Im Rahmen der vorliegenden Arbeit wurde eine neuartige Methode und die entsprechenden Katalysatoren für die heterogen katalysierte Gasphasen-Epoxidation von Propen entwickelt und optimiert. Das Propen wurde an FeOx/SiO2-Katalysatoren mit N2O als Oxidationsmittel epoxidiert. Die Katalysatoren wurden mittels XRD, TEM, XPS, Physi- und Chemisorption, TPR/TPO, TPD und IR untersucht und charakterisiert. Der Einfluß der Reaktionsbedingungen auf die Oxidationsergebnisse wurde bestimmt und Untersuchungen zum Reaktionsablauf durchgeführt. Es wurden Selektivitäten zu Propenoxid von 40-70%, bei Propenumsätzen von 3-12%, erreicht. Die maximalen erzielten PO-Ausbeuten betrugen über 5%, und sind damit den berichteten Ergebnisse aus der Literatur überlegen.

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.

Stickoxide (NOx) und Distickstoffoxid (N2O) entstehen bei der Verbrennung fossiler Brennstoffe in Gegenwart von Luft und gehören auf Grund ihrer toxischen bzw. klimaschädigenden Wirkung zu den Luftschadstoffen. In der Arbeit wird die simultane Reduktion von NOx und N2O an nickelbeladenen Zeolithen vom Typ H-ZSM-5 mit Propen als Reduktionsmittel untersucht. Die experimentellen Arbeiten wurden unter realitätsnahen Bedingungen mit einem Katalysatorbett durchgeführt. Der Einfluss des Nickelgehalts und der Acidität des zeolithischen Trägermaterials auf Umsatz und Selektivität der Reduktion werden diskutiert. Ausgehend von den gewonnenen Ergebnissen wird ein wahrscheinlicher Reduktionsmechanismus vorgeschlagen. / Nitric and nitrous oxides (NOx, N2O) are part of toxic and climate damaging airborne pollutants and will be produced by combustion of fossil fuels in present of air. In this work the simultaneous reduction of NOx and N2O with propene has been investigated using nickel impregnated zeolites of type H-ZSM-5 as catalytic active material. The experiments have been done using one catalyst bed and a synthetic gas mixture according to real existing environment conditions. The influence of nickel content as well as acidity of the support material on conversion and selectivity have been discussed. Using the experimental results a possible reaction mechanism has been submitted.

Le dioxyde de carbone (CO2), le méthane (CH4) et l’oxyde nitreux (N2O) sont trois des principaux gaz à effet de serre (GES) influençant les changements climatiques (IPCC, 2014). La variabilité des concentrations fluviales de ces GES est souvent liée à l’utilisation du territoire, aux caractéristiques internes de la rivière et au régime hydrique. Cependant, peu d’études se sont penchées sur l’influence de ces facteurs sur la dynamique couplée de ces trois gaz au fil des saisons. Pour cette étude, nous avons mesuré les concentrations et flux de CO2, CH4 et N2O le long d’une rivière tempérée : la Rivière du Nord, une fois par saison durant trois années consécutives. Le long du bassin versant de cette rivière la géologie diffère entrainant un changement radical d’utilisation du territoire. De fortes différences saisonnières ont été observées : les concentrations de CO2 et N2O étaient plus élevées en hiver, tandis que celles de CH4 étaient plus importantes l’été. Les sites de confluence majeure avaient les émissions les plus élevées. Les concentrations ont été influencées par l’utilisation des terres, les plus fortes concentrations de tous les GES se trouvant où les activités urbaines et agricoles sont les plus intensives. Cependant, la variabilité spatiale fut minimisée pendant les périodes de fort débit. Bien que l’utilisation du territoire ait influencé la variabilité spatiale des concentrations le long de la rivière, les changements de températures et de régime hydrique provoqués par les saisons ont influencé, respectivement, l’importance relative des gaz et leurs concentrations et émissions globales. / Carbon dioxide (CO2), methane (CH4), and nitrous dioxide (N2O) are three of the main greenhouse gases (GHGs) that influence climate change (IPCC, 2014). Variability in the riverine concentrations of these three GHGs is often related to land use, within river features, and hydrologic regimes. However, few studies have looked at the interacting influence of these factors on the coupled dynamics of these gases across seasons. Here, we measured CO2, CH4, and N2O concentrations and fluxes along a 146.6 km stretch of the main stem of a north temperate river, with a change in geology resulting in a sharp shift in land use once per season for three consecutive years. Strong seasonal differences in gas concentrations were observed: CO2 and N2O were both higher overall during winter but were occasionally undersaturated, whereas summer had the highest concentrations of CH4. Sites of major confluence had the highest emissions, acting as vents. Concentrations were influenced by land use, with the highest concentrations of all gases found in the lower reaches where urban and agricultural activity are most intensive. However, spatial variability was minimized during periods of high flow when the river acted more like a pipe. This suggests that how major gases are coupled is largely a function of differential processes across seasons. Although land use influenced the spatial variability in concentrations along the river, seasonal changes in temperature influenced the relative importance of the gases, and hydrology mediated their overall concentrations and emissions.

No description available.

Indiana University-Purdue University Indianapolis (IUPUI) / Riparian buffers have well documented capacity to remove nitrate (NO3-) from runoff and subsurface flow paths, but information on field-scale N2O emission from these buffers is lacking. This study monitored N2O fluxes at two agricultural riparian buffers in the White River watershed (Indiana) from December 2009 to May 2011 to assess the impact of landscape and hydrogeomorphologic factors on emission. Soil chemical and biochemical properties were measured and environmental variables (soil temperature and moisture) were monitored in an attempt to identify key drivers of N2O emission. The study sites included a mature riparian forest (WR) and a riparian grass buffer (LWD); adjacent corn fields were also monitored for land-use comparison. With the exception of net N mineralization, most soil properties (particle size, bulk density, pH, denitrification potential, organic carbon, C:N) showed little correlation with N2O emission. Analysis of variance (ANOVA) identified season, land-use (riparian buffer vs. crop field), and site geomorphology as major drivers of N2O emission. At both study sites, N2O emission showed strong seasonal variability; the largest emission peaks in the riparian buffers (up to 1,300 % increase) and crop fields (up to 3,500 % increase) occurred in late spring/early summer as a result of flooding, elevated soil moisture and N-fertilization. Nitrous oxide emission was found to be significantly higher in crop fields than in riparian buffers at both LWD (mean: 1.72 and 0.18 mg N2O-N m-2 d-1) and WR (mean: 0.72 and 1.26 mg N2O-N m-2 d-1, respectively). Significant difference (p=0.02) in N2O emission between the riparian buffers was detected, and this effect was attributed to site geomorphology and the greater potential for flooding at the WR site (no flooding occurred at LWD). More than previously expected, the study results demonstrate that N2O emission in riparian buffers is largely driven by landscape geomorphology and land-stream connection (flood potential).

Irish agriculture is becoming increasingly regulated, with restrictions on fertiliser application rates and stocking rates to reduce nitrate (NO₀⁻) leaching losses. However these regulations have been, to date, based on minimal field research. The purpose of this study was to determine the actual leaching losses of nitrate from Irish dairy pasture at a range of stocking rates, and to investigate the effectiveness of the nitrification inhibitor DCD at reducing nitrate leaching losses where these are deemed excessive. In grazed pastures, a major source of leached nitrate is the urine patch, where a high rate of N is applied in one application. This trial recorded the losses from urine and non-urine areas of pasture separately. Nitrate leaching losses from three soils were recorded using lysimeters at Johnstown Castle, Co. Wexford, over two years. Total nitrate losses were higher from the freely drained Clonakilty and Elton soils than from the heavy Rathangan soil. Mean nitrate losses from urine patches ranged from 16 - 233 kg nitrate-N / ha⁻¹, and were reduced by up to 53% when DCD was applied. DCD also reduced peak and mean nitrate-N concentrations in many cases. In addition, DCD halved the nitrous oxide (N₂O) emission factor on the Rathangan soil, caused increases in pasture N content, and increased herbage yield in some treatments. The distribution of urine patches under dairy grazing was recorded using GPS at Kilworth, Co. Cork. Cows were also found to deposit 0.359 urine patches per grazing hour. A model was produced to predict field-scale nitrate leaching losses from dairy pasture at a range of stocking rates. At 2.94 cows per hectare, the highest stocking rate, annual field N loss was below 34 kg nitrate-N ha⁻¹, mean drainage N concentrations were below 5.65 mg nitrate-N L⁻¹ (the EU drinking water guideline value), and the worst-case-scenario autumn peak concentration did not exceed 21.55 mg nitrate-N L⁻¹ (above the EU Maximum Allowable Concentration (MAC) but below the World Health Organisation (WHO) drinking water limit). DCD reduced total annual field N loss by 21% (a conservative estimate), and also reduced mean and peak nitrate concentrations. Provided fertiliser application rates are at or below 291 kg N ha⁻¹, and based on current legislative values for drinking water quality, this trial does not support any blanket restrictions on the stocking rate of Irish dairy farms. However where particularly high water quality is required, DCD shows potential as a useful tool to achieve low nitrate concentrations.

New Zealand’s 5.3 million strong dairy herd returns approximately 106 million litres of urine to pasture soils daily. The urea in that urine is rapidly hydrolysed to ammonium (NH₄⁺), which is then nitrified, with denitrification of nitrate (NO₃⁻) ensuing. Nitrous oxide (N₂O), a potent greenhouse gas (GHG), is produced via nitrification and denitrification, which are enzyme-catalysed processes mediated by soil microbes. Thus microbes are linked intrinsically to urine patch chemistry. However, few previous studies have investigated microbial dynamics in urine patches. Therefore the objective of these four experiments was to investigate the effects on soil microbial communities of cow urine deposition. Methods used included phospholipid fatty acid (PLFA) analyses of microbial community structure and microbial stress, dehydrogenase activity (DHA) assays measuring microbial activity, and headspace gas sampling of N₂O, ammonia (NH₃) and carbon dioxide (CO₂) fluxes. Experiment 1, a laboratory study, examined the influence of soil moisture and urinary salt content on the microbial community. Both urine application and high soil moisture increased microbial stress, as evidenced by significant changes in PLFA trans/cis and iso/anteiso ratios. Total PLFAs and DHA showed a short-term (< 1 week) stimulatory effect on microbes after urine application. Mean cumulative N₂O-N fluxes were 2.75% and 0.05% of the nitrogen (N) applied, from the wet (70% WFPS) and dry (35% WFPS) soils, respectively. Experiment 2, a field trial, investigated nutrient dynamics and microbial stress with plants present. Concentrations of the micronutrients, copper, iron and molybdenum, increased up to 20-fold after urine application, while soil phosphorus (P) concentrations decreased from 0.87 mg kg ⁻¹ to 0.48 mg kg⁻¹. Plant P was also lower in urine patches, but total PLFAs were higher, suggesting that microbes had utilised the available nutrients. Microbial stress again resulted from urine application but, in contrast to experiment 1, the fungal biomass recovered after its initial inhibition. Studies published during the course of this thesis reported that hippuric acid (HA) and its hydrolysis product benzoic acid (BA) significantly reduced N₂O-N emissions from synthetic cow urine, thus experiment 3 investigated this effect using real cow urine. Cumulative N₂O-N fluxes were 16.8, 5.9 and 4.7% of N applied for urine (U) alone, U+HA and U+BA, respectively. Since NH₃-N volatilisation remained unchanged, net gaseous N emissions were reduced. Trends in total PLFAs and microbial stress were comparable to experiment 1 results. Experiment 4 studied HA effects at different temperatures and found no inhibition of N₂O-N fluxes from HA-amended urine. However, mean cumulative N₂O-N fluxes were reduced from 7.6% of N applied at 15–20°C to 0.2% at 5–10°C. Total cumulative N emissions (N₂O-N + NH₃-N) were highest at 20°C (17.5% of N applied) and lowest at 10°C (9.8% of N applied). Microbial activity, measured as potential DHA, increased with increasing temperature. This work has clearly shown that the stimulation and inhibition of the soil microbial community by urine application are closely linked to soil chemistry and have significant impacts not only on soil nutrient dynamics but also on N₂O-N emissions and their possible mitigation.

No description available.

Made available in DSpace on 2011-05-04T12:36:15Z (GMT). No. of bitstreams: 0 Previous issue date: 2010 / Em inúmeras ações humanas ocorrem emissões de gases que podem contribuir sobre maneira para o aumento na concentração dos gases estufa, dentre eles o óxido nitroso, acarretando danos ambientais locais e globais. Na busca de contribuir para o entendimento das causas para as mudanças climáticas globais há necessidade de compreender e conhecer os fluxos de óxido nitroso emitidos por diversos setores da atividade humana, inclusive em Estações de Tratamento de Esgoto. Aliando à técnica aspectos ambientais importantes a serem considerados no planejamento para implantação de uma tecnologia de tratamento de esgotos e proporcionando uma integração de campos de conhecimento, o estudo tem como objetivo analisar a correlação entre a aeração e a emissão de óxido nitroso em sistema de tratamento de esgotos. Tendo como metodologia o estudo de caso em Estação de Tratamento de Esgotos na Região Serrana do Estado do RJ, a pesquisa é caracterizada como pesquisa bibliográfica documental, exploratória e descritiva, com análises realizadas em laboratório. Este estudo é original em países tropicais, sendo o único estudo anterior feito na Universidade de New Hampshire / EUA em 1995. Visa, portanto, contribuir com a atualização de dados referentes às Mudanças Climáticas, possibilitando o aprofundamento futuro do tema. / In many human actions occurring gas emissions that can contribute significantly to the increased concentration of greenhouse gases, among them the oxide, causing environmental damage locally and globally. In seeking to contribute to the understanding of the causes of global climate change need to know and understand the flow of nitrous oxide emitted by various sectors of human activity, including waste treatment stations. Combining the technical environmental aspects to be considered in planning for deployment of a technology for treating wastewater and providing an integration of fields of knowledge, the study aims to analyze the correlation between the aeration and the emission of nitrous oxide system in wastewater treatment. Since the methodology as a case study in Station Sewage Treatment in the mountainous region of the state of RJ, the search is characterized as documentary literature, exploratory and descriptive, with analysis performed in the laboratory. This study is unique in tropical countries, the only previous study of the University of New Hampshire / USA in 1995. Aim, therefore contribute to the updating of data to climate change, enabling the further development of the theme.