While hundreds of papers have been published on frustrated Lewis pairs (FLPs) – the combination of bulky Lewis acids and bases which cannot form adducts – few of these use aluminum-based Lewis acids. The research outlined in this thesis expands the small molecule activation chemistry of FLPs to include Al.Combinations of bulky phosphines and AlX3 (X = halide or C6F5) with CO2 leads to the rapid activation to form the complexes R3P(CO2)(AlX3)2 (R = otol, Mes). Subsequent treatment with ammonia borane (AB) results in the rapid reduction of the CO2 fragment to methanol after water quench. Subsequent reactivity studies have established that AB adducts of AlX3, which react with CO2, are key intermediates in this chemistry. Further studies with Mes3P(CO2)(AlX3)2 revealed that these can reduce exogenous CO2 to CO, along with the generation of Mes3P(C(OAlX2)2O)(AlX3) and [Mes3PX][AlX4]. Detailed experimental and theoretical mechanistic investigations outline a possible mechanism involving direct CO2 insertion into free AlX3, followed by nucleophilic attack by PMes3 resulting in the expulsion of CO. Reactions with olefins were also investigated. While addition products of the type R3P(CH2CH2)AlX3 could be obtained with ethylene, C–H bond activation occurred with bulkier olefins. The resulting allyl species underwent subsequent C–C bond forming reactions with other olefins or CO2. Hydrogen was also activated using PR3/AlX3 FLPs to form species of the general formula, [R3PH][(H)(AlX3)2] (X = I, C6F5). These were found to reduce unactivated olefins, generating the redistributed products [R3PH][AlX4] and RAlX2 (R = alkyl). Attempts to circumvent this redistribution and favour alkyl protonation, thus generating a catalytic hydrogenation catalyst, are also discussed. Finally, the activation of N2O was also examined. While addition products could be formed, unexpected aromatic or benzylic C–H bond activation chemistry occurred in the presence of excess Al. A radical reaction pathway is proposed

Increased floodplain and wetland restoration activity has raised concerns about potential impacts on the release of greenhouse gases (GHGs) to the atmosphere due to restored connectivity between aquatic and terrestrial ecosystems. Research has shown GHG fluxes from hydrologically active landscapes such as floodplains and wetlands vary spatially and temporally in response to primary controls including soil moisture, soil temperature, and available nutrients. In this study, we performed a semimonthly sampling campaign measuring GHG (CO2, CH4, and N2O) fluxes from six locations within a third-order stream floodplain. Site locations were based on dominant landscape positions and hydrologic activity along a topographic gradient including a constructed inset floodplain at the stream margin, the natural levee, an active slough, the general vegetated floodplain, a convergence zone fed by groundwater, and the upland area. Flux measurements were compared to abiotic controls on GHG production to determine the most significant factors affecting GHG flux from the floodplain. We found correlations between CO2 flux and soil temperature, organic matter content, and soil moisture, CH4 flux and pH, bulk density, inundation period length, soil temperature, and organic matter content. But minimal correlations between N2O flux and the measured variables. Spatially, our results demonstrate that constructed inset floodplains have higher global warming potential in the form of CH4 than any other site and for all other GHGs, potentially offsetting the positive benefits incurred by enhanced connectivity. However, at the reach scale, total CO2 flux from the soil remains the greater influence on climate since the area covered by these inset floodplains is comparatively much smaller than the rest of the floodplain. / Master of Science

Niedermoore sind durch Grundwasser beeinflusste Standorte, in denen Torf gebildet wird oder oberflächig ansteht. Sie emittieren durch mikrobiologische Prozesse Treibhausgase (THG). Wird der Grundwasserstand gesenkt, steigen Kohlendioxid und Lachgas Emissionen, während bei einer Anhebung vermehrt Methan emittiert wird. Weltweit wird davon ausgegangen, dass Moore 5 % der anthropogen verursachten Emissionen verursachen. Um THG-Emissionen entgegenzuwirken, wird die Anhebung des Grundwasserstandes diskutiert. Dies führt durch eingeschränkte Befahrbarkeit und geringeres Kulturartenspektrum zu einer kaum gegebenen Wirtschaftlichkeit. Es fehlt ein Vergleich der THG-Emissionen und der Rentabilität der Bewirtschaftungssysteme verschiedener Landnutzungssysteme für Niedermoorstandorte der gemäßigten Klimazone. Die bodenbürtigen THG-Emissionen wurden mit einer Metaanalyse zu Veröffentlichungen von THG-Messungen in Niedermooren der gemäßigten Klimazone ermittelt. Ebenfalls wurden die bewirtschaftungsabhängigen Emissionen ermittelt und zu Gesamtemissionen zusammengefasst. Für den Vergleich der Rentabilität der Bewirtschaftungssysteme wurden Kosten und Erlöse berechnet. Abschließend wurden Treibhausgasvermeidungskosten abgeschätzt Bei zunehmender Landnutzungsintensität und größeren Grundwasserflurabstand nahmen die Gesamt-THG-Emissionen zu. Durch die Bewirtschaftung verursachte Emissionen spielten im Vergleich zu den bodenbürtigen Emissionen kaum eine Rolle. Zur THG-Einsparung und der Torferhaltung sollte die Bewirtschaftung extensiviert werden. Im Rentabilitätsvergleich erwiesen sich intensive, im Vergleich zu extensive Bewirtschaftungssysteme ohne Förderung als wirtschaftlich. Subventionen und Förderungen um torf- und klimaschonende Praktiken zu unterstützen, sind unverzichtbar. Mit dieser Arbeit wurde erstmalig für Niedermoore ein systematischer Überblick über die Gesamt-THG-Emissionen und die Rentabilität gängiger Bewirtschaftungssysteme verschiedener Landnutzungssysteme gegeben. / Fens are sites influenced by the groundwater where peat is formed in or located in the upper soil layer. They emit greenhouse gases (GHG) through microbiological processes in which the main influencing factor is the groundwater level. The lowering of the groundwater level increases carbon dioxide and dinitrogen monoxide emissions, while higher groundwater levels lead to methane emissions. It is assumed that fens cause 5% of global anthropogenic GHG emissions. In order to save peat and reduce GHG emissions, rewetting fens has been discussed and applied. This leads to low profitable land use due to limited trafficability and cultivation options. There is a lack of comparison of management systems in different land use systems regarding GHG emissions and profitability on fenlands in the temperate climate zone. The soil-borne GHG emissions for the land use systems were identified with a meta-analysis of published measurements of GHG emissions on fenlands in the temperate climate zone. The GHG emissions due to cultivation and possible land use changes were identified and summarized as the overall emissions. Costs and revenues were calculated for comparability purposes of profitability of management systems. GHG abatement costs were estimated too. Results indicated that overall GHG emissions increase with higher land use intensity and deeper groundwater level. Management induced GHG emissions are negligible compared to the soil-borne emissions. Fenlands should be extensified to save peats and reduce GHG emissions. The comparison of profitability showed that management systems of intensive land use systems, in contrast to extensive land use systems, with the low groundwater level are broadly profitable without subsidies. Subsidies and grants are indispensable to promote peat-saving and climate-friendly practices. This thesis provides a systematic overview of overall GHG emissions and profitability of common management systems of fenlands.

Submitted by Leticia Schettini (leticia@ufrrj.br) on 2016-10-03T15:58:13Z No. of bitstreams: 1 2011 - Paula Fernanda Chaves Soares.pdf: 2114719 bytes, checksum: 6297f456308144b9c0a8b946d61316f4 (MD5) / Made available in DSpace on 2016-10-03T15:58:13Z (GMT). No. of bitstreams: 1 2011 - Paula Fernanda Chaves Soares.pdf: 2114719 bytes, checksum: 6297f456308144b9c0a8b946d61316f4 (MD5) Previous issue date: 2011-02-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPQ / The Histosols are characterized by high organic content, distinguishing this class from others in the Brazilian System of Soil Clasification. Because of this characteristic they are more fragile in face of agricultural use and management than mineral soils. The agricultural drainage is the most important practice that changes soil properties and it is the cause of subsidence, which impacts on other attributes. On the other hand, Histosols are an important natural reservoir of carbon in the soil. However, there are few studies on the dynamics of carbon and nitrogen and potential contribution of greenhouse gases as a result of agricultural usage. The study aims to identify changes in edaphic attributes and dynamics of carbon and nitrogen of Histosols in a floodplain environment in State of Rio de Janeiro, according to types of land use and agricultural management. Three areas with different managements were selected. Two areas are located in Macae municipality, under pasture and annual crop rotation, and the third in Santa Cruz, in Rio de Janeiro city, cultivated with cassava (Manihot esculenta). They were evaluated: chemical and physical attributes, including aggregate stability and specific attributes of Histosols; content soil organic matter (SOM), carbon in the fractions - humin (HUM-C), humic acid (HAF-C) and fulvic acid (C-FAF); stocks of C and N; and flux of gases CO2 and N2O from soil to atmosphere. In general, the area cultivated with cassava had the highest values for the exchangeable cations at all depths; in the first sampling the H value varied from 32.1 to 33.2 cmolc kg-1, and Ca from 20.4 to 15.7 cmolc kg-1. In the second sampling K and P (5.16 to 4.36 cmol c kg-1, and 4 mg kg-1, respectively) were highest in the cassava crop area. The levels of (SOM) were highest in the pasture for the two sampling periods, with values ranging from 306.3 to 249.0 g kg-1 (WB method) and 297.8 to 278,5 g kg-1 (oven method) for the first sampling, and from 303.2 to 153.9 g kg-1 (WB) and 322.9 to 176.1 g kg-1 (oven) in the second period, indicating that this usage is less aggressive to the soil. The physical properties of Histosols may be used to indicate degree of subsidence. Thus, the high values of particle density and bulk density (1.9 and 0.8 Mg m-3); the total volume of pores that ranged from 54 to 60% with the lowest values in the two samplings; and minimum residue and mineral material highest than other usages (0.49 to 0.44 cm and 85.1 cm-1 to 80.7%, respectively) in the cassava area point to the high subsidence ot these soil. As for SOM chemical fractionation, the C_HUM indicated that this fraction had highest expression in all areas. In the second sampling the cassava area showed the lowest values of C-HUM (79.05 to 76.27 g kg-1), followed by C_FAH (44.56 to 40.05 g kg-1) and C_FAF (20.37 to 14.36 g kg-1). The stocks of C and N were highest in the pasture area, indicating better preservation of SOM, with values from 72.93 to 117.12 mg kg-1 for C and from 8.35 to 2,67 mg kg-1 for N. The values of CO2-C flux were within the range of variation proposed by the IPCC, where the highest emission value corresponded to 0.09 Mg CO2 ha-1 day-1 in the pasture area. The values of N2O-N flux were lower than the emission rate proposed by the IPCC, with the highest value around 270 g N2O-N m-2 day-1 in the area with beans. In general, the area with pasture management stood up as management that caused the least damage to the Histosols properties, among the land use evaluated. / Os Organossolos caracterizam-se pelo alto teor de material org?nico, que distingue essa classe das demais no Sistema Brasileiro de Classifica??o de Solo. Ainda, por essa caracter?stica s?o solos mais fr?geis diante do uso e manejo agr?cola que solos com dom?nio de minerais. Dentre as pr?ticas que mais alteram as propriedades ed?ficas, a drenagem ? a mais importante e ? respons?vel pelo processo de subsid?ncia com impactos em v?rios atributos. Por outro lado, os Organossolos s?o importante reservat?rio natural de carbono no solo. Ainda assim s?o poucos os estudos sobre a din?mica de carbono e nitrog?nio e o potencial de contribui??o com gases de efeito estufa diante do manejo agr?cola. O estudo visa identificar altera??es nos atributos ed?ficos e na din?mica de carbono e nitrog?nio de Organossolos em ambiente de v?rzea no Estado do Rio de Janeiro, em fun??o de tipos de uso e manejo agr?cola. Foram selecionadas tr?s ?reas com manejos distintos. Duas ?reas localizam-se em Maca?, com pastagem e rota??o de culturas anuais, e a terceira em Santa Cruz, no Rio de Janeiro, com mandioca (Manihot esculenta). Foram avaliados: atributos qu?micos e f?sicos, incluindo estabilidade de agregados e atributos espec?ficos de Organossolos; teores de mat?ria org?nica do solo (MOS) e o teor de C nas fra??es humina (C-HUM), ?cido h?mico (C-FAH) e ?cido f?lvico (C-FAF); estoques de C e N; e fluxos dos gases CO2 e N2O do solo para a atmosfera. Em geral, a ?rea com mandioca apresentou os maiores valores para o complexo sortivo em todas as profundidades; na primeira coleta o H variou de 32,1 a 33,2 cmolc kg-1, e o Ca entre 20,4 e 15,7 cmolc kg-1. Na segunda coleta destacam-se os valores de K e P (5,16 e 4,36 cmolc kg-1 e 4 mg kg-1, respectivamente) tamb?m maiores na ?rea com mandioca. A MOS mostrou maior teor na ?rea de pastagem para as duas coletas, com valores variando entre 306,3 a 249,0 g kg-1 (m?todo WB) e 297,8 a 278,5 g kg-1 (m?todo da mufla) na primeira coleta, e para a segunda coleta de 303,2 a 153,9 g kg-1 (WB) e 322,9 a 176,1 g kg-1 (mufla), o que indica que esse manejo ? menos agressivo ao solo. As propriedades f?sicas dos Organossolos podem indicar o seu grau de subsid?ncia. Assim, os valores altos de densidade da part?cula e densidade do solo (em torno de 1,9 e 0,8 Mg m-3) mais o volume total de poros, que variou de 54 a 60% sendo os menores nas duas coletas, e o res?duo m?nimo e material mineral com valores maiores (0,49 a 0,44 cm cm-1 e 85,1 a 80,7%, respectivamente) indicam para a ?rea de mandioca maior grau de subsid?ncia. No fracionamento qu?mico da MOS o C_HUM indicou que essa fra??o teve maior express?o em todos as ?reas. Na segunda coleta a ?rea de mandioca apresentou os menores valores de CHUM (79,05 a 76,27 g kg-1) seguidos de C_FAH (44,56 a 40,05 g kg-1) e C_FAF (20,37 a 14,36 g kg-1). Os estoques de carbono e nitrog?nio foram mais altos no solo sob pastagem, indicando melhor conserva??o da MOS, com valores entre 117,12 e 72,93 Mg kg-1 para C e 8,35 e 2,67 Mg kg-1 para N. Os valores de fluxo de C-CO2 estiveram dentro da faixa de varia??o proposta pelo IPCC, em que o maior valor de emiss?o correspondeu a 0,09 Mg CO2 ha-1 dia-1 na ?rea de pastagem. Os valores de N-N2O foram menores que a taxa de emiss?o proposta pelo IPCC, com o valor mais elevado em torno de 270 ?g N-N2O m-2 dia-1 e na ?rea com feij?o. Em geral, a pastagem se destacou como o manejo que causou menor altera??o nas propriedades dos Organossolos, dentre as formas de uso da terra avaliadas.

Ziel der Arbeit ist die Gesamtbilanzierung der Treibhausgasemissionen eines Anbausystems unter Bewässerung auf einem Sandboden. Die dazu aufgestellte Treibhausgasbilanz basiert auf langjährigen Datenreihen zu Erträgen und Corg-Vorräten eines Dauerfeldversuchs sowie auf zweijährigen im Feldversuch durchgeführten N2O-Messungen. Die durchgeführten Untersuchungen zum Einfluss der Bewässerung auf die Corg-Vorräte zeigen, dass der Einsatz von mineralischem Stickstoffdünger und Bewässerung auf einem leichten Standort unter den klimatischen Bedingungen Nord-Ost-Deutschlands positive Effekte hat. Die N2O-Emissionen eines Sandbodens unter den klimatischen Bedingungen Brandenburgs sind sehr niedrig. Die Applikation von mineralischem Stickstoffdünger hat nur schwache und Bewässerung hat aufgrund der der hohen Bodendurchlüftung des Sandbodens keine Effekte auf die Höhe der N2O-Emissionen. Die direkten und indirekten Emissionen aus dem Maschinen- und Betriebsmitteleinsatz erhöhen sich bei Bewässerung und steigender Stickstoffdüngung deutlich. Bei den indirekten Treibhausgasemissionen nehmen die Emissionen der Herstellung des mineralischen Stickstoffdüngers einen bedeutenden Anteil der Gesamttreibhausgasemissionen ein. Bewässerung führt durch den erhöhten Dieselverbrauch hauptsächlich zu einer Erhöhung der direkten Emissionen. Unter Bewässerung kann jedoch ein Teil der Emissionen durch zunehmende Corg-Vorräte kompensiert werden. Somit sind in einigen Fällen die Gesamttreibhausgasemissionen pro Hektar bei Bewässerung geringer als ohne Bewässerung. Die aus Stickstoffdüngung und Bewässerung resultierenden Ertragserhöhungen führen dazu, dass die Gesamttreibhausgasemissionen bezogen auf die Ertragseinheit in den meisten bewässerten Varianten deutlich geringer sind als in den unbewässerten. Daraus lässt sich ableiten, dass Bewässerung auf einem Sandboden zu einer Verminderung der Treibhausgasemissionen beitragen kann. / The aim of this work is the estimation of the net greenhouse gas emissions by a greenhouse balance for an irrigated cropping system on a sandy soil in north-east Germany under various nitrogen fertilizer intensities. The balances are based on data of yields and SOC stocks of an irrigated long term field experiment as well as on results of N2O-measurements over two years. The results of the analysis of the long term response of irrigation and nitrogen fertilization have shown that irrigation and mineral nitrogen fertilization led to significant increases in yields and harvest residues. The increased carbon inputs from above ground harvest residues had positive effects on the SOC stocks. The results of N2O measurements indicated that N2O emissions from a sandy soil are very low. Mineral nitrogen fertilization had only marginal effects. Irrigation showed no effects on the amount of N2O emissions. On the one hand the analysis of the prepared greenhouse gas balances showed that irrigation and increased nitrogen fertilization lead to a strong increase of direct and indirect emissions from machinery and maintenance resource use. The indirect emissions of nitrogen fertilizer production took up a main part of the net greenhouse gas emissions. Irrigation mainly increased greenhouse gas emissions of fuel use and fuel production as well as the emissions of the machinery production. On the other hand the increasing SOC stocks especially in the fertilized variants under irrigation led to a compensation of a huge part of the additional emissions. Thus, in many cases the net greenhouse gas emissions per unit area was lower under irrigation. Due to the increased yields under irrigation the net greenhouse gas emissions per unit yield were lower than that under non-irrigated conditions.

In der vorliegenden Arbeit wird über 1,3-dipolare Cycloadditionen mit Lachgas (N2O) unter milden Reaktionstemperaturen (≈ RT) berichtet. N2O ist ein sehr unreaktives 1,3-dipolares Reagenz. Bisher in der Literatur durchgeführte 1,3-dipolare Cycloadditionen mit N2O benötigten immer sehr drastische und gefährliche Reaktionsbedingungen (bis zu 300°C und 500 atm.). Dabei entstanden nach einer (postulierten) einleitenden 1,3-dipolaren Cycloaddition von N2O an Olefine oder Alkine immer nur stickstofffreie Reaktionsprodukte. Durch den Einsatz von hochreaktiven Cycloalkinen als 1,3-Dipolarophile konnten erstmals 1,3-dipolare Cycloadditionen mit N2O bei deutlich milderen Bedingungen (–25°C bis +60°C) als den bisher bekannten durchgeführt werden. Dabei war es mit Cyclooctin und Cycloocten-5-in erstmals möglich, stabile und vollständig charakterisierbare Reaktionsprodukte zu erhalten, die alle drei Atome des addierten N2O-Moleküls enthalten. Mit 4,5-Didehydro-2,3,6,7-tetrahydro-3,3,6,6-tetramethylthiepin konnte sogar erstmals ein alpha-Diazoketon durch 1,3-dipolare Cycloaddition von N2O erhalten und dieses bei –25°C NMR-spektroskopisch untersucht werden. Diese alpha-Diazoketone entstehen aus der elektrocyclischen Ringöffnung der entsprechenden 1,2,3-Oxadiazole welche aus der Cycloaddition von N2O und dem eingesetzten Cycloalkin stammen. Mit alpha-substituierten Cyclooctinen konnten auch 1,3-dipolare Cycloadditionen mit N2O bei milden Temperaturen durchgeführt werden, um stickstofffreie Reaktionsprodukte zu erhalten.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The managedment of the pig manure, in the slurry or solid form (deep bedding), and how it is applied to the soil, in the surface or incorporated, must affect the dynamics of the C and the N in the soil. The objectives of this work were: 1) to evaluate the dynamics of the C and the N in soil and to evaluate the N supply to maize which were applied pig manure in the slurry and solid form, in no-tillage and minimum tillage system; and 2) to use the STICS model (BRISSON et al., 1998) to simulate the dynamics of N and water in the soil-plant system with the use of pig slurry in maize under no-tillage system. To reach the first objective, three experiments were realized. Two of them in the field conditions, during the period of 2002/03 in the Experimental Area of the UFSM/RS Soil Department in a typic Hapludult and one of them in laboratory conditions. The treatments consisted in the application or no application of pig manure in the slurry and solid form (deep bedding) on the crop oats residues with and without incorporation to the soil in the maize. Aiming to reach the second objective, a data set generated in the Experimental Area of the UFSM Soil Department during the period of 1998 to 2002, involving the N dynamics in the soil-plant system, with the use of pig slurry in notillage system was used. The gotten results had indicated that the N losses by NH3 volatilization were higher with the application of pig slurry than with the application of solid manure and that these losses decrease with the incorporation of the manure to the soil. The amounts of mineral N in the soil layer of 0-90 cm did not differ between the treatments with and without incorporation of the manure in spite of the lost N amount by volatilization has been higher in the treatment without incorporation. The incorporation of the manure to the soil did not increase the straw C decomposition and nor the N immobilization. The presence of the oats straw stimulated the immobilization of the ammoniacal N applied with the pig slurry. The solid manure presented low nitrogenous fertilizing otential to the maize when compared to the pig slurry in terms of the low mineralization rate of the organic N, present in the deep bedding. The N-N2O emission increased with the application of the pig slurry on the oats straw in relation to the system with straw and without pig slurry. The pig slurry ammoniacal 15N recovery by the maize in physiological maturation stage was only 14.9%. In the same period, only 49.2% of the ammoniacal 15N applied with the slurry pig slurry were recuperated in the soil and the plant (aerial part + roots), indicating that more than a half of the ammoniacal N applied with the pig slurry was lost through the volatilization, lixiviation and denitrification processes. The STICS model underestimates the amount of N lost by ammonia volatilization after the pig slurry application. The use of a factor in STICS to express the N losses by ammonia volatilization provided an improvement in the simulations of the N dynamics in the soil. The water dynamics in the soil layer of 0 - 60 cm was simulated by STICS with an error lower than 13.5%. These work results showed that the STICS reparametred model presents potential to be used in subtropical weather conditions in the simulation of the N and water dynamics in no-tillage system with the use of pig manure. / A forma como os dejetos de suínos são manejados, se na forma líquida ou sólida (cama sobreposta), e o modo de aplicação dos mesmos no solo, se na superfície ou incorporados, devem afetar a dinâmica do C e do N no solo. Os objetivos deste trabalho foram: 1) avaliar a dinâmica do C e do N no solo e o fornecimento de N ao milho com uso de dejetos de suínos na forma líquida e sólida, em sistema plantio direto e preparo reduzido do solo; e 2) utilizar o modelo STICS (BRISSON et al., 1998) para simular a dinâmica do N e da água no sistema solo-planta com o uso de dejetos líquidos de suínos em sistema plantio direto de milho. Para atingir o primeiro objetivo, foram realizados três experimentos, sendo dois em condições de campo, no período de 2002/03 na área Experimental do Departamento de Solos da UFSM/RS, em solo Argissolo Vermelho distrófico arênico, e um em condições de laboratório. Os tratamentos consistiram da aplicação ou não de dejetos de suínos na forma líquida e sólida (cama sobreposta), sobre os resíduos culturais de aveia com e sem incorporação ao solo, na cultura do milho. Com vistas ao alcance do segundo objetivo, foi utilizado um conjunto de dados gerados na área Experimental do Departamento de Solos da UFSM no período de 1998 a 2002 envolvendo a dinâmica do N no sistema solo-planta com o uso de dejetos líquidos de suínos em sistema plantio direto. Os resultados obtidos indicaram que as perdas de N por volatilização de NH3 foram maiores com a aplicação de dejetos líquidos de suínos do que com a aplicação de dejetos sólidos e que essas perdas diminuíram com a incorporação dos dejetos ao solo. As quantidades de N mineral na camada de 0-90 cm do solo não diferiram entre os tratamentos com e sem incorporação dos dejetos apesar da quantidade de N perdida por volatilização ter sido maior no tratamento sem incorporação. A incorporação dos dejetos ao solo não aumentou a decomposição do C da palha e nem a imobilização de N. A presença da palha de aveia estimulou a imobilização do N amoniacal aplicado com os dejetos de suínos. Os dejetos sólidos apresentaram baixo potencial fertilizante nitrogenado ao milho, comparado aos dejetos líquidos, em função da baixa taxa de mineralização do N orgânico presente na cama sobreposta. A emissão de N-N2O aumentou com a aplicação dos dejetos líquidos sobre a palha de aveia em relação ao sistema com palha e sem dejetos. A recuperação do 15N amonical dos dejetos líquidos pelo milho no estádio de maturação fisiológica foi de apenas 14,9%. Nesse mesmo período, apenas 49,2% do 15N amoniacal aplicado com os dejetos líquidos de suínos foram recuperados no solo e na planta (parte aérea + raízes), indicando que mais da metade do N amoniacal aplicado com os dejetos foi perdido através dos processos de volatilização, lixiviação e desnitrificação. O modelo STICS subestimou a quantidade de N perdida por volatilização de amônia, após a aplicação dos dejetos de suínos. O uso de um fator em STICS para expressar a perdas de N por volatilização de amônia proporcionou uma melhora nas simulações da dinâmica do N no solo. A dinâmica da água na camada 0 60 cm do solo foi simulada por STICS com um erro inferior a 13,5%. Os resultados desse estudo evidenciaram que o modelo STICS reparametrado apresenta potencial para ser utilizado em condições de clima subtropical na simulação da dinâmica do N e da água em sistema plantio direto com o uso de dejetos de suínos.

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In der vorliegenden Arbeit wird über 1,3-dipolare Cycloadditionen mit Lachgas (N2O) unter milden Reaktionstemperaturen (≈ RT) berichtet. N2O ist ein sehr unreaktives 1,3-dipolares Reagenz. Bisher in der Literatur durchgeführte 1,3-dipolare Cycloadditionen mit N2O benötigten immer sehr drastische und gefährliche Reaktionsbedingungen (bis zu 300°C und 500 atm.). Dabei entstanden nach einer (postulierten) einleitenden 1,3-dipolaren Cycloaddition von N2O an Olefine oder Alkine immer nur stickstofffreie Reaktionsprodukte. Durch den Einsatz von hochreaktiven Cycloalkinen als 1,3-Dipolarophile konnten erstmals 1,3-dipolare Cycloadditionen mit N2O bei deutlich milderen Bedingungen (–25°C bis +60°C) als den bisher bekannten durchgeführt werden. Dabei war es mit Cyclooctin und Cycloocten-5-in erstmals möglich, stabile und vollständig charakterisierbare Reaktionsprodukte zu erhalten, die alle drei Atome des addierten N2O-Moleküls enthalten. Mit 4,5-Didehydro-2,3,6,7-tetrahydro-3,3,6,6-tetramethylthiepin konnte sogar erstmals ein alpha-Diazoketon durch 1,3-dipolare Cycloaddition von N2O erhalten und dieses bei –25°C NMR-spektroskopisch untersucht werden. Diese alpha-Diazoketone entstehen aus der elektrocyclischen Ringöffnung der entsprechenden 1,2,3-Oxadiazole welche aus der Cycloaddition von N2O und dem eingesetzten Cycloalkin stammen. Mit alpha-substituierten Cyclooctinen konnten auch 1,3-dipolare Cycloadditionen mit N2O bei milden Temperaturen durchgeführt werden, um stickstofffreie Reaktionsprodukte zu erhalten.

L'effetto dei gas serra sul cambiamento climatico ha portato molti esperti a considerare la riduzione delle emissioni di gas serra come strategia per il riscaldamento globale. In particolare tale fenomeno è causato dall’anidride carbonica (CO2), metano (CH4) e il protossido di azoto (N2O). E 'ampiamente accettato che la principale fonte antropica di gas a effetto serra (tranne CO2) è dovuta alle attività agricole. Lo scopo di questo studio è quello di definire concetti e strumenti per facilitare il settore agricolo a ridurre le emissioni di gas serra. In particolare, abbiamo posto la nostra attenzione ai sistemi di misurazione delle emissioni dal suolo, testando un nuovo sistema (SASSFlux) e le sue caratteristiche a confronto con due strumenti ampiamente utilizzati (Bruel & Kjaer e gascromatografia). Inoltre abbiamo testato due modelli di simulazione (DNDC e SPACSYS) valutando i dati simulati e quelli misurati su un esperimento effettuato su lisimetri. In fine abbiamo applicato le conoscenze acquisite in pieno campo per la valutazione delle emissioni di CO2 e N2O con diversi concimi e lavorazione del terreno. La tesi si propone di fornire una visione completa dei diversi aspetti da affrontare nella valutazione delle emissioni di gas serra provenienti da diversi scenari di gestione agricola. / The effect of greenhouse gases (GHG) on climate change led many experts to consider the reduction of GHGs emissions as a crucial strategy to tackle the predicted global warming. In particular, atmospheric warming is caused mainly by carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). It is widely accepted that the main anthropogenic source of GHG (except CO2) is due to agriculture activities. The purpose of this study was to help define concepts and tools to facilitate agricultural sector to reduce greenhouse gas emissions. In particular we based our focus on measuring systems for CO2 emissions, testing the performance of novel system (SASSFlux) and its features in different condition with two widely used instruments (Bruel&Kjaer and gas chromatography). Moreover we testing two process-based models, DNDC and SPACSYS, evaluating their performance and the agreement between simulated and measured data on a experiment carried out on lysimeters. At the end we applied all the knowledge acquired on a field experiment evaluating CO2 and N2O emissions from different organic and mineral fertilizers and tillage. The complete thesis aims to provide a comprehensive view of the different aspects to be addressed in the assessment of GHG emissions from different scenarios of agricultural management.