[ES] Las zeolitas son sólidos cristalinos microporosos con canales y cavidades de tamaños moleculares, que pueden presentar gran variedad de estructuras y composición química, lo que las hace útiles como catalizadores en gran variedad de procesos químicos. En la presente tesis doctoral, se han estudiado en profundidad las propiedades estructurales de zeolitas con estructura RTH y MFI pura sílice y aluminosilicato, utilizando fundamentalmente la técnica de resonancia magnética nuclear (RMN). Además, se han estudiado catalizadores zeolíticos tipo Ag-FAU para una reacción de interés medioambiental como la Oxidación Catalítica Selectiva de NH3 (NH3-SCO). En esta tesis, las zeolitas tipo MFI y RTH se han sintetizado utilizando tetraalquilamonios y tetralquilfosfonios como ADEs y HF como agente mineralizante. Los resultados referentes a la zeolita MFI pura sílice indican que el ADE utilizado afecta al orden local de la estructura, a la distribución de flúor y a la formación de defectos de red. En la síntesis de la zeolita tipo MFI aluminosilicato, se ha observado que el ADE utilizado y la relación Si/Al produce diferencias significativas en los espectros de RMN de 27Al, que se atribuyen normalmente a variaciones en la distribución del aluminio en diferentes sitios cristalográficos. Sin embargo, las diferencias desaparecen después de la calcinación, lo que cuestiona esta interpretación. La zeolita tipo RTH pura sílice se ha sintetizado con el catión iPr3MeP+ variando los tiempos y la temperatura de síntesis. Estos parámetros afectan tanto a la estructura local de los átomos de silicio como a la distribución del flúor en la zeolita. Se ha observado también la transformación de la estructura tipo STF a RTH durante la síntesis. La modificación con fósforo de zeolitas tipo aluminosilicato, que normalmente se realiza por impregnación, estabiliza el aluminio de la red en condiciones hidrotermales, lo que tiene importantes implicaciones en las aplicaciones industriales. En esta tesis, se han incorporado cantidades variables de fósforo en las zeolitas MFI y RTH aluminosilicatos utilizando mezclas de alquilamonios y alquilfosfonios como ADEs. Los resultados indican que el fósforo permanece en las zeolitas después de la calcinación estabilizando el aluminio de red. La caracterización detallada de las muestras ha permitido proponer las especies Al-P formadas, responsables de la estabilización de la red. Además, las zeolitas P-RTH y P-ZSM-5 se han utilizado como catalizadores para la reacción de metanol a olefinas. Por último, se ha estudiado la influencia de diferentes parámetros como la relación Ag/Al, la presencia de cationes alcalinos o la acidez Brønsted en zeolitas Ag-FAU y sus repercusiones en el comportamiento catalítico para la reacción de NH3-SCO. Los catalizadores se han caracterizado exhaustivamente antes, durante y después de la reacción, observándose que las partículas de plata metálica, que son los centros activos, se re-dispersan y oxidan en condiciones de reacción. / [CA] Les zeolites són sòlids cristal·lins i microporosos amb canals i cavitats de dimensions moleculars, que poden presentar una gran varietat d' estructures i composició química, això les fa molt interessants com a catalitzadors en un ampli nombre de reaccions químiques. En la present tesi doctoral, s'ha estudiat en profunditat les propietats estructurals de les zeolites amb estructura RTH i MFI pura sílice i amb sílici i alumini, utilitzant fonamentalment la tècnica de ressonància magnètica nuclear. A més, s'han estudiat catalitzadors basats en Ag-FAU zeolites per a una reacció d'interès mediambiental com es l' Oxidació Catalítica Selectiva d'amoníac (NH3-SCO). En aquesta tesi, les zeolites tipus MFI i RTH s'han sintetitzat amb l'ús de cations tetraalquilamoni i tetraalquilfosfoni i HF com agent mineralitzant. Els resultats obtinguts per a la zeolita MFI pura sílice mostren com l'ADE utilitzat juga un paper important en l'ordre local dels àtoms de silici, la distribució de fluor i la formació de defectes zeolítics. En la síntesi de la zeolita MFI aluminosilicat, s'ha observat que la natura dels ADEs i la relació Si/Al produeix diferències significatives a l'espectre de 27Al de RMN, normalment associades a una localització diferent de l'alumini. Però eixes diferències desapareixen amb la calcinació de les zeolites. La zeolita RTH pura sílice ha sigut sintetitzada amb el catió iPr3MeP+ modificant les condicions de síntesi (temps i temperatura). Els resultats mostren que l'ordre local dels àtoms de l' estructura zeolítica o la distribució de fluor es veu influenciada per aquests paràmetres. També s'ha pogut observar que en determinades condicions de síntesi es produeix la transformació de la estructura tipus STF en RTH en el procés de síntesi. La modificació amb fòsfor de les zeolites que contenen alumini, que normalment es realitza per impregnació, estabilitza l'alumini de l'estructura zeolítica en condicions hidrotermals, la qual cosa té una importància crucial per a les aplicacions industrials d'aquests materials. En aquesta tesi, s'han incorporat quantitats creixents de fòsfor a les zeolites RTH i MFI aluminosilicats utilitzant mescles d'alquilamonis i alquilfosfonis com ADEs. Els resultats indiquen que tot el fòsfor introduït roman a la zeolita després de la calcinació, estabilitzant l'alumini en la zeolita. La caracterització dels materials ha permès proposar les espècies Al-P formades a l'interior de les zeolites, que són les responsables de l'alta estabilitat hidrotermal de l'alumini a l'estructura zeolítica. A més, les zeolites RTH i MFI modificades amb fòsfor han sigut utilitzades com a catalitzadors en la reacció de metanol a olefines (MTO). Per últim, s'ha estudiat la influència de alguns paràmetres com la relació Ag/Al, la presència de cations alcalins o centres àcids de BrØnsted als catalitzadors tipus Ag-FAU i les seues repercussions per a la reacció de NH3-SCO. Els catalitzadors s'han caracteritzat abans, durant i després de la reacció i els resultats mostren que les nanopartícules de plata metàl·lica són el centre actiu de la reacció i que es re-dispersen i oxiden en condicions de reacció. / [EN] Zeolites are microporous crystalline solids containing channels and cavities of molecular dimensions, which can present different structures and chemical composition, making them especially interesting as catalysts in several chemical processes. In this doctoral thesis, we have deeply studied the structural properties of pure silica and aluminosilicate RTH- and MFI-type zeolites mainly using nuclear magnetic resonance (NMR) spectroscopy. Moreover, we have studied the properties of Ag-FAU zeolites as catalysts for the selective catalytic oxidation of ammonia (NH3-SCO), which is a reaction of great interest for the environmental. Here, zeolites RTH and MFI have been synthesized in the presence of tetraalkilammonium and phosphonium cations as OSDAs and in fluoride media. The results obtained for the MFI zeolites show that the OSDAs has a strong influence on the local order of the framework, the fluorine distribution and the formation of siloxy/silanol defects. The results for the aluminosilicate MFI-type (ZSM-5) zeolite show that the shape of the 27Al NMR spectrum changes depending on both the OSDA and the Si/Al ratio, which is usually attributed to a different Al sitting in the zeolite. These differences disappear after the calcination of the zeolites, questioning the classical interpretation. RTH-type zeolite has been synthesized using the iPr3MeP+ cation varying the synthesis conditions (time and temperature). The results show that these parameters affect the local environment of the silicon atoms and the fluorine distribution inside the zeolite. It has been also possible to identify the zeolitic transformation of the STF structure into the RTH-type during the synthesis. The introduction of phosphorus in the aluminosilicate zeolites, usually done by the impregnation procedure, stabilizes the framework aluminium under steam conditions, with important implications in industrial processes. In this doctoral thesis, we have varied the P/Al molar ratios using the dual-template synthesis technique. All phosphorus from the P-based OSDAs remain inside the zeolites after the thermal/hydrothermal treatments. The exhaustive characterization of the materials has allowed us to propose the Al-P species formed inside the zeolites responsible of the aluminium stabilization. Moreover, some phosphorus modified RTH and MFI zeolites were tested in the methanol to olefins (MTO) reaction. Finally, we have studied the influence of different parameters such as the Ag/Al ratio, the alkali cations or the presence of BrØnsted acid sites in the Ag-FAU zeolites and its implications in the NH3-SCO reaction. The Ag-FAU catalysts have been deeply characterized before, during and after the catalytic tests, identifying the Ag0 specie, which is the active centre for this reaction, and that metal particles are re-dispersed and oxidized under reaction conditions. / Martínez Ortigosa, J. (2021). Caracterización estructural de zeolitas por Resonancia Magnetica Nuclear y su aplicación como catalizadores [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/165576 / TESIS

<p>Cilj ove disertacije je razvoj modela zasnovanog na analizi tokova<br />materijala (MFA) i analizi tokova supstanci (SFA) sistema<br />upravljanja biorazgradivim otpadom sa naglaskom na upravljanje<br />fosforom kao resursom. U zemljama u tranziciji kao što je Srbija<br />upravljanje biorazgradivim otpadom predstavlja poseban problem jer<br />se dovodi u direktnu vezu sa emisijama gasova sa efektom staklene<br />bašte i generisanjem procednih voda. Kako bi se razvila strategija<br />upravljanja biorazgradivim otpadom u skladu sa zahtevima EU<br />direktiva, razvijeni model je primenjen na sistem upravljanja<br />biorazgradivim otpadom u Srbiji, i dva alternativna scenarija. Na<br />osnovu rezultata primenjenog modela, sva tri razvijena scenarija<br />upravljanja biorazgradivim otpadom su evaluirana i izvršeno je<br />njihovo poređenje.</p> / <p>The aim of this dissertation is biodegradable waste management system model development based on material flow analysis (MFA) and substance flow analysis (SFA) with an emphasis on phosphorus management as a resource. In transition countries like Serbia, biodegradable waste management is a particular problem due to direct linkage with greenhouse gas emissions and leachate generation. In order to develop a biodegradable waste management strategy in accordance with the requirements of EU directives, developed model was applied to the biodegradable waste management system in Serbia, and two alternative scenarios. Based on the results of the applied model, evaluation and comparison of all three developed scenarios of biodegradable waste management is performed.</p>

Dans un contexte de lutte contre la dégradation de notre environnement, les lois et règlementations issues du Grenelle de l'environnement, obligent de trouver des solutions permettant de répondre à des normes tout en remplaçant des composés nocifs. Dans ce souci de respect de l'environnement, certains changements doivent s'opérer dans le domaine de la sécurité contre les incendies, puisqu'actuellement, les systèmes retardateurs de flammes contiennent des composés halogénés. Pour répondre à cette problématique, l'approche choisie a été d'introduire, des composés phosphorés et/ou azotés préalablement greffés ou imprégnés sur de la silice dans différentes matrices polymères. Les composites ont alors été réalisés à l'aide du procédé d'extrusion en introduisant, au sein d'un polypropylène ou d'un polybutylène téréphtalate, un faible taux de charges modifiées ou non, à savoir 10% en masse. Les études morphologique, rhéologique, thermogravimétrique mais également du comportement au feu des composites ont été réalisées et des relations entre toutes ces propriétés ont pu être établies. Dans le cas du polypropylène, l'ajout de silice non traitée a globalement entrainé un meilleur comportement au feu que l'ajout de silices modifiées, ce qui a été expliqué par des différences morphologiques et rhéologiques. Pour le polybutylène téréphatalate, les meilleures propriétés ont été observées lors de l'ajout de silices modifiées par les différents composés phosphorés. Grâce à ces résultats des liens étroits entre type de composé ignifugeant, viscoélasticité, formation d'une couche barrière protectrice et amélioration du comportement au feu ont été mis en évidence / In order to protect our environment, toxic compounds have to be replaced to meet the new regulations as well as industrial standards. Therefore, to be environmental friendly, some solutions have to be found in terms of fire safety, since halogenated compounds are still used in fire retardant systems. The way studied to solve this problem was to add silica fillers modified by phosphorous or nitrogen agents into two polymer matrices (polypropylene and polybutylene terephthalate). Two different techniques were used to modify the silica surface: the first by grafting and the second by impregnation. Only 10% by weight of untreated or modified fillers was introduced into the polymers thanks to extrusion process. Morphology studies, rheological and fire behaviors as well as thermogravimetric analyses were performed on composites and relationship between those properties have been established. In the case of polypropylene, the untreated fillers induce the most significant reduction of peak of Heat Release Rate while the surface modification by phosphorous agents does not lead to the expected effect on the fire behavior of PP composite. The origin of this phenomenon was deeply studied and was related to the difference of morphology and rheological behavior between the several PP composites. Concerning polybutylene terephthalate, the best fire performances were obtained for composites containing phosphorous modified silica. Given these results, relationships between the type of flame-retardant compound, the viscoelasticity, the formation of a fire protective layer and the improvement of fire behavior has been identified

The aim of this study was to assess the effect of composting process of cow manure and rice straw with application of cow urine and to evaluate the quality of composting products. There were two treatment piles, in which one pile was applied with cow urine every week and another pile without urine application. Each pile was set up by one tone cow manure and 500kg rice straw. The piles were half-covered by plastic foil to protect from rain and turned one a week. The composting duration lasted 8 weeks. The parameters such as temperature, pH, DM, density and nitrogen were monitored and observed during the 8-week period. The results showed that there was a significant difference in temperature, compost quality and duration between two piles with and without cow urine application. The application of cow urine increased significant nitrogen and phosphorous content and shortened the composting process. This study recommends that cow urine should be applied for composting process of cow manure and rice straw in order to increase the quality of compost. The final product was in the range of matured compost level and can be used directly for agriculture crop. / Mục tiêu của nghiên cứu nhằm đánh giá ảnh hưởng đến chất lượng phân compost của việc bổ sung nước tiểu vào trong quá trình ủ phân từ nguyên liệu phân bò và rơm rạ. Thí nghiệm được thực hiện trên hai đống ủ phân, một đống ủ được bổ sung nước tiểu bò hàng tuần và một đống ủ không bổ sung nước tiểu bò như là một nghiệm thức đối chứng. Mỗi đống ủ được trộn 1 tấn phân bò và 500kg rơm. Đống ủ phân được đậy kín một nửa phía trên nhằm ngăn cản ảnh hưởng của mưa và được đảo trộn một lần mỗi tuần. Quá trình thí nghiệm được tiến hành trong 8 tuần. Các chỉ tiêu như nhiệt độ, pH, DM, mật độ và chất dinh dưỡng Nitơ và Phốt Pho được quan trắc trong thời gian ủ. Kết quả cho thấy có sự khác biệt đáng kể giữa hai đống phân ủ đối với các chỉ tiêu như nhiệt độ, chất lượng phân compost và thời gian ủ. Đống ủ phân có bổ sung nước tiểu có hàm lượng Nitơ và Phốt pho cao hơn và thời gian ủ ngắn hơn. Kết quả nghiên cứu khuyến cáo nên bổ sung nước tiểu bò cho quá trình ủ phân compost nhằm tăng hàm lượng chất dinh dưỡng cho sản phẩm phân compost. Sản phẩm sau quá trình ủ đạt mức độ phân hữu cơ và có thể sử dụng cho cây trồng.

No description available.

Soil degradation is a common occurrence in Haiti that is mainly caused by the cultivation of marginal lands and deforestation, which both contribute to the excessive erosion rate seen in the country today. The Central Plateau of Haiti is a mountainous region in which a majority of the population is rural and practices subsistence agriculture on hillsides and steeply-sloping land. Essential plant nutrients, such as nitrogen (N) and phosphorus (P), are commonly a limiting factor in crop production, yet fertilizer is unavailable or is too expensive for smallholder farmers to purchase. This study was conducted to a) evaluate organic matter and nutrient stocks of various soils in the Central Plateau region, along with other chemical and physical characteristics and b) to evaluate the phosphorus-scavenging ability of commonly-grown crops to isolate those that may benefit subsequent smallholder yields. Soils from four locations in the Central Plateau were assessed for organic matter in labile and non-labile fractions as well as for cation exchange capacity (CEC), total organic carbon (C) and N, pH, texture, and other characteristics. Results indicated that most of the soil (92%) was contained within aggregates, and organic matter was mainly present in stable, slowly-decomposing fractions. Seven species were evaluated in a controlled-environment pot experiment for bulk and rhizosphere soil P and pH, plant dry weight, and above- and below-ground P tissue content as indicators of the species' ability to solubilize P from the soil. Velvet bean (Mucuna pruriens (L.) DC) produced the most biomass and was able to take up the most P, though lablab (Lablab purpureous (L.) Sweet), took up comparable amounts of P. / Master of Science / LTRA-6 (A CAPS program for the Central Plateau of Haiti)

<p>This report is commissioned by the Water and Sewage Agency in The City of Mariehamn, Åland. The basic aim is to investigate positive or negative effects of a relocation of the sewage pipe from a wastewater treatment plant, Lotsbroverket. The environmental licence of Lotsbroverket is to be revised and The Environmental Appeal Board at Åland’s Government and Administrative Board has made demands that several possible locations in an outer water area should be examined. The present location of the sewage pipe is in Svibyviken, which has been classified as an “inner water area”.</p><p>The objective of this work is to study to which extent the nutrient loading from Lotsbroverket influence the environmental conditions in Svibyviken, and to investigate the suitability of different locations of the wastewater pipe from Lotsbroverket.</p><p>The way a coastal area looks, i.e., its morphometry, determines to a large extent its ecological characteristics. The investigated coastal area was digitalized from a nautical chart. The software used for this was Roots 3.3 and the GIS-tool ArcGIS 8.3. The localization of the coastal boundaries for the entire coastal area and for investigated sub-areas was determined according to the topographical bottleneck method, i.e., the boundary lines were drawn where the exposure of the coast to the open sea is minimized.</p><p>A process-based dynamic mass-balance model for total phosphorous has been used in this study. Using this model, one can estimate and quantify the effects of different nutrient sources in coastal areas. All the fluxes of phosphorous to, from and within the defined areas were studied and ranked. Model simulations have shown how changes in any of the phosphorous fluxes influence the mean monthly concentrations of total phosphorous. The situation for total nitrogen was determined with a statistical/empirical regression model between phosphorous and nitrogen concentrations. To estimate the expected ecological effects from a change in the nutrient loading from Lotsbroverket, statistical/empirical correlations between modelled nutrient concentrations and ecological effect variables have been used. Standard effect variables for the study of eutrophication effects in coastal areas are, e.g., the chlorophyll concentration, Secchi depth and oxygen saturation in deep water. These variables have also been used in this study.</p><p>It has been shown that (1) the nutrient concentrations of the Baltic Sea controls the concentration of nutrients in the studied areas to a very large extent, (2) that the nutrient fluxes from Lotsbroverket are small compared to the nutrient fluxes from the Baltic Sea and hence also of minor importance for the nutrient state of the receiving water system, (3) that the influence of the nutrient emissions from Lotsbroverket are most noticeable in the present inner recipient, Svibyviken, and (4) that the impact logically decreases with distance between the location of the sewage pipe and boundary line to the open sea. The overall conclusion is that no major improvement of the conditions in Svibyviken can be expected by a reduction or a relocation of the nutrient emissions from Lotsbroverket.</p> / <p>Detta examensarbete är ett uppdrag av VA-verket vid Mariehamns stad, Åland, med syfte att utreda effekter av en eventuell flyttning av avloppsreningsverket Lotsbroverkets utloppsledning. Inför en revidering av Lotsbroverkets miljötillstånd har Miljöprövningsnämnden vid Ålands landskapsregering ställt villkor på att tillståndshavaren skall utreda möjligheter till att avleda det renade avloppsvattnet till ett yttre vattenområde. Utloppsledningen mynnar i dagsläget i Svibyviken, vilken har klassificerats som ett inre vattenområde.</p><p>Målsättningen med detta arbete är att belysa vilka ekologiska effekter näringsämnesutsläppet från Lotsbroverket har på primärrecipienten Svibyviken samt att undersöka några andra områdens lämplighet som mottagare av avloppsvattnet. Ett kustområdes utseende och form, det vill säga dess morfometri, avgör i stor utsträckning dess ekologiska förhållanden. För att få en god bild av det undersökta områdets morfometri digitaliserades området utifrån ett sjökort i digitaliseringsprogrammet Roots 3.3, varefter data bearbetades med GIS-verktyget ArcGIS 8.3. Avgränsning av kustområdet som helhet och av undersökta delområden gjordes enligt den topografiska flaskhalsmetoden, det vill säga så att kustens öppenhet mot utanförliggande hav eller vattenområde minimeras (Håkanson et al., 1984; Pilesjö et al., 1991).</p><p>För arbetet har en processbaserad, dynamisk massbalansmodell för totalfosfor använts. Modellen har tagits fram för att eutrofieringseffekter i kustområden skall kunna studeras (Håkanson & Karlsson, 2001). Vid användandet av modellen kan effekter av olika näringsämneskällor uppskattas och kvantifieras. Samtliga totalfosforflöden till, från och inom olika avgränsade områden har studerats och rangordnats. Modellsimuleringar har visat hur förändringar i något av fosfortillflödena inverkar på recipientens månadsmedelkoncentration av totalfosfor. Situationen för kväve har undersökts med hjälp av en statistisk/empirisk regressionsmodell mellan fosfor- och kvävehalt. För att belysa de ekologiska effekter som kan förväntas efter en förändring av Lotsbroverkets fosfor- och kväveutsläpp har statistiska/empiriska kopplingar gjorts mellan näringsämneskoncentrationer och ekologiska effektvariabler. Bra effektvariabler vid undersökning av eutrofieringseffekter är exempelvis klorofyllhalt, siktdjup samt syrgashalt i bottenvattnet. Dessa variabler har också använts i detta arbete.</p><p>Resultaten visar att (1) närsaltskoncentrationerna i de studerade områdena i hög grad styrs av den allmänna eutrofieringsnivån i Östersjön, (2) att utsläppet av näringsämnen från Lotsbroverket inte inverkar på recipientens näringsstatus i någon stor utsträckning, (3) att Lotsbroverkets påverkan är störst på nuvarande recipient, Svibyviken, (4) och att påverkan sedan successivt minskar ju längre ut mot öppna havet utloppsledningen lokaliseras. Slutsatsen av utredningen är att en reduktion av Lotsbroverkets utsläpp eller nylokalisering av utloppsledningen inte kan förväntas ge någon omfattande förbättring av tillståndet i Svibyviken.</p>

This report is commissioned by the Water and Sewage Agency in The City of Mariehamn, Åland. The basic aim is to investigate positive or negative effects of a relocation of the sewage pipe from a wastewater treatment plant, Lotsbroverket. The environmental licence of Lotsbroverket is to be revised and The Environmental Appeal Board at Åland’s Government and Administrative Board has made demands that several possible locations in an outer water area should be examined. The present location of the sewage pipe is in Svibyviken, which has been classified as an “inner water area”. The objective of this work is to study to which extent the nutrient loading from Lotsbroverket influence the environmental conditions in Svibyviken, and to investigate the suitability of different locations of the wastewater pipe from Lotsbroverket. The way a coastal area looks, i.e., its morphometry, determines to a large extent its ecological characteristics. The investigated coastal area was digitalized from a nautical chart. The software used for this was Roots 3.3 and the GIS-tool ArcGIS 8.3. The localization of the coastal boundaries for the entire coastal area and for investigated sub-areas was determined according to the topographical bottleneck method, i.e., the boundary lines were drawn where the exposure of the coast to the open sea is minimized. A process-based dynamic mass-balance model for total phosphorous has been used in this study. Using this model, one can estimate and quantify the effects of different nutrient sources in coastal areas. All the fluxes of phosphorous to, from and within the defined areas were studied and ranked. Model simulations have shown how changes in any of the phosphorous fluxes influence the mean monthly concentrations of total phosphorous. The situation for total nitrogen was determined with a statistical/empirical regression model between phosphorous and nitrogen concentrations. To estimate the expected ecological effects from a change in the nutrient loading from Lotsbroverket, statistical/empirical correlations between modelled nutrient concentrations and ecological effect variables have been used. Standard effect variables for the study of eutrophication effects in coastal areas are, e.g., the chlorophyll concentration, Secchi depth and oxygen saturation in deep water. These variables have also been used in this study. It has been shown that (1) the nutrient concentrations of the Baltic Sea controls the concentration of nutrients in the studied areas to a very large extent, (2) that the nutrient fluxes from Lotsbroverket are small compared to the nutrient fluxes from the Baltic Sea and hence also of minor importance for the nutrient state of the receiving water system, (3) that the influence of the nutrient emissions from Lotsbroverket are most noticeable in the present inner recipient, Svibyviken, and (4) that the impact logically decreases with distance between the location of the sewage pipe and boundary line to the open sea. The overall conclusion is that no major improvement of the conditions in Svibyviken can be expected by a reduction or a relocation of the nutrient emissions from Lotsbroverket. / Detta examensarbete är ett uppdrag av VA-verket vid Mariehamns stad, Åland, med syfte att utreda effekter av en eventuell flyttning av avloppsreningsverket Lotsbroverkets utloppsledning. Inför en revidering av Lotsbroverkets miljötillstånd har Miljöprövningsnämnden vid Ålands landskapsregering ställt villkor på att tillståndshavaren skall utreda möjligheter till att avleda det renade avloppsvattnet till ett yttre vattenområde. Utloppsledningen mynnar i dagsläget i Svibyviken, vilken har klassificerats som ett inre vattenområde. Målsättningen med detta arbete är att belysa vilka ekologiska effekter näringsämnesutsläppet från Lotsbroverket har på primärrecipienten Svibyviken samt att undersöka några andra områdens lämplighet som mottagare av avloppsvattnet. Ett kustområdes utseende och form, det vill säga dess morfometri, avgör i stor utsträckning dess ekologiska förhållanden. För att få en god bild av det undersökta områdets morfometri digitaliserades området utifrån ett sjökort i digitaliseringsprogrammet Roots 3.3, varefter data bearbetades med GIS-verktyget ArcGIS 8.3. Avgränsning av kustområdet som helhet och av undersökta delområden gjordes enligt den topografiska flaskhalsmetoden, det vill säga så att kustens öppenhet mot utanförliggande hav eller vattenområde minimeras (Håkanson et al., 1984; Pilesjö et al., 1991). För arbetet har en processbaserad, dynamisk massbalansmodell för totalfosfor använts. Modellen har tagits fram för att eutrofieringseffekter i kustområden skall kunna studeras (Håkanson &amp; Karlsson, 2001). Vid användandet av modellen kan effekter av olika näringsämneskällor uppskattas och kvantifieras. Samtliga totalfosforflöden till, från och inom olika avgränsade områden har studerats och rangordnats. Modellsimuleringar har visat hur förändringar i något av fosfortillflödena inverkar på recipientens månadsmedelkoncentration av totalfosfor. Situationen för kväve har undersökts med hjälp av en statistisk/empirisk regressionsmodell mellan fosfor- och kvävehalt. För att belysa de ekologiska effekter som kan förväntas efter en förändring av Lotsbroverkets fosfor- och kväveutsläpp har statistiska/empiriska kopplingar gjorts mellan näringsämneskoncentrationer och ekologiska effektvariabler. Bra effektvariabler vid undersökning av eutrofieringseffekter är exempelvis klorofyllhalt, siktdjup samt syrgashalt i bottenvattnet. Dessa variabler har också använts i detta arbete. Resultaten visar att (1) närsaltskoncentrationerna i de studerade områdena i hög grad styrs av den allmänna eutrofieringsnivån i Östersjön, (2) att utsläppet av näringsämnen från Lotsbroverket inte inverkar på recipientens näringsstatus i någon stor utsträckning, (3) att Lotsbroverkets påverkan är störst på nuvarande recipient, Svibyviken, (4) och att påverkan sedan successivt minskar ju längre ut mot öppna havet utloppsledningen lokaliseras. Slutsatsen av utredningen är att en reduktion av Lotsbroverkets utsläpp eller nylokalisering av utloppsledningen inte kan förväntas ge någon omfattande förbättring av tillståndet i Svibyviken.

In recent years there is an increasing awareness of the importance of chiral phosphorus ligands in transition metal organometallic chemistry because of the utility of such complexes in homogeneous catalytic reactions. This thesis deals with synthetic, spectroscopic and X-ray crystallographic studies on ruthenium complexes of chiral and achiral P-N-P type ligands, known as "diphosphazanes", with emphasis on ruthenium carbonyl clusters. Several ruthenium carbonyl clusters have been synthesized and characterized by elemental analyses, ER and NMR (lH, nC and 3lP) spectroscopic data. In several instances, the molecular structures of the clusters have been confirmed by single crystal X-ray diffraction studies. Chapter 1 provides a brief overview of various types of chiral phosphorus ligands and general synthetic routes to diphosphazanes. A brief review of the transition metal chemistry of diphosphazanes and diphosphazane chalcogenides (published since 1994) is presented A review of the literature on the carbonyl clusters of the group-8 transition metals (Fe, Ru, Os) bearing mono- and diphosphines is also included in this chapter The scope and aim of the present investigation is outlined at the end of this chapter. Chapter 2 provides the results obtained in the present investigation and a detailed discussion of the spectroscopic and crystallographic data. The essential feature of the work is summarized at the end of the chapter. Chapter 3 gives a detailed account of the experimental procedure for the synthesis of the compounds and spectroscopic and analytical measurements. The experimental details of X-ray structure determination are also given in this chapter. To save space, the coordinates of the H-atoms and the calculated and observed structure factor tables are not included. In some cases, reference to CCDC deposition number is included. The references of the literature are compiled at the end of the thesis and are indicated in the text by appropriate numbers appearing as superscripts. The compounds synthesized in the present study are represented by bold Arabic numerals and are listed in Appendix I. The abbreviations employed in the thesis conform to those generally used in Chemical Abstracts.

Made available in DSpace on 2014-12-17T14:01:59Z (GMT). No. of bitstreams: 1 DanyheltonDFD.pdf: 1227676 bytes, checksum: c8754b4250e0bb6e5391c5ffbe8423a3 (MD5) Previous issue date: 2009-04-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Top-down (grazing) and bottom-up (nutrient, light) controls are important in freshwater ecosystems regulation. Relative importance of these factors could change in space and time, but in tropical lakes bottom-up regulation has to been appointed as more influent. Present study aimed to test the hypothesis that phytoplankton growths rate in Armando Ribeiro reservoir, a huge eutrophic reservoir in semi-arid region of Rio Grande do Norte state, is more limited by nutrient available then zooplankton grazing pressure. Bioassay was conduced monthly from September (2008) to August (2009) manipulating two levels of nutrients (with/without addition) and two level of grazers (with/without removal). Experimental design was factorial 2X2 with four treatments (X5), (i) control with water and zooplankton from natural spot ( C ), (ii) with nutrient addition ( +NP ), (iii) with zooplankton remove ( -Z ) and (iv) with zooplankton remove and nutrient addition ( -Z+NP ). For bioassay confection transparent plastic bottles (500ml) was incubate for 4 or 5 days in two different depths, Secchi`s depth (high luminosity) and 3 times Secchi`s depth (low luminosity). Water samples were collected from each bottle in begins and after incubates period for chlorophyll a concentration analysis and zoopalnktonic organisms density. Phytoplankton growths rates were calculated. Bifactorial ANOVA was performance to test if had a significant effect (p<0,005) of nutrient addition and grazers remove as well a significant interaction between factors on phytoplankton growths rates. Effect magnitude was calculated the relative importance of each process. Results show that phytoplankton growth was in generally stimulated by nutrient addition, as while zooplankton remove rarely stimulated phytoplankton growth. Some significant interactions happening between nutrient additions and grazers remove on phytoplankton growth. In conclusion this study suggests that in studied reservoir phytoplankton growth is more controlled by ascendent factors than descendent / A produ??o prim?ria dos ecossistemas aqu?ticos ? regulada por fatores ascendentes, (disponibilidade de luz e nutrientes), e por fatores descendentes (herbivoria). A import?ncia relativa desses fatores pode variar no tempo e no espa?o, mas em lagos tropicais tem sido sugerido que os fatores ascendentes s?o geralmente mais importantes. O presente estudo teve como principal objetivo testar a hip?tese de que o crescimento fitoplanct?nico no reservat?rio Armando Ribeiro Gon?alves, um grande reservat?rio eutr?fico na regi?o semi-?rida do Rio Grande do Norte, ? mais limitado pela disponibilidade de nutrientes do que pela press?o de herbivoria do zoopl?ncton. Bioensaios foram realizados mensalmente entre Setembro (2007) e Agosto (2008), manipulando-se dois n?veis de nutrientes (com/sem adi??o) e dois n?veis de herb?voros (com/sem remo??o). O desenho experimental foi do tipo fatorial 2X2 com quatro tratamentos (x5), (i) controle contendo a ?gua e o pl?ncton natural do ambiente ( C ), (ii) com adi??o de nutrientes ( +NP ), (iii) com remo??o de zoopl?ncton ( -Z ) e (iv) com remo??o de zoopl?ncton e adi??o de nutrientes ( -Z+NP ). Nos bioensaios foram incubadas garrafas pl?sticas transparentes de 500 mL por 4 ou 5 dias em duas profundidades distintas: na profundidade do disco de Secchi (alta luminosidade) e em uma profundidade 3x maior do que a anterior (baixa luminosidade). Amostras de ?gua foram coletadas de cada garrafa no inicio e ap?s o per?odo de incuba??o para an?lises das concentra??es de clorofila a e densidades de organismos zooplanct?nicos. Foi calculada a taxa de crescimento fitoplanct?nico. Uma ANOVA bifatorial foi realizada para testar se houve efeito significativo (p<0,05) da adi??o de nutrientes e da remo??o de herb?voros bem como uma intera??o significativa entre ambos os fatores sobre as taxa de crescimento do fitopl?ncton. A magnitude de cada efeito tamb?m foi calculada para quantificar a import?ncia relativa de cada processo. Os resultados mostram que o crescimento fitoplanct?nico foi geralmente estimulado pela adi??o de nutrientes enquanto a remo??o do zoopl?ncton raramente estimulou o crescimento fitoplanct?nico. Algumas intera??es significativas ocorreram entre os efeitos da adi??o de nutrientes e da remo??o de herb?voros sobre o crescimento fitoplanct?nico. Como conclus?o, esta pesquisa sugere que o crescimento fitoplanct?nico no reservat?rio estudado, ? mais fortemente controlado por fatores ascendentes do que por fatores descendentes