(MCHC). Data hematological parameters were subjected to analysis of variance (ANOVA) and when there was a significant difference between treatments , the averages were compared in pairs through the Tukey's HSD test (α=0,05).LC50-96h of theun - ionized ammonia (NH3) to fingerlings the hybrid tambacu was 1,63m g L-1. After 96h exposure to 0,35 mg L-1NH3, fish showed significant reductions in hematocrit and the MCV and significant increase in MCHC. Already Hb,RBC and MCH did not differ significantly between treatments and time 0. The exposure to fingerlins tambacu for short period to 0,19 mg L -1 of un-ionized ammonia (NH3) does not cause significant changes in hematological parameters of these fish.

En la presente tesis doctoral se realiza un estudio experimental de la intensificación del proceso de absorción de amoniaco por parte de la mezcla NH3/LiNO3 en absorbedores de burbuja por medio del uso de superficies avanzadas y nanotubos de carbono. Las condiciones de operación de los ensayos experimentales fueron obtenidas a partir de una simulación termodinámica de un ciclo de absorción de simple efecto con NH3/LiNO3 a las condiciones de operación de interés para una enfriadora por absorción activada por fuentes de energía a baja temperatura y enfriada por aire. Los experimentos se llevaron a cabo en un banco de prueba experimental diseñado para la evaluación del desempeño de absorbedores a las condiciones deseadas. El estudio del proceso de absorción se realizo en dos tipos de intercambiadores de calor trabajando como absorbedores; un intercambiador de calor de placas y un intercambiador de calor tubular. Los resultados experimentos en el absorbedor tubular muestran que las superficies avanzadas y nanotubos de carbono usados mejoran significativamente el proceso de absorción de amoniaco en el absorbedor de burbuja estudiado en comparación con un absorbedor de tubo liso con el fluido base. Las mejoras máximas alcanzadas fueron superiores al 50%.
This thesis deals with an experimental study on intensification of the ammonia absorption process in the NH3/LiNO3 mixture in vertical bubble mode absorbers using advanced surfaces and nanoparticles of carbon nanotubes (CNTs). Operating conditions selected for the absorber test were obtained from a thermodynamic analysis of a single effect absorption cycle with NH3/LiNO3 driven by low temperature heat sources and head released by air. The experiments were conducted in an experimental test facility designed for evaluating the absorber performance at the desired operating conditions. Intensification of the ammonia absorption process was studied using two types of heat exchangers working as bubble absorbers; a plate heat exchanger and a tubular heat exchanger. Experimental results showed that the advanced surfaces and CNTs used significantly improve the ammonia absorption process in the tubular bubble absorber analyzed in comparison with results in the smooth tube absorber with the base fluid. The maximum improvements achieved were higher than 50 %.

Le projet de thèse a eu pour but l’étude de la formation et de l’élimination du N2O par des catalyseurs cuivre-zéolithe ou fer-zéolithe, utilisés pour le procédé de réduction catalytique sélective des NOx par l'ammoniac (NH3-SCR). Dans ce processus de réduction des NOx, les principales voies de formation de N2O sont la décomposition du nitrate d’ammonium (NH4NO3) et l’oxydation de NH3. L’étude bibliographique a montré une contribution plus importante de la décomposition du nitrate d’ammonium. La recherche s’est donc focalisée dans l’étude de la décomposition du nitrate d’ammonium en empruntant deux axes : la décomposition du NH4NO3 commercial et la formation in situ suivi de la décomposition du nitrate d’ammonium.Les catalyseurs, utilisés pour cette étude, ont été, tout d'abord, amplement caractérises par différentes techniques d’analyse physico-chimique afin de connaitre particulièrement la concentration et forme de déposition des métaux, l’acidité et la taille des cristaux.Après avoir abordé la décomposition du NH4NO3 commercial sans catalyseur, l'étude s'est orientée sur l'effet de l'interaction avec un catalyseur. La nature du gaz vecteur, les conditions hydrodynamiques et la quantité de NH4NO3 ont aussi été évaluées.La décomposition sous conditions statiques, i.e. sans entrainement du NH4NO3 liquide, conduit principalement le N2O. En revanche, les chemins réactionnels suivis sous conditions dynamiques dépendent du mode de déposition du nitrate d’ammonium. Les agrégats solides de nitrate d'ammonium en contact avec la surface externe du catalyseur se décomposent directement en N2O, surtout quand le nitrate d’ammonium liquide ne peut pas être entrainé par le gaz vecteur. L’absence de catalyseur favorise la décomposition vers l’azote par l’interaction entre le NH3 et du HNO3 libérés lors de la dissociation du NH4NO3. D’autre part, en présence d’un catalyseur, le NH3 formé tend à s’adsorber et à s’oxyder à plus haute température. La variation du gaz vecteur n'engendre pas d'effet significatif sur la décomposition du NH4NO3.La décomposition du nitrate d’ammonium formé in situ a été réalisée dans le but de se rapprocher des conditions du procédé NH3-SCR, où le nitrate d’ammonium se forme par l’interaction entre le NH3 et le NO2. La méthode expérimentale a été conçue pour maximiser la formation du nitrate d’ammonium selon les deux cas extrêmes pouvant être trouvés dans un système SCR : la saturation préalable du catalyseur en NH3 puis en NO2 (« NH3 experiment ») et l’inverse, saturation en NO2 puis NH3 (« NO2 experiment »). Dans ce cas plusieurs catalyseurs ont été préparés afin d’isoler certaines caractéristiques et évaluer leur impact. Les effets de la teneur en cuivre, du type de métal (Cu ou Fe), de la structure de la zéolite (CHA ou FER), de la méthode de préparation, de l’atmosphère de calcination et du gaz vecteur pendant la décomposition ont été étudiés. Les effets obtenus ont été corrélés avec les résultats de la caractérisation physicochimique des catalyseurs afin de déterminer les paramètres prépondérants des différences observées.La formation du N2O lors du « NH3 experiment » est toujours plus importante que celle obtenue dans le « NO2 experiment » et dépend fortement de la concentration en sites acides de Brönsted quelle que soit la structure de la zéolithe. En revanche, dans le « NO2 experiment », ce sont plutôt les espèces métalliques et sa localisation qui influencent la décomposition du nitrate d’ammonium. La taille des cristaux a aussi une influence. La méthode de préparation et l’atmosphère de calcination n’ont pas un effet très significatif. Le gaz vecteur influence seulement les émissions à haute température : la formation du N2O est plus importante en présence d’oxygène
The thesis project focused on the study of the formation and elimination of N2O by copper-zeolite or iron-zeolite catalysts, used for selective catalytic reduction of NOx with ammonia (NH3-SCR). In the NOx reduction process the main N2O formation routes are the decomposition of the ammonium nitrate (NH4NO3) and the NH3 oxidation. Still, a literature review showed a more important contribution from the decomposition of ammonium nitrate. Therefore, the study was then concentrated on the decomposition of the ammonium nitrate in two axes: the decomposition of commercial NH4NO3 and the in situ formation followed by decomposition of ammonium nitrate.Besides, the catalysts used for this study, have been thoroughly characterized by different physicochemical techniques in order to, particularly, assess the concentration and deposition form of metals, the acidity and the size of the crystals.After performing the decomposition of commercial NH4NO3 without catalyst, the study has focused on the effect of interaction with a catalyst. The effect of the carrier gas, the hydrodynamic conditions and concentration of NH4NO3 were also studied.Under static conditions, i.e. without liquid NH4NO3 entrainment, the decomposition of the commercial ammonium nitrate mostly leads to N2O. In contrast, the reaction pathway under dynamic conditions depends on the deposition method of ammonium nitrate onto the catalyst. The solid aggregates in the outer surface of the catalyst decompose directly to N2O, especially when the liquid ammonium nitrate cannot be entrained by the carrier gas. The absence of a catalyst promotes the decomposition into nitrogen, formed by the interaction between the NH3 and HNO3 released upon the dissociation of NH4NO3. On the other hand, in the presence of a catalyst NH3 tends to adsorb and to be oxidized at higher temperatures. The carrier gas composition did not have a significant effect in the decomposition of NH4NO3.The decomposition of ammonium nitrate formed in situ was performed in order to get closer from what happens under SCR conditions, where the ammonium nitrate is formed by the interaction between NH3 and NO2. The experimental method was designed to maximize the formation of ammonium nitrate according to the two extreme conditions that may be found in a SCR system: firstly catalyst saturation by NH3 and then by NO2 (“NH3 experiment”) and then the reverse, saturation by NO2 and then by NH3 (“NO2 experiment”). In this study several catalysts were prepared in order to isolate certain characteristics and assess their impact. The effects of the copper loading, the type of metal (Cu and Fe), the structure of the zeolite (CHA or FER), the method of preparation, the calcination atmosphere and the carrier gas during decomposition were studied. These effects were correlated to the results of the physico-chemical characterization of the catalysts with the purpose of find the cause of the faced differences.The formation of N2O during the “NH3 experiment” is always greater than that obtained on the “NO2 experiment”, and strongly depends on the concentration of the Brönsted acid sites, regardless the zeolite structure. However, on the “NO2 experiment”, it is rather the metal species and its location that influence the decomposition of ammonium nitrate. The size of the crystals also has an influence. The preparation method and the calcination atmosphere do not have a significant effect. The carrier gas impacts on the high temperature emission: the formation of N2O is greater in the presence of oxygen

The road transportation is a big source for the release of NOx emissions. NOx has been confirmed to cause negative affect on the air-quality especially in the urban areas, there are therefore regulations for allowed released amount from vehicles. The most adopted technology used for the reduction of these NOx emissions from the diesel exhaust gas is the ammonium selective catalytic reduction (NH3-SCR) using a Cu-zeolite as the catalyst in the system. The SCR catalyst can be deactivated through different mechanism, whereas poisoning by sulfur has been documented to be an important factor for the deactivation. The degree of deactivation of the catalyst has been suggested to vary depending on the catalytic material and which sulfur conditions the catalyst is exposed to, where SO3 has been indicated to cause more sever deactivation compared to SO2.  The aim of this project has been to investigate the deactivation mechanism of Cu-zeolites at different SOx conditions and evaluate potential regeneration mechanism. The project was carried out by evaluating the catalysts, Cu-BEA and Cu-SSZ-13, over different reactions that occurs in the SCR system, investigating the deactivation effect caused by SO2 poisoning and the regeneration potential. The project was then continued with the focus on the Cu-SSZ-13 catalyst investigating different SOx poisoning and regeneration conditions were investigated. In order to investigate the SO3 poisoning a generator using oxidation of SO2 to SO3 was successfully build during this project.  A kinetic model over the Cu-SSZ-13 NH3-SCR reactions was also built based on literature studies and the experimental data obtained. The results from the sulfur poisoning of Cu-BEA are based on the master thesis by Maria Arvanitidou. The fresh samples Cu-Beta and Cu-SSZ-13 exhibited similar activity, with the exception of the high formation of N2O observed over Cu-Beta under SCR conditions. The SO2 causes deactivation, especially at low temperatures. Cu-SSZ-13 exhibited more loss in activity but was able to recover more through the elevated SCR regeneration steps than the Cu-Beta. When SO2 exposure was performed together with NH3, larger deactivation was observed, likely due to ammonium sulfate species formed on the surface. The ammonium sulfate species were less thermally stable than copper sulfates, making it easier to recover the loss of activity in the Cu-SSZ-13. SO3 caused a much more sever deactivation of the SCR reactions than that of the SO2 poisoning and continued to show the lowest NOx removal activity after the regeneration process.  A difference in initial deactivation and recovery of activity between standard and fast SCR reactions was observed, indicating that the different mechanisms used are affected differently by the poisoning. The kinetic model for NH3-SCR over the Cu-SSZ-13 was successfully created when compared to the experimentally obtained data.

Nitrogen is an essential plant nutrient in the biosphere. Although N is necessary and beneficial for life, it is also a common pollutant in the atmosphere and hydrosphere as it may be lost to the atmosphere as ammonia (NH3) or nitrous oxide (N2O) gases or to groundwater as nitrate (NO3-) following fertilization. Polymer coated urea (PCU) is one type of N fertilizer which uses temperature-controlled diffusion to control N release to better match plant demand and mitigate environmental losses of N. The objectives of this project were to simultaneously compare the effects of PCU on gaseous (as N2O and NH3) and aqueous (as NO3-) N losses to the environment as compared to uncoated urea in grass systems over the entire PCU N-release period and to investigate the viability of photoacoustic infrared spectroscopy as a method to ascertain N2O and NH3 losses following fertilization. Two field studies were conducted on established turfgrass sites with a mixture of Kentucky bluegrass (KBG; Poa pratensis L.) and perennial ryegrass (PRG; Lolium perenne L.) in sand (Site 1) and loam (Site 2) soils. Each study compared an untreated control to 200 kg N ha-1 applied as either uncoated urea or PCU (Duration 45 CR®). In these studies PCU reduced NH3 emissions by 41-49% and N2O emissions by 16-54%, while improving growth and verdure. Leachate NO3- observations were inconclusive at each site. Glasshouse studies were conducted to compare N2O and NH3 emissions from PCU and uncoated urea to an untreated control utilizing a non-static, non-flow-through chamber in conjunction with photoacoustic infrared spectroscopy (PAIRS) for gas collection and analysis. Three short-term studies (17-21 d) were done with sand, sandy loam, and loam soils and a full-term (45 d) study with the loam soil. Each study was done in maize (Zea mays L.). Volatilization of ammonia was reduced by 72% and 22% in the sandy loam and loam soils, respectively, in 2008-2009 and by 14% in the loam in 2010. Evolution of N2O was reduced by 42% and 63% in the sandy loam and loam soils in 2008-2009 and by 99% in the loam in 2010. Overall, PCU decreased gaseous losses of N following fertilization while providing a steady supply of N to the plant. The utilization of PAIRS is a viable analysis method which gives higher temporal resolution analysis than is typically reported. These considerable decreases in environmental losses of N are major steps toward conserving natural resources and mitigating the negative environmental impacts associated with N fertilization in grass systems.

The reaction mechanism for the Selective Catalytic Reduction (SCR) of NO by NH3 on V2O5 surface was simulated by means of density functional theory (DFT) calculations performed at B3LYP/6-31G** level. As the initiation reaction, ammonia activation on V2O5 was investigated. Coordinate driving calculations showed that ammonia is adsorbed on Brø
nsted acidic V-OH site as NH4 + species by a nonactivated process with a relative energy of -23.6kcal/mol. Vibration frequencies were calculated as 1421, 1650, 2857 and 2900cm-1 for the optimized geometry, in agreement with the experimental literature. Transition state with a relative energy of -17.1kcal/mol was also obtained. At the end of the Lewis acidic ammonia interaction calculations, it was observed that ammonia is hardly adsorbed on the surface. Therefore, it is concluded that the SCR reaction is initiated more favorably by the Brø
nsted acidic ammonia adsorption. As the second step of the SCR reaction, NO interaction with the preadsorbed NH4 + species was investigated. Accordingly, NO interaction results in the formation of gas phase NH2NO molecule with a relative energy difference of 6.4kcal/mol. For the rest of the reaction sequence, gas phase decomposition of NH2NO was considered. Firstly, one of the hydrogen atoms of NH2NO migrates to oxygen. It then isomerizes in the second step. After that, the reaction proceeds with the isomerization of the other hydrogen. Finally, a second hydrogen atom migration to the oxygen leads to the formation of N2 and H2O. Total relative energy for this reaction series was obtained as -60.12kcal/mol, in agreement with the literature.

CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
Um espectrômetro de massa tipo tempo-de-vôo, montado no Laboratório Nacional de Luz Síncrotron (Campinas - SP), foi utilizado para analisar os íons dessorvidos de uma amostra de amônia condensada (temperaturas de análise: 25 a 150 K) ao ser impactada por fragmentos de fissão do 252Cf. O espectrômetro permite identificar e determinar as abundâncias das espécies iônicas dessorvidas. Quanto à parte teórica, foram feitos cálculos para determinar as estruturas mais estáveis dos agregados de NH3 e para determinar suas dinâmicas de emissão de íons secundários observados na parte experimental. A amônia foi escolhida por sua semelhança com a água, uma molécula muito bem estudada. Outra razão é o atual interesse em determinar a formação de compostos orgânicos nas superfícies de corpos interestelares, uma vez que está comprovada a presença da amônia naquelas superfícies. Nos espectros obtidos observa-se a formação de agregados de amônia que podem ser representados por (NH3)nNHm ± com n = 0-30 e m = 0-5, para íons positivos, e com n = 0- 3 para íons negativos. Uma forma de evidenciar a possibilidade de formação de novos compostos foi realizar experiências com a mistura NH3-CO, com a mesma montagem experimental utilizada para a amônia. Observa-se no espectro obtido (antes da sublimação do CO a 30 K) linhas de massa resultantes de reações primárias que correspondem a íons moleculares híbridos com estrutura CnOmHl+.Os cálculos teóricos referentes às estruturas dos agregados foram realizados través do programa Jaguar 5.5 e Jaguar 6.0. O objetivo é determinar as estruturas mais estáveis dos agregados iônicos da amônia através da teoria DFT (Teoria do Funcional de Densidade) por meio da minimização da energia. Encontrou-se uma relação direta entre as estabilidades determinadas e as abundâncias relativas no espectro de massa. Finalmente foram realizados cálculos com o modelo teórico de dessorção iônica induzida por elétrons. Os resultados de distribuição de velocidades e energias foram comparados com os dados experimentais dos agregados da amônia (n = 0, 4), apresentando uma concordância razoável em valor absoluto, mas moderada em forma.
A time-of-flight mass spectrometer, mounted at the Laboratório National de Luz Síncrotron (Campinas - SP), was used to analyze desorbed ions of a condensed ammonia sample (analyzing temperatures: 25 - 150 K) being impacted by 252Cf fission fragments . The spectrometer allows identifying and determining the relative yields of ionic desorbed species. Besides, it had been made theoretical calculations to determine the most stable cluster structures as well as to determine the emission dynamics of NH3 clusters observed in the experimental part. The ammonia was chosen because of its similarity with the water molecule (very well studied). Another reason is the current interest in determining the organic compounds formation in the interstellar surfaces, now that it is proven the presence of ammonia in those surfaces. The measured spectra show the formation of ammonia clusters that can be represented by (NH3)nNHm ± with n = 0 - 30 and m = 0 - 5 for positive ions, and n = 0 - 3 for negative ones. One way to evidence the formation possibility of new compound is to perform experiments with CO-NH3 mixture samples, using the same experimental set up used for the ammonia. In the spectrum measured before CO sublimation (30 K), mass lines, product of primary reactions, corresponding to hybrid molecular ions having the CnOmHl + structure were observed. Theoretical calculations referring to cluster structures had been carried out using the programs Jaguar 5,5 and Jaguar 6.0. The objective is to determine the most stable structures of the ammonia clusters through the Density Functional Theory (DFT) by means of energy minimizations. A direct relation between the computed stabilities and the relative abundances in the mass spectra was found. Finally calculations with the Secondary Electron Induced Desorption (SEID) model had been carried out. Results of velocity and energy distributions had been compared with the experimental data of ammonia clusters (n = 0, 4), presenting a good agreement in absolute values but moderate agreement in shape.

Na busca de alternativas para mensurar a emissão foliar de amônia (NH3) e minimizar as perdas de N-NH3 em pastagens, foram realizados três trabalhos. Os dois primeiros com objetivo de verificar se o absorvedor com espuma, já utilizado na quantificação da volatilização de N-NH3, também é eficiente para mensurar a emissão foliar, sem causar alterações no processo de perda de nitrogênio. O terceiro trabalho, realizado em pastagem de capim Colonião (Panicum maximum Jacq. cv. Colonião) no verão, inverno e primavera, avaliou o efeito da aplicação de lâminas de água, após a adubação com uréia, sobre as perdas de N-NH3 do solo por volatilização e emissão foliar. O absorvedor de amônia com espuma não causa alteração no processo de perda de N-NH3 e colocado 1 cm acima das folhas superiores, é efetivo em capturar o N-NH3 perdido por emissão foliar da pastagem, quando se fertiliza em superfície com nitrato de amônio e uréia. A aplicação de água imediatamente após a adubação com uréia é eficiente para reduzir as perdas de NNH3 por volatilização. No verão, a aplicação de 3,2 mm de água foi suficiente para reduzir as perdas de N-NH3 para menos de 3,1 % do N aplicado, enquanto na ausência de irrigação ocorreram perdas de 30,5%. A taxa de volatilização é influenciada pela quantidade de água disponível no solo, sendo baixa quando a uréia é aplicada em solo seco ou quando o solo seca rapidamente, mesmo que a temperatura ambiente seja elevada. A emissão foliar de N-NH3 não foi influenciada pela aplicação ou não de água, após a adubação com uréia.
In search of alternatives to measure ammonia (NH3) foliar emission and minimize N-NH3 losses in pasture three research works were accomplished. The two first works aimed at checking whether or not the foam absorber, which was already used to quantify N-NH3 volatilization, is also efficient to measure foliar emission without interfering in nitrogen loss process. The third one was performed in Panicum maximum Jacq. cv. Colonião pasture during three different seasons and evaluated the use of irrigation levels after urea fertilization on N-NH3 losses through volatilization and foliar emission. The ammonia foam absorber does not alter N-NH3 loss process and when place at height of 1 cm from the upper leaves it is effective in capturing N-NH3 lost through foliar emission when fertilization is done superficially with ammonium nitrate and urea. Water application immediately after fertilization is efficient to reduce N-NH3 losses through volatilization. During summer the use of 3.2 mm water was enough to decrease N-NH3 loss to less than 3.1% of applied N, while the lack of irrigation caused 30.5% losses. Volatilization rate is influenced by the quantity of water available in the soil, being low when urea is applied to dry soil or when the soil dries fast even if the environment temperature is high. N-NH3 foliar emission was not influenced by water application after urea fertilization.

The molecular compositions of the atmospheres of the giant planets (Jupiter, Saturn, Uranus and Neptune) are fundamental to understanding the processes which formed these planets and the solar system as a whole. Microwave observations of these planets probe regions in their atmospheres from approximately 0.1 to several bars, a process otherwise unachievable by visible and infrared means. Many gases and various cloud layers influence the millimeter wave spectra of the outer planets; however phosphine and ammonia are the main microwave absorbers at Saturn at pressures less than two bars. Understanding the pressure induced absorption of both constituents at observational frequencies is therefore vital to the analysis of any observational data. Laboratory measurements have been conducted to measure the microwave absorptivity and refractivity of phosphine and ammonia at Ka-band (32-40 GHz) and W-band (94 GHz), under conditions characteristic of the atmosphere of Saturn. The results were used to verify the accuracy of the phosphine formalism created by Hoffman et. al (2001) for use at millimeter wavelengths. Based on the laboratory measurements conducted, new formalisms were also created to express the opacity of ammonia at the measured frequencies. An important method for the study of planetary atmospheres is the radio occultation experiment ??method that uses radio links between Earth, and the spacecraft which passes behind the planet. The Cassini mission to Saturn, which will be conducting such experiments at Ka-band as well as S (2.3 GHz) and X (8.4 GHz) bands, has prompted the development of a radio occultation simulator used to calculate excess Doppler shifts and attenuation profiles for Saturn, utilizing the newest formalisms for phosphine and ammonia. The results indicate that there will be unambiguous detection and profiling of phosphine and ammonia, and predictions are made for the pressures at which loss of signal is anticipated.

Past nuclear weapon production activities have left a significant legacy of uranium (U) contamination in the vadose zone (VZ) of the Department of Energy (DOE) Hanford Site. This U is a source of groundwater (GW) contamination. There is a concern that elevated U concentration would slowly infiltrate through the VZ, reach the GW water table, and then end up in nearby rivers and lakes. Remediation of U-contaminated low moisture content soil is a challenging task considering the VZ depth, where contamination is found between 70 and 100 m below the ground surface, and the formation of highly soluble and stable CaUO2CO3 complexes is influenced by Hanford’s soil rich in carbonate. Injection of reactive gasses (e.g., NH3) is a promising technology to decrease U migration in through the VZ. The NH3 injection creates alkaline conditions that would alter the pore water chemistry (e.g., dissolving some aluminosilicates). Over time as the pH neutralizes, U(VI) could precipitate as uranyl mineral (e.g., Na-boltwoodite). Also, the dissolved U(VI) could be incorporated into the structure of some mineral phases or be coated by non-U minerals. These chemical reactions could control the U(VI) mobility to the GW. However, there is a lack of knowledge on how the VZ pore water constituents (e.g., Si, Al3+, HCO3-, and Ca2+) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of the major pore water constituents on the U(VI) removal and evaluated the uranyl minerals that could precipitate from a variety of SPW solutions. Results showed that the percentage of U(VI) removal was controlled by Si/Al ratios and Ca2+ concentration regardless of HCO3- concentration tested. XRD revealed the presence of uranyl minerals by analyzing precipitates formed from SPW solutions, but none of them were identified as uranyl silicates as expected from speciation modeling. The SEM images displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentage in some samples. U(VI) silicate and carbonate minerals were predicted by the speciation modeling.

The reaction mechanism for the selective catalytic reduction (SCR) of nitric oxide by ammonia on (010) V2O5 surface represented by a V2O9H8 cluster was simulated by density functional theory (DFT) calculations. The computations indicated that SCR reaction consisted of three main parts. In the first part ammonia activation on Brø
nsted acidic V-OH site as NH4+ species by a nonactivated process takes place. The second part includes the interaction of NO with pre-adsorbed NH4 + species to eventually form nitrosamide (NH2NO). The rate limiting step for this part as well as for the total SCR reaction is identified as NH3NHO formation reaction. The last part consists of the decomposition of NH2NO on the cluster which takes advantage of a hydrogen transfer mechanism between the active V=O and V-OH groups. Water and ammonia adsorption and dissociation are investigated on (101) and (001) anatase surfaces both represented by totally fixed and partially relaxed Ti2O9H10 clusters. Adsorption of H2O and NH3 by H-bonding on previously H2O and NH3 dissociated systems are also considered. By use of a (001) relaxed Ti2O9H10 cluster, the role of anatase support on SCR reaction is investigated. Since NH2NO formation on Ti2O9H10 cluster requires lower activation barriers than on V2O5 surface, it is proposed that the role of titanium dioxide on SCR reaction could be forming NH2NO. The role of vanadium oxide is crucial in terms of dissociating this product into H2O and N2. Finally, NH3 adsorption is studied on a V2TiO14H14 cluster which represents a model for vanadia/titania surface.

This thesis studies the interaction between the bare Cu{311} surface with NO and NH3,individually and co-adsorbed using reflection-absorption infrared spectroscopy (RAIRS). In addition to the bare Cu{311} surface, the interaction of NO and NH3 with the various oxygen phases of the Cu{311} surface phases was also studied. Several other techniques were used in tandem to support the study, such as low energy electron diffraction (LEED) and temperature programmed desorption (TPD) experiments using mass spectrometry. The study was carried out in pursuit an understanding of the underlying mechanism of the selective catalytic reduction (SCR) of NO using NH3 in current diesel engines. The dosing of NO onto the Cu{311} surface at 100 K leads to the initial adsorption of intact NO. After an exposure threshold is reached, individual NO molecules react with another NO molecule to form (NO)2 dimers. These dimer species subsequently form N2O, leaving O(a) on the surface. Oxygen was found to be an inhibitor for the reaction, either due to the reaction in a self-poisoning process or from oxygen pre-dosing onto the Cu{311} surface. Temperature plays a minor role with regards to NO/Cu{311}, as it only affects the amount of NO on the surface along with adsorbate surface mobility. Similarly, NH3 was found to adsorb intact onto the Cu{311} surface and not to react or dissociate at 100 K. Oxygen acts as a site blocker for the adsorption, but can also stabilise NH3 to remain on the surface at higher temperatures due to electronic effects. At 300 K, it was found that both the bare and oxygen pre-covered Cu{311} surface was able to dissociate NH3 into NH2. The co-adsorption of NO and that of NH3 onto the Cu{311} surface were found to be largely independent of each other and the interaction is dominated by the displacement of NO by NH3. However, as NO adsorption on the Cu{311} surface forms O(a), it indirectly affects the adsorption of NH3 by creating an oxygen covered Cu{311} surface, which changes how NH3 adsorbs onto the surface.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
Nitrogen is the most required mineral nutrient for almost all agricultural crops and the one that promotes maize yields mostly. Pastillation is a technology that allows blending urea with other mineral elements like sulfur and zinc homogeneously, aims at subsiding N losses, therefore enhancing the agronomic efficiency of the fertilizers. The aim of the first paper was to establish the recommendation of N rates and to evaluate the agronomic performance of pastille urea and its blend with sulfur and zinc, as well as commercial N sources sidedress applied to maize under the conditions of the Médio Sertão and Southern Sergipe. The experiments were carried out during the 2014 and 2015 seasons in both sites. The experimental design was Complete Blocks with 3 replications in split-plot arrangement with an additional Control treatment (TEST). In the plot 3 rates of N applications were tested: 75, 150 and 300 kg ha-1, while in the subplots the following products were evaluated: Pastille urea (UP), Pastille urea with elemental S (UP+S), Pastille urea with ammonium sulfate (UP+SA), Pastille urea with ammonium sulfate and elemental S (UP+SA+S), Pastille urea with ammonium sulfate and zinc sulfate (UP+SA+Zn), Prilled urea (UR) and Ammonium sulfate (SA). Leaf N and S contents as well as maize yield were evaluated to assess the agronomic performance of the products and to calculate the appropriate N recommendation. Economic assessments of the price for the commercial products and the corn grains allowed estimating the rate of maximum economic efficiency (DMEE). The greater the rate of N applied the higher leaf N content and grain yields of maize. Leaf S contents increased with increasing doses of S applied with the tested fertilizers. Yields with Ammonium sulfate were higher than UR, UP and UP+S in both seasons in Umbaúba (Acrisol) (Southern Sergipe). The DMEE for UR was 128 and 119 kg N ha-1 for Nossa Senhora das Dores (Acrisol) and Umbaúba, respectively. The recommended dose of SA was 119 kg ha-1, since it provided the greater incomes for both sites. In the second paper, the aim was to evaluate the agronomic performance and the losses of N through ammonia volatilization of N fertilizers sidedress applied to maize. Ammonia volatilization, leaf N content and maize yield were evaluated in all products tested in the first paper when applied at a rate of 150 kg ha-1 of N and in the TEST treatment. Three replications were used. All fertilized treatments showed higher leaf N contents and grain yields than TEST. The treatment SA showed yields higher than UP+SA+S. Of all N-NH3 lost by volatilization, 92.5% took place in the first 5 days after application. The UP+SA treatment reduced ammonia volatilization and did not differ statistically from SA and TEST. Leaf N content correlates positively and N volatilization negatively with grain yield.
O nitrogênio é o elemento mais requerido pela maioria das culturas e o que proporciona os maiores incrementos no rendimento do milho. O pastilhamento da ureia é uma tecnologia que permite a adição de outros elementos, como enxofre e zinco, e visa diminuir as perdas de N, e consequentemente melhorar a eficiência agronômica dos fertilizantes. No primeiro artigo, o objetivo foi a recomendação de doses de N e avaliação da eficiência agronômica da ureia pastilhada, e de suas complexações com enxofre e zinco, e fontes convencionais de N aplicados em cobertura na cultura do milho nas condições do Médio Sertão e Sul sergipanos. O delineamento experimental foi em blocos ao acaso, com 3 repetições, em esquema de parcelas subdivididas com tratamento adicional. As parcelas foram compostas pelas doses: 75, 150 e 300 kg ha-1 de N, e as subparcelas pelos fertilizantes: ureia pastilhada pura (UP), ureia pastilhada com S elementar (UP+S), ureia pastilhada com sulfato de amônio (UP+SA), ureia pastilhada com sulfato de amônio e S elementar (UP+SA+S), ureia pastilhada com sulfato de amônio e sulfato de zinco (UP+SA+Zn), ureia perolada (UR), sulfato de amônio cristal (SA), e o tratamento adicional testemunha (TEST). Foram avaliados o teor de N e S foliar, produtividade de grãos, e recomendadas doses de máxima eficiência econômica (DMEE). A adubação nitrogenada proporcionou maiores teores de N foliares, e produtividade de grãos, e estas variáveis aumentaram com o acréscimo das doses de N. Os teores de S foliares aumentaram com o incremento das doses de S. O SA proporcionou maior produtividade que a UR, UP e UP+S na média das safras no Argissolo Acinzentado. As DMEE para a UR foram de 128 kg ha-1 de N no Argissolo Vermelho-Amarelo, e 190 kg ha-1 de N no Argissolo Acinzentado. A dose indicada de SA foi de 119 kg ha-1 de N para ambos os solos, e este tratamento proporcionou as maiores rendas. No segundo artigo, o objetivo foi a avaliação da eficiência agronômica e as perdas por volatilização da amônia pela aplicação em cobertura no milho de fertilizantes nitrogenados convencionais e pastilhados, e em suas complexações com enxofre e zinco. Foram avaliados a volatilização da amônia, o teor de N foliar, a produtividade de grãos, e a relação entre estas variáveis. Os tratamentos avaliados foram UP; UP+S; UP+SA; UP+SA+S; UP+SA+Zn; UR e SA, todos na dose de 150 kg ha-1 de N, além da testemunha não adubada (TEST), com 3 repetições. Os tratamentos fertilizados apresentaram os maiores teores de N foliares e produtividade de grãos. O SA apresentou produtividade superior ao tratamento UP+SA+S. Do total de N-NH3 perdido por volatilização, 92,5% ocorreram até o quinto dia após a fertilização. A UP+SA reduziu a volatilização da amônia, não diferindo estatisticamente do SA e TEST. O teor foliar de N correlacionou-se positivamente, enquanto a taxa de volatilização, negativamente, com a produtividade de grãos.
São Cristóvão, SE

The possibility of using methylamines instead of ammonia as a nitrogen precursor for the CVD of nitrides is studied using quantum chemical computations of reaction energies: reaction electronic energy (Δ𝑟𝐸𝑒𝑙𝑒𝑐) reaction enthalpy (Δ𝑟𝐻) and reaction free energy (Δ𝑟𝐺). The reaction energies were calculated for three types of reactions: Uni- and bimolecular decomposition to more reactive nitrogen species, adduct forming with trimethylgallium (TMG) and trimethylaluminum (TMA) followed by a release of methane or ethane and surface adsorption to gallium nitride for both the unreacted ammonia or methylamines or the decomposition products. The calculations for the reaction entropy and free energy were made at both STP and CVD conditions (300°C-1300°C and 50 mbar). The ab inito Gaussian 4 (G4) theory were used for the calculations of the decomposition and adduct reactions while the surface adsorptions were calculated using the Density Functional Theory method B3LYP. From the reactions energies it can be concluded that the decomposition was facilitated by the increasing number of methyl groups on the nitrogen. The adducts with mono- and dimethylamine were more favorable than ammonia and trimethylamine. 𝑁𝐻2 was found to be most readily to adsorb to 𝐺𝑎𝑁 while the undecomposed ammonia and methylamines was not willingly to adsorb.

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In this work were synthesized the materials called vanadyl phosphate, hydrogen vanadyl phosphate and vanadyl phosphate doped by transition metals with the aim in adsorption the following compounds: ammonia, hydrogen sulfide and nitrogen oxide. To characterize the starting compounds was used DRX, FTIR, FRX and TG analysis. After the characterization of substrates, proceeded de adsorption of NH3 and H2S gases in reactor, passing the gases with continuous flow for 30 min and room temperature. Gravimetric data indicate that the matrices of higher performance in adsorption of ammonia was those doped by aluminum and manganese, obtaining results of 216,77 mgNH3/g and 200,40 mgNH3/g of matrix, respectively. The matrice of higher performance in adsorption of hydrogen sulfide was that doped by manganese, obtaining results of 86,94 mgH2S/g of matrix. The synthesis of substrates VOPO4.2H2O and MnVOPO4.2H2O with nitrogen oxide was made in solution, aiming the final products VOPO4.G.nH2O and MnVOPO4.G.nH2O (G = NO and n = number of water molecules). The thermo analytical behavior and the infrared spectroscopy are indicative of formation of VOPO4.2,5NO.3H2O compound. Results of scanning electron microscopy (SEM) and Energy dispersive spectroscopy (EDS) of materials vanadyl phosphate and vanadyl phosphate modified after reaction in solid state or in solution with the gases show morphology changes in substrates, beyond the formation of orthorhombic sulfur crystals over their respective hosts when these adsorb hydrogen sulfide
Neste trabalho foram sintetizados os materiais denominados fosfato de vanadila, hidrogeno fosfato de vanadila e fosfatos de vanadila dopados por metais de transi??o com fins na adsor??o de am?nia, sulfeto de hidrog?nio e ?xido de nitrog?nio. Para a caracteriza??o dos compostos de partida, recorre-se ?s t?cnicas de DRX, FTIR, FRX e TG. Ap?s a caracteriza??o dos substratos, procedeu-se a adsor??o dos gases NH3 e H2S em reator, passando os gases a vaz?o cont?nua durante 30 min e temperatura ambiente. Dados gravim?tricos indicam que as matrizes de maior desempenho na adsor??o de am?nia foram ?quelas dopadas por alum?nio e mangan?s, obtendo resultado de 216,77 mgNH3/g e 200,40 mgNH3/g de matriz, respectivamente. A matriz de maior desempenho para a adsor??o de sulfeto de hidrog?nio foi ?quela dopada por mangan?s, obtendo resultado de 86,94 mgH2S/g de matriz. As s?nteses dos substratos VOPO4.2H2O e MnVOPO4.2H2O com o g?s ?xido de nitrog?nio foram realizadas em solu??o, objetivando-se os produtos finais VOPO4.G.nH2O e MnVOPO4.G.nH2O (G = NO e n = n?mero de mol?culas de ?gua). O comportamento termoanal?tico e a espectroscopia na regi?o do infravermelho s?o indicativos da forma??o do composto VOPO4.2,5NO.3H2O. Resultados de microscopia eletr?nica de varredura (MEV) e espectroscopia de energia dispersiva (EDS) dos materiais fosfatos de vanadila e fosfatos de vanadila dopados ap?s rea??o no estado s?lido ou em solu??o com os gases indicam mudan?a na morfologia dos substratos, al?m da forma??o de cristais de enxofre ortorr?mbico sobre seus respectivos hospedeiros quando estes adsorvem sulfeto de hidrog?nio

Atmosphärendruckplasmen sind aufgrund ihrer vergleichsweise einfachen Anlagentechnik, potentiell geringen Betriebs- und Investitionskosten sowie ihrer Flexibilität bezüglich Substratgröße seit vielen Jahren von großem Interesse. Die Nutzung von Plasmaquellen mit hoher Precursoranregungseffizienz und ausgedehnter Beschichtungszone ist in diesem Zusammenhang besonders vorteilhaft. In der vorliegenden Arbeit wird deshalb erstmals eine neuartige Langlichtbogenplasmaquelle vom Typ LARGE (Long Arc Generator) zur plasmagestützten Synthese von Schichten bei AP (Atmosphärendruck) eingesetzt. Bei der Remoteaktivierung des Precursors erweisen sich insbesondere sauerstoff- sowie stickstoffhaltige Plasmagase als geeignet, um einen signifikanten Anteil der Plasmaenergie in den Remotebereich zu transferieren. Die entwickelte bogenbasierten PECVD (Plasma Enhanced Chemical Vapour Deposition) unter Atmosphärendruckbedingungen ist durch die Erzeugung hochenergetischer Plasmen gekennzeichnet, der Precursor wird stark fragmentiert und ursprüngliche Bindungen des Precursormoleküls werden vollkommen aufgebrochen. Die Ergebnisse der Gasphasencharakterisierung mittels optischer Emissions- sowie Infrarotspektroskopie lassen beim Prozess der Precursorfragmentierung im Remoteplasma auf eine zentrale Bedeutung metastabiler sowie dissoziierter Spezies schließen. Weiterhin sind hohe Plasmaleistungen, Molekulargasanteile im Plasmagas und große Plasmagasflüsse für eine wirkungsvolle Remoteaktivierung des Precursors von Vorteil. Einen wichtigen Aspekt des Verfahrens stellt darüber hinaus die Möglichkeit der Synthese sauerstofffreier Schichtmaterialien dar. Es konnte gezeigt werden, dass sowohl der genutzte Atmosphärendruckreaktoraufbau mit seinem Gasschleusenkonzept, als auch die Gasreinheit des verwendeten Prozessgases zu keiner nennenswerten Einlagerung von Sauerstoff in die Schicht führt. Die Schichthärte synthetisierter Siliziumnitrid-Schichten lässt sich ohne zusätzliche Substratheizung durch Prozessparameteroptimierung bis auf eine Härte von 17 GPa steigern. Die dynamische Abscheiderate ist mit 39 nm∙mm/s ebenfalls für eine technische Anwendung ausreichend hoch. Eine eingehende Analyse aller Daten legt den Schluss nahe, dass das Schichtwachstum bei der Atmosphärendruck Remote-PECVD häufig kinetisch gehemmt ist und nicht im thermodynamischen Gleichgewicht stattfindet. Der Wachstumsprozess ist in diesem Fall durch das Phänomen des DLG (Diffusion Limited Growth) gekennzeichnet. Homogennukleation bzw. Gasphasennukleation spielt anders als bislang angenommen auch bei Atmosphärendruckbedingungen keine bzw. eine nur untergeordnete Rolle und ist damit nicht limitierend für die erzielbare mechanische und chemische Stabilität der gebildeten Schichten. Mit steigender Diffusionslimitierung des Schichtbildungsvorganges wird eine Zunahme der Schichtrauheit beobachtet, daraus und aus dem Zuwachs an strained sowie dangling Bonds in der Schicht resultiert eine gesteigerte Affinität der synthetisierten Schichten gegenüber Sauerstoff. Als Schlüsselparameter bezüglich Schichtmorphologie sowie Topographie wird der DLG-Quotient angesehen, welcher das Verhältnis aus Oberflächendiffusionskoeffizient und Auftreffrate schichtbildender Spezies auf dem Substrat darstellt. Damit wurden im Rahmen dieser Arbeit die entscheidenden und verfahrenslimitierenden Aspekte identifiziert und die Grundlage für die weitere Optimierung dieses und anderer Remote-AP-PECVD-Verfahren geschaffen. In ähnlicher Weise wie dies auch durch die Bereitstellung einer verbesserten thermischen Aktivierung des Diffusionsprozesses schichtbildender Spezies auf der Substratoberfläche geschieht, lässt sich mit Hilfe eines niedrigen Stickingkoeffizienten eine Diffusionslimitierung des Schichtbildungsvorgangs bei AP-PECVD unterdrücken. In diesem Zusammenhang besitzt insbesondere Ammoniak im Remotegas einen günstigen Einfluss auf die entstehende Schichtmorphologie und Konformalität der Beschichtung.

The constructed wetlands, which have been being created in the Czech Republic since early 90s, are designed so they do not allow successful removal of ammonia nitrogen. Almost all of these 300 registered constructed wetlands suffer from the colmatage which leads to the lowest effectiveness of treatment in nearly all parameters. The main effort of the Institute of landscape water management is to get rid of bad reputation and to clarify the reason that leads to unsatisfactory conditions of constructed wetlands. The diploma thesis focuses on the selected constructed wetland in Dražovice (850 EO), which removes ammonia nitrogen with the effect just below the limit values in the long term. The pressure of the Morava river basin and Department of environment (Building Authority in Bučovice) has led to the necessity of taking measures leading to the increase of treatment efficiency especially ammonia nitrogen. The diploma thesis includes both, actual project documentation concentrating on the adjustment of watercourse to nitrify ammonia nitrogen, and effective choice of suitable filtration material supported by testing method in situ. The practical part of the thesis deals with the implementation of the technical solution according to the project documentation. The adjustment of the constructed wetland is now nearly before completion. Last adjustments will be taking place during the spring 2017, the final inspection as well as the evaluation of the reconstruction will take place at the end of this year.

O N é um nutriente empregado em grandes quantidades nos sistemas de produção agrícola e o mais limitante para a produção de gramíneas. A ureia é o fertilizante nitrogenado (N-fertilizante) mais usado no mundo e o principal foco da indústria mundial de fertilizantes tecnologicamente aperfeiçoados, sendo altamente suscetível à perdas por volatilização de amônia (NH3), quando aplicada sobre superfície do solo. Com intuito de minimizar o impacto ambiental e aumentar a eficiência de N, o uso de inibidores de urease é uma das tecnologias mais promissoras e menos onerosas. Adicionalmente, inibidores de urease inorgânicos constituídos por elementos essenciais às plantas, como ácido bórico (H3BO3) e sulfato de cobre (CuSO4), podem suplementar nutricionalmente os sistemas agrícolas de produção. Neste contexto, foram desenvolvidos dois experimentos, em condições controladas de laboratório e casa de vegetação, com os seguintes objetivos: i) quantificar as perdas por volatilização de NH3 a partir da aplicação superficial da ureia tratada com doses variadas de H3BO3 e CuSO4, em câmara fechada; ii) avaliar a eficiência de uso de N e B em dois estádios vegetativos do milho a partir da aplicação em superfície da 15N-ureia tratada com H3BO3 e CuSO4, em condições controladas de casa de vegetação. No experimento de laboratório, não houve interação entre as doses de B e Cu ou qualquer efeito do Cu sobre as perdas de NH3 por volatilização. O aumento de H3BO3 no tratamento da U atrasou as perdas diárias de NH3 e reduziu (P<0,001) as perdas cumulativas de volatilização de NH3. As doses de B apresentaram ajuste quadrático e, com base na análise de regressão, a dose estimada de máxima eficiência é atingida com 0,88% B no recobrimento da U. Em condições de casa de vegetação, os inibidores de urease atrasaram e reduziram as perdas de NH3 por volatilização. Ao longo de 15 dias após a fertilização, o tratamento com H3BO3 promoveu reduções na volatilização de NH3 que variaram de 6 a 17% em relação à ureia não tratada, ocorrendo diferenciação entre doses de B. Os tratamentos com maiores doses de B não diferiram do tratamento com N-(n-butil) tiofosfórico triamida (NBPT) em produção de biomassa de milho. A altura de plantas, diâmetro de colmo e índice de área foliar não apresentaram diferenças entre N-fertilizantes. A morfologia do sistema radicular do milho foi afetada pelo uso de inibidores no estádio V8. O aumento de H3BO3 no revestimento da ureia aumentou em média 10% a eficiência de uso do N-fertilizante (EUN-F), em relação à ureia não tratada. Em VT, não houve diferença para EUN-F entre os tratamentos NBPT e maior dose de H3BO3 (0,88% B). O tratamento da ureia com H3BO3 aumentou proporcionalmente o acúmulo de B na planta. A adição de CuSO4 não afetou a volatilização de NH3 e a EUN-F. O recobrimento da ureia com H3BO3 foi uma estratégia eficiente em reduzir as perdas de N, aumentar a EUN-F e fornecer B às plantas.
N is a nutrient used in large quantities in agricultural production systems and it is the most limiting element for production of grasses. Urea is the most widely used nitrogen fertilizer (N fertilizer) in the world and the main focus of the worldwide industry of fertilizers technologically improved, being highly susceptible to losses by volatilization of ammonia (NH3) when applied on soil surface. In order to minimize environmental impact and increase N efficiency, the use of urease inhibitors is one of the most promising and least expensive technologies. In addition, inorganic urease composed for essential elements for plants, such as boric acid (H3BO3) and copper sulfate (CuSO4), can nutritionally supplement agricultural production systems. In this context, two experiments were carried out under controlled conditions (laboratory and greenhouse) with the following objectives: i) laboratory: to quantify NH3 volatilization losses from the surface application of urea treated with different rates of H3BO3 and CuSO4, using closed chamber; (ii) greenhouse: to evaluate the N and B use efficiency from surface application of 15N urea treated with H3BO3 and CuSO4 in two vegetative stages of maize. In the laboratory experiment, there was no interaction between B and Cu rates or any Cu effect on NH3 losses by volatilization. The increase of H3BO3 in the treatment of urea delayed the daily losses of NH3 and reduced (P<0.001) the cumulative volatilization losses of NH3. The rates of B showed a quadratic adjustment and, based on the regression analysis, the estimated rate of maximum efficiency was 0.88% B. Under greenhouse conditions, urease inhibitors delayed and decresed the losses of NH3 by volatilization. Over 15 days after fertilization, treatment with H3BO3 promoted reductions in NH3 volatilization ranging from 6 to 17% compared to untreated urea, and occur differentiation between B rates. The treatments with higher rates of B did not differ from the treatment with N-(n-butyl) thiophosphoric triamide (NBPT) in maize biomass production. The plant height, stem diameter and leaf area index did not show differences between N fertilizers. The morphology of the maize root system was affected by the use of urease inhibitors only in stage V8. The increase of H3BO3 in the urea coating increased on average 10% the efficiency of use of N fertilizer (NUE-F) in relation to untreated urea. In VT growth stage, there was no difference for NUE-F between treatments NBPT and higher rate of H3BO3 (0.88% B). Treatment of U with H3BO3 increased proportionally the accumulation of B in the plant. The addition of CuSO4 did not affect volatilization of NH3 and NUE-F. Urea coating with H3BO3 was an efficient strategy to reduce N losses, to increase the NUE-F and to supply B for plants.

Graphene has been shown to be very powerful as a transducer in many biosensor applications due to its high sensitivity. This enables smaller surfaces and therefore less material consumption when producing sensors and concequently cheaper and more portable sensors compared to the commercially available sensors today. The electrical properties of graphene are very sensitive to gas exposure why presence of molecules or small changes in concentration could easily be detected when using graphene as a sensing layer. Graphene is sensitive towards many molecules and in order to detect and possibly identify gas molecules the surface needs to be functionalized. The intention of this project was to use nanoparticles (NPs) to further increase sensitivity and specificity towards selected molecules and also enable biofunctionalization of the NPs, and by that tune the electrical properties of the graphene. This study proposes the use of Fe3O4 and TiO2 NPs to enable sensitive detection of volatile gases and possibly further functionalization of the NPs using biomolecules as a detecting agent in a liquid-phasebiosensor application. The interaction between graphene and NPs have been investigated using several surface charactarization methods and electrical measurements for detection of gaseous molecules and also molecules in a liquid solution. The characterizing methods used are XPS, AFM with surface-potential mapping and Raman spectroscopy with reflectance mapping in order to investigate the NPs interaction with the graphene surface. Sensors where manufactured for gas-phase detection of CO, formaldehyde, benzene and NH3 specifically and display differences in sensitivity and behavior of the Fe3O4 and TiO2 NPs respectively. For liquid measurements the difference in behavior in two buffers was investigated using an in-house flow-cell setup. The surface charecterizing measurements indicated that just a small difference could be found between the two NPs, however a significant change in sensor response could be detected as a function of coverage. The liquid and gas-phase measurements rendered information on differences in sensitivity between the NPs and between analytes where TiO2 showed a higher level of sensitivity towards most of the gases investigated. Both Fe3O4 and TiO2 NP coated graphene showed capability to detect formaldehyde and benzene down to 50 ppb and 5 ppb respectively. The sensitive gas detection could help protecting individuals being exposed to a hazardous level of volatile gases if concentrations increase rapidly or at a long term exposure with lower concentrations, improving saftey and health where these gases are present.

The temperature and/or entropy of electrically polarisable materials can be altered by changing electric field E. Research into this electrocaloric (EC) effect has focussed on increasing the size of the EC effects, with the long-term aim of building a cooler with an EC material at its heart. Materials and experimental methods are briefly reviewed. A ‘resetting’ indirect route to isothermal entropy change ∆S for hysteretic first-order transitions is described. An indirect route to adiabatic temperature change ∆T, without the need for field-resolved heat capacity data, is also described. Three temperature controllers were built: a cryogenic probe for 77-420 K with ∼5 mK resolution, a high-temperature stage with vacuum enclosure for 295-700 K with ∼15 mK resolution, and a low-temperature stage for 120-400 K with electrical access via micropositioners. Automation enables dense datasets to be compiled. Single crystals of inorganic salts (NH4)2SO4 , KNO3 and NaNO2 were obtained. Applying 380 kV cm−1 across (NH4)2SO4 , it was found that |∆S| ∼ 20 J K−1 kg−1 and |∆T | ∼ 4 K, using the indirect method near the Curie temperature TC = 223 K. Without the ‘resetting’ indirect method, |∆S| ∼ 45 J K−1 kg−1 would have been spuriously found. Preliminary indirect measurements on KNO3 and NaNO2 give |∆S| ∼ 75 J K−1 kg−1 for ∆E ∼ 31 kV cm−1 near TC = 400 K and |∆S| ∼ 14 J K−1 kg−1 for ∆E ∼ 15 kV cm−1 near TC = 435 K, respectively. A cation-ordered PbSc0.5Ta0.5O3 ceramic showing a nominally first-order transition at 295 K was obtained. The Clausius-Clapeyron phase diagram is revealed via indirect measurements where |∆S| ∼ 3.25 J K−1 kg−1 and |∆T | ∼ 2 K, and direct measurements where |∆T | ∼ 2 K. Clamped samples show broadening of the field-induced transition. Epitaxial, ∼64 nm-thick SrTiO3 films were grown by pulsed laser deposition on NdGaO3 (001) substrates with a La0.67Sr0.33MnO3 bottom electrode. The indirect method gives |∆S| ∼ 8 J K−1 kg−1 and |∆T | ∼ 3.5 K near 180 K with |∆E| = 780 kV cm−1. Finite element modelling (FEM) was used to optimise the geometry of multilayered capacitors (MLCs) for EC cooling. Intrinsic cooling powers of 25.9 kW kg−1 are predicted for an optimised MLC based on PVDF-TrFE with Ag electrodes.

Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (i.e. nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques.

The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures.

Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well.

Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger vis-à-vis Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups.

Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.

Crucial features in gas sensors for environmental monitoring are the gas sensitivity in the low ppb range and the ability to discriminate variations of a certain polluting gas from other interfering gases. Monitoring of ammonia gas concentrations is mandatory to reduce the hazard for human health and vegetation determined by the widespread use of ammonia derivatives as agricultural nitrogen fertilizers, industrial production and traffic. In particular, ammonia, besides being a toxic molecule is one of the main precursors of secondary fine particulate matter (PM10, PM2.5). Ammonia could hence be used as a local marker of secondary fine particulate formation, allowing indirect control of particulate emission sources. In spite of this urgency, the detection of NH3 concentrations in urban areas with chemiresistor gas sensors (CGSs) has been so far widely overlooked, since the average levels are usually low, i.e. in the 20-30 ppb range, while the CGSs are generally tested by exposure to ammonia in the ppm range. Carbon nanotubes (CNTs), discovered more than 20 years ago, are well known and studied systems for many applications, among which (of course) gas sensing. With respect to commercial electrochemical sensors (mostly based on metal oxide materials), CNTs show a higher physical and chemical stability, better transport of charge to the electrodes and a wide range of possible hybrid architectures and operational features, among which the operation at room temperature, that make them unique materials for gas detection. The main goal of this thesis is to increase the sensitivity to [NH3] and to lower the detection limit (DL), exploring sample preparation strategies of low-cost single walled carbon nanotubes (SWCNT)-based gas sensors operating at room temperature, considering also the response to other interfering gases. Furthermore, effects of metal oxide nanoparticles functionalization and gas response of hybrid layers have been also investigated.

Aqueous solutions were studied using photoelectron and Auger spectroscopy, based on synchrotron radiation and a liquid micro-jet setup. By varying the photon energy in photoelectron spectra, we depth profiled an aqueous tetrabutylammonium iodide (TBAI) solution. Assuming uniform angular emission from the core levels, we found that the TBA+ ions were oriented at the surface with the hydrophobic butyl arms sticking into the liquid. We investigated the association between ions and their neighbors in aqueous solutions by studying the electronic decay after core ionization. The (2p)−1 decay of solvated K+ and Ca2+ ions was studied. The main features in the investigated decay spectra corresponded to two-hole final states localized on the ions. The spectra also showed additional features, related to delocalized two-hole final states with vacancies on a cation and a neighboring water molecule. These two processes compete, and by comparing relative intensities and using the known rate for the localized decay, we determined the time-scale for the delocalized process for the two ions. We compared to delocalized electronic decay processes in Na+, Mg2+, and Al3+, and found that they were slower in K+ and Ca2+, due to different internal decay mechanisms of the ions, as well as external differences in the ion-solute distances and interactions. In the O 1s Auger spectra of aqueous metal halide solutions, we observed features related to delocalized two-hole final states with vacancies on a water molecule and a neighboring solvated anion. The relative intensity of these feature indicated that the strength of the interaction between the halide ions and water correlated with ionic size. The delocalized decay was also used to investigate contact ion pair formation in high concentrated potassium halide solutions, but no concrete evidence of contact ion pairs was observed.
Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 726

碩士
淡江大學
化學學系
86
In this dissertation, the vibrational spectroscopy of ammoniated ammonium ions NH4+(NH3)n (n=1~6) and clusters of water molecular (H2O)m (m=6,8,10) were studied by theoretical calculations : Ab Initio (MP2) and DFT (B3LYP).In ammoniated ammonium ions NH4+( NH3)n (n=0~6) parts. For n=0 and 1, The geometries of the clusters are optimized at MP2, CCD, QCISD and B3LYP levels with several basis sets, and the bonding energies are compared to experimental results to find the cheap and reliable methods for the calculations of larger clusters. For n=2~6, the geometry optimizations and vibrational configurations are performed at the MP2 and B3LYP levels with 6-31+G* basis set. The bonding energies are corrected by the BSSE (basis set superposition errors) and ZPVE (zero-point vibrational energies). In addition, the barriers of proton transfer between two heavy atoms and the internal rotation of NH3 molecule along the N-H axis in NH4+ in NH4+(NH3)n were estimated at several levels.In water molecular (H2O)m (m=6,8,10) parts. The clusters which possessed 2- and 3-coordinated H2O were chosen to investigate the difference of the free-OH stretching frequencies of 2- and 3 - coordinated H2 O. The geometries were optimized at B3LYP/6-31+G* level. The calculated frequencies are scaled by 0.973. The effects of the directionality of hydrogen bonds and the types of the neighbour waters will affect the amplitude of the frequency red-shia of free-OH stretching in water clusters.

博士
國立臺灣科技大學
化學工程系
98
In this thesis, the density functional theory (DFT) calculations were applied to investigate the adsorptions of NHx (x = 0–3) species and N2, and the ammonia oxidation on the RuO2(110) and IrO2(110) surfaces. In the adsorption part, the analyses of density of states (DOS), electron density difference (EDD) and charge difference (?惶) provide the detailed adsorbate–surface interactions. The results demonstrate that each adsorbate has very similar interactions with both the RuO2(110) and IrO2(110) surfaces in this work. The major difference in adsorptions between these two surfaces is that the vacant state of the Ircus atom is closer to the Fermi level and could form stronger ? bonding with the adsorbates. This phenomenon causes the higher binding energies of the adsorbates on the IrO2(110) surfaces than those on the RuO2(110) surfaces. In the ammonia oxidation part, calculated results show that the oxidation mechanisms on the RuO2(110) and IrO2(110) surfaces are also very similar. The ammonia oxidation reactions include three major steps: NHx dehydrogenation, H2O formation and desorption, and N-containing products formation. The oxygen-rich environment is required for ammonia oxidation over the two surfaces, because the additional Ocus atoms make the surface having sufficient oxygen species to complete the dehydrogenation. In addition, Ocus atom is also the major oxidant in the formation of oxidation products. The energetic analysis demonstrates different behavior in the formation of N2 and NO on these two surfaces. However, on both surfaces, the selectivity toward N2 and NO is dominated by the coverage of Ocus atoms on the surfaces; a higher coverage of Ocus atoms results in greater production of NO, and a lower coverage results in the production of N2.