Thesis (doctoral)--Landbouwuniversiteit Wageningen, 1995.

Nitrous oxide (N2O) emisison from paddy soil via the soil nitrification and denitrification processes makes an important contribution to atmospheric greenhouse gas concentrations. The soil N2O emission processes are controlled not only by biological, physical and chemical factors but also by farming practices. In recent years, modeling approach has become popular to predict and estimate greenhouse gas fluxes from field studies. In this study, the DeNitrification–DeComposition (DNDC) model were calibrated and tested by incorporating experimental data with the local climate, soil properties and farming management, for its simulation applicability for the irrigated rice system in Duy Xuyen district, a delta lowland area of Vu Gia-Thu Bon River Basin regions. The revised DNDC was then used to quantitatively estimate N2O emissions from rice fields under a range of three management farming practices (water management, crop residue incorporation and nitrogen fertilizer application rate). Results from the simulations indicated that (1) N2O emissions were significantly affected by water management practices; (2) increases in temperature, total fertilizer N input substantially increased N2O emissions. Finally, five 50-year scenarios were simulated with DNDC to predict their long-term impacts on crop yield and N2O emissions. The modelled results suggested that implementation of manure amendment or crop residue incorporation instead of increased nitrogen fertilizer application rates would more efficiently mitigate N2O emissions from the tested rice-based system. / Phát thải nitơ ôxít (N2O) từ canh tác lúa nước (thông qua quá trình nitrat hóa và phản nitrat hóa) đóng góp đáng kể vào tổng lượng khí nhà kính có nguồn gốc từ sản xuất nông nghiệp. Quá trình phát thải N2O là không chỉ phụ thuộc vào các yếu tố sinh-lý-hóa học mà còn phụ thuộc các phương pháp canh tác. Trong những năm gần đây, việc ứng dụng mô hình hóa nhằm tính toán và ước lượng sự phát thải khí nhà kính ngày càng trở lên phổ biến. Trong nghiên cứu này, số liệu quan trắc từ thí nghiệm đồng ruộng và dữ liệu về đất đai, khí hậu, biện pháp canh tác được sử dụng để kiểm nghiệm và phân tích độ nhạy của mô hình DNDC (mô hình sinh địa hóa). Sau đó, mô hình được sử dụng để tính toán lượng N2O phát thải trong canh tác lúa nước dưới các phương thức canh tác khác nhau (về chế độ tưới, mức độ vùi phụ phẩm, bón phân hữu cơ, phân đạm) tại huyện Duy Xuyên, thuộc vùng đồng bằng thấp của lưu vực sông Vu Gia-Thu Bồn. Kết quả kiểm định chỉ ra rằng (1) sự phát thải N2O bị ảnh hưởng đáng kể do sự thay đổi chế độ tưới; (2) nhiệt độ tăng và lượng phân bón N tăng sẽ làm tăng phát thải N2O. Kết quả mô phỏng về tác động lâu dài (trong 50 năm) của các yếu tố đến năng suất cây trồng và phát thải N2O cho thấy: Việc sử dụng phân hữu cơ và phụ phẩm nông nghiệp thay thế cho việc bón phân đạm sẽ giúp giảm phát thải N2O đáng kể.

This study resulted in a comparative analysis of greenhouse gas emissions (GHGE) for rice production with different infield rice straw management practices based on an experiment conducted in An Giang Province of Vietnam, during the autumn - winter season of 2016. Direct field GHGE was analyzed based on in-situ measurement and the total direct and indirect GHGE were estimated by applying the life cycle assessment using Ecoinvent3 database which is incorporated in SIMAPRO software. The experiment was conducted based on a completely random design with three treatments and three replications. The three treatments are [T1] Incorporation of straw and stubbles treated with Trichoderma; [T2] Incorporation of stubbles and removal of straw; and [T3] In-field burning straw. Closed chamber protocol and gas chromatography (SRI 8610C) was used to measure and analyse CH4 and N2O. CH4 emission rate was not significantly different (p>0.05) among the three treatments during sampling dates except on the days 17 and 24 after sowing (DAS). N2O emission rate was not significantly different (p>0.05) either. However, there were high variations of N2O emission after the dates of urea applied. Direct field emissions of CH4, N2O and CO2 equivalent (CO2eq) are not significantly different among the three treatments, but the amount of CO2eq per kg straw in T1 of incorporating rice straw treated with Trichoderma is significantly higher than in T3 of in-field burning straw. LCA based analysis resulted in total GHGE in the range of 1.93-2.46 kg CO2-eq kg-1 paddy produced consisting of 53-66% from direct soil emissions. Incorporationof straw treated with Trichoderma did not indicate the improvement of paddy yield. However, the organic matter, N-NH4+, and N-NO3- of this treatment was higher than those of the other researched treatments. This research was just conducted in one crop season, however, the results have initial implications for the other crop seasons. / Nghiên cứu này phân tích phát thải khí nhà kính từ sản xuất lúa theo các biện pháp quản lý rơm rạ khác nhau dựa vào thí nghiệm được thực hiện ở vụ Thu Đông năm 2016 tại tỉnh An Giang, Việt Nam. Lượng phát thải khí nhà kính từ đất đã được phân tích dựa vào kết quả đo đạt tại ruộng và tổng lượng phát thải khí nhà kính trực tiếp và gián tiếp được ước tính bằng phương pháp vòng đời sử dụng cơ sở dữ liệu Ecoinvent3 gắn kết với phần mềm SIMAPRO. Thí nghiệm được bố trí hoàn toàn ngẫu nhiên gồm 3 nghiệm thức và 3 lần lặp lại. Các nghiệm thức gồm [T1] vùi rơm và rạ với Trichoderma, [T2] lấy rơm ra khỏi ruộng và vùi rạ và [T3] đốt rơm. Kỹ thuật buồng kín (closed chamber protocol) và máy sắc ký khí (SRI8610C) được sử dụng để đo đạt và phân tích khí CH4 và N2O. Tốc độ phát thải khí CH4 không khác biệt giữa ba nghiệm thức, ngoại trừ kết quả ở lần lấy mẫu 17 và 24 ngày sau sạ. Tốc độ phát thải N2O cũng không có sự khác biệt giữa các nghiệm thức. Tuy nhiên, tốc độ phát thải biến động rất lớn sau các ngày bón phân đạm. Lượng phát thải trực tiếp từ ruộng của CH4, N2O và CO2 tương đương (CO2-eq) không có sự khác biệt giữa ba nghiệm thức, nhưng lượng CO2-eq/kg rơm ở nghiệm thức vùi rơm và rạ với Trichoderma (T1) cao hơn nghiệm thức đốt rơm (T3). Kết quả phân tích LCA cho thấy lượng phát thải khí nhà kính dao động trong khoảng 1,93 – 2,46 kg CO2-eq/kg lúa với 53 – 66% lượng phát thải trực tiếp từ trong đất. Vùi rơm rạ với Trichoderma chưa cải thiện được năng suất lúa. Tuy nhiên, phần trăm chất hữu cơ và hàm lượng đạm hữu dụng trong đất của nghiệm thức này cao hơn so với hai nghiệm thức còn lại của thí nghiệm. Nghiên cứu này chỉ mới được thực hiện một vụ, nhưng đã mang lại nhiều kết quả có thể ứng dụng cho các vụ sau.

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.

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.

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.

Energie und Rohstoffe auf Basis von Biomasse gelten als wichtiger Beitrag, um den anthropogen begründeten Klimawandel zu mindern. Diese publikationsbasierte Arbeit analysiert, inwiefern Aussagen über Vorzüglichkeit von Biomassenutzung im direkten Vergleich oder auch in komplexeren wirtschaftlichen Nutzungssystemen durch Unsicherheiten in den Treibhausgasemissionen (THG) oder durch die Anwendung der Bewertungsmethodik beeinflusst werden. Eine Fallstudie zur stationären Biostromerzeugung aus der Vergasung von Pappelhackschnitzeln zeigte mittels Monte-Carlo-Analyse, dass dieser Biostrom trotz Unsicherheiten weniger THG emittiert bzw. sogar Kohlendioxid sequestrieren könnte. Die zweite Fallstudie analysierte Biomassenutzung im Systemzusammenhang. Sie bezog neben THG-Emissionen als Bewertungskriterien sowohl den Bedarf an Agrarfläche als auch an fossilen Ressourcen mit ein. Für das Beispiel der Häuserdämmung mittels Hanffasern oder Styropor konnte aus den drei Kriterien auch unter Berücksichtigung mehrerer Szenarien keine eindeutige Vorzugslösung der Biomassenutzung abgeleitet werden. Basierend auf dem Produktivitätskonzept stellt der dritte Beitrag mit CUDe (Carbon Utilization Degree) einen Ansatz vor, wie die Nutzungseffizienz des in der Biomasse bereitgestellten Kohlenstoffs bewertet werden könnte. THG-Minderungsrechnungen erfordern eine fundierte Kenntnis der Methode als auch des Produktionssystems in seinem regionalen Kontext. Als Landnutzungseffekte sollten neben Änderungen im Bodenkohlenstoffgehalt auch Unterschiede in Lachgas-Hintergrundemissionen von annuellen gegenüber mehrjährigen Kulturen berücksichtigt werden. Trade-Offs sprechen dafür, Biomassenutzungssysteme nicht nur hinsichtlich Klimawirksamkeit zu optimieren. Ergänzend könnte Kohlenstoff auch als Ressource betrachtet und mit Effizienzkriterien bewertet werden. Biomassenutzung ließe sich so optimieren, dass gemeinsam mit Klimaschutz weitere aktuelle Handlungsfelder adressiert werden. / Biomass-based energy and materials are considered important for the mitigation of human-induced climate change and as relevant bioeconomic feedstock. This publication-based dissertation aims to contribute to the discussion about the reliability of mitigation assessment of biomass applications in an increasingly bio-based, low-carbon economy that also fulfils sustainability constraints of resource conservation. It analysed how preference of biomass use in direct comparison as well as in larger economic context is affected by single uncertainties as well as by mitigation calculation methods. A case study on stationary bioelectricity generation from poplar wood chip gasification with a Monte Carlo approach showed that such bioelectricity could emit less greenhouse gases (GHG) or even sequester carbon despite existing uncertainties. The second case study analysed biomass use in a systemic context. Besides GHG emissions also resource demand of cropland and fossil fuels were used to assess two strategies to isolate buildings. From the three criteria, none of the strategies would clearly be preferred. The third case study presented an approach to assess the efficiency of biomass carbon use (CUDe; Carbon Utilization Degree) and applied it exemplarily to a biogas and a hemp insulation system. GHG mitigation analyses of biomass use must be performed with profound knowledge of the methodology and the biomass system in its regional context. In land use change assessment, emissions resulting from deviating nitrous oxide baselines from annual and perennial crops should be considered in addition to carbon stock changes. Optimization of biomass applications only with respect to GHG emissions (or other single criteria) might overlook trade-offs. However, multi-criteria analyses might yield ambiguous results. A resource-efficient viewpoint on biogenic carbon use instead of its sole GHG implications might help to foster a transformation to bio-based, low-carbon economies.

No description available.

Kleine Moleküle wie Treibhausgase, aber auch Distickstoff und Disauerstoff stehen im Fokus der chemischen Forschung. Solche Moleküle sind durch ihr Vorkommen in der Atmosphäre ubiquitär vorhanden, preiswert und könnten als Synthesebausteine für die Darstellung von komplexeren Molekülen verwendet werden. In dieser Arbeit wurde die Reaktion koordinativ ungesättigter Diketiminato-Nickelkomplexe ([LNi] Komplexe) mit kleinen Molekülen untersucht. Zunächst wurden die Mechanismen der N2-Aktivierung durch reduzierte [LtBuNiI]- und [LMe6NiI] Komplexe miteinander verglichen. Dabei konnte das distickstoffaktivierende Schlüsselintermediat identifiziert und strukturell charakterisiert werden. Weiter wurden die N2-Komplexe [(LtBuNiI)( 1 1 N2)] bzw. K2[(LtBuNiI)( 1 1 N2)], die Vorläufer für [LNiI]- und [LNi0]– Komplexfragmente darstellen, hinsichtlich ihrer Potentials zur Aktivierung der reaktionsträgen Treibhausgase SF6 und NF3 untersucht. Über Reaktionen von Übergangsmetallkomplexen mit NF3 war bis dahin noch nicht berichtet worden; zur Umsetzung von SF6 existierten wenige Publikationen, in denen aber sehr viele mechanistische Fragen offengeblieben sind. Die Mechanismen der SF6- und NF3-Aktivierung wurden durch Kombination einer Vielzahl von ex- und in situ Analysen beleuchtet. Im Falle der SF6 Aktivierung gelang es zudem, ein Nickel(I)-Intermediat zu isolieren. Ein Produkt beider Systeme war der Fluorido-Nickel(II)-Komplex [LtBuNiIIF], dessen Reaktionsverhalten ebenfalls studiert wurde. Doch nicht nur Komplexe mit Nickelatomen in niedrigen Oxidationsstufen erwiesen sich für die Aktivierung kleiner Moleküle geeignet, sondern auch kationische [LtBuNiII(D)]+-Komplexe. Diese Nickel(II)-Komplexe reagierten mit fluorierten Molekülen, N2O sowie O2, was bemerkenswert ist, da Nickel(II)-Komplexe üblicherweise inert gegenüber O2 sind. Im Zuge der O2-Studien wurde ein metastabiler Oranoperoxidkomplex isoliert und strukturell charakterisiert, was beispiellos in der Literatur ist. / Current research focuses on the activation of small molecules like greenhouse gases, thermodynamically stable molecules like N2 and kinetically stabilized molecules like O2, which are all abundant in the atmosphere. Thus, it appears to be alluring to use them as cheap and readily available building blocks for the synthesis of value-added compounds. This dissertation deals with the reaction of low-coordinate diketiminate nickel complexes [LNi] and such small molecules. Initially, the mechanisms of the dinitrogen activation by reduced [LtBuNiI] and [LMe6NiI] complexes were studied. As a result, the key intermediate [(LtBuNiI)x(3 Br)xKx] (x > 1) was identified and structurally characterized. Subsequently, the nickel complexes [(LtBuNiI)( 1 1 N2)] and K2[(LtBuNiI)( 1 1 N2)], which represent sources for [LtBuNiI] and [LtBuNi0]– moieties, were applied to the activation of the inert, but very efficient greenhouse gases SF6 and NF3. Prior to these investigations, no transition metal complex had been reported to react with NF3. Publications dealing with the conversion of SF6 had been scarce, too, while at same time, the mechanisms involving its activation had been speculative. The mechanisms of the NF3 and SF6 activation reactions were deduced combining numerous ex-situ and in situ analytical methods. In case of the SF6 activation, even an intermediate could be isolated. In both systems, the nickel fluoride complex [LtBuNiIIF] was formed and its reaction behaviour was also studied. Furthermore, not only [LtBuNiI]- and [LtBuNi0]– moieties proved to be reactive towards small molecules, but also cationic [LtBuNiII(D)]+ complexes, which were specifically developed for this purpose. The reactions of [LtBuNiII(D)]+ complexes with fluorinated molecules (e. g. PhF, NF3), O2 and N2O were studied. In course of the O2 activation, a metastable organoperoxide complex was isolated and structurally characterized, which is unparalleled in the literature.