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.

Methane (CH4) is included in the direct greenhouse gases listed in the Kyoto protocol. The composting of anaerobic digestion (henceforth AD) material is a source of CH4. CH4 is the major contributor to overall CO2 emissions. Therefore, it is important to know the formation of this gas from different stages and substrates of the composting process. This study investigated CH4, CO2 and O2 profiles in two open-windrows in composting plants treating AD material. One composting windrow was turned one a week; whereas another was turned twice a week using a special windrow turner. To assess the gaseous formation in the composting windrows, CH4, CO2 and O2 volume concentrations were measured at different depths. Active aeration has been considered as a method to reduce CH4 generation during composting. However, our results showed that frequent turned windrow generated more CH4 than less turned windrow. The highest CH4 concentrations were found at a depth of 1 m, and were 45% and 37% for 2 times a week turned windrow and 1 time a week turned windrow respectively. Gas concentrations of CH4, O2 and CO2 in both windrows differed. Concentrations of CO2 and CH4 increased with depth, whereas concentration of O2 decreased from the surface to the lowest point. The O2 and CO2 are important factors in determining whether the windrows are anaerobic or aerobic. / Khí mê tan (CH4) là một trong những khí nhà kính được liệt kê trong nghị định thư Kyoto. Quá trình ủ phân compost từ các chất thải của hầm ủ biogas là nguồn phát sinh loại khí này. Khí mê tan đóng góp chủ yếu trong tổng lượng khí nhà kính phát thải vào khí quyển. Do đó, những hiểu biết về quá trình hình thành loại khí này trong các giai đoạn khác nhau của quá trình ủ phân compost từ chất thải hầm ủ biogas là rất quan trọng. Nghiên cứu này tìm hiểu sự phát thải khí CH4, CO2 và O2 trong 2 luống ủ ngoài trời tại các nhà máy xử lý rác thải hữu cơ bằng phương pháp kỵ khí. Luống ủ 1 được đảo trộn một lần một tuần trong khi luống ủ số 2 được đảo trộn 2 lần 1 tuần. Để đo đạc lượng khí phát thải từ các luống ủ phân compost, nồng độ các khí CH4, CO2 và O2 được đo ở các độ sâu khác nhau. Việc cung cấp khí oxy được coi như là một biện pháp để làm giảm sự hình thành khí mê tan. Tuy nhiên, kết quả đo đạc của chúng tôi chứng minh rằng việc đảo trộn thường xuyên phát thải nhiều khí mê tan hơn ít đảo trộn. Nồng độ khí mê tan cao nhất 45% và 37% đo được ở khoảng cách 1m từ bề mặt đối với luống ủ đảo trộn hai lần và một lần. Nồng độ các khí CH4, CO2 và O2 khác nhau ở hai luống trong thí nghiệm. Nồng độ khí CH4 và CO2 tăng theo độ sâu, trong khi O2 giảm theo độ sâu. Nồng độ khí CO2 và O2 đóng vai trò quyết định luống ủ được cung cấp đủ oxy cho quá trình phân hủy hiếu khí hay không.

Die vorliegende Dissertation präsentiert eine detaillierte quantenchemische Untersuchung der H-Abstraktion von Methan durch MgO und Li dotiertes MgO. Motiviert wurde die durch das UniCat-Excellenz-Cluster, welches sich zum Ziel gesetzt hat, die oxidative Kupplung von Methan (OCM) im Detail zu verstehen. Basierend auf der Hypothese, dass Li+O•– Spezies für den H-Abstraktion Schritt verantwortlich sind, wurden kleine kationische MgO- und Li dotierte MgO-Cluster (die O•– Sites modellieren) untersucht. Zur Erstellung von möglichst realen Gasphasen-Modell-Systemen, wurde die globalen Minima der Gasphasencluster mittels eines genetischen Algorithmus bestimmt. Zum Vergleich wurden auch die Strukturen von neutralen MgO-Cluster bestimmt, um eventuelle strukturelle Unterschiede zu erkennen. Anschließend wurden die optimierten Cluster in Bezug auf ihre Eignung zur C-H-Bindungsaktivierung von Methan untersucht. Die Verwendung von kleinen Cluster-Größen ermöglicht es, die Reaktion im Detail zu studieren und verschiedene Methoden der Berechnung zu vergleichen. Die Ergebnisse für die kleinen Cluster wurden anschließend mit realistischeren Modellen verglichen, die eine genauere Beschreibung der Li dotierten Oberflächen ermöglichen, wie zum Beispiel non-embedded und embedded-Cluster und slab Modelle. Unerwartete Ergebnisse für die Betrachtung der Li+O•– Spezies haben zur Untersuchung von zusätzliche Arten von Defekten in MgO (wie niedrig koordinierten O2-Seiten, O-Leerstellen mit unterschiedlicher Ladung und Verunreinigungen) geführt, die als aktive Zentren in OCM fungieren können. Insbesondere wurden morphologische Defekte und verschiedene Arten von F Zentren untersucht. Die Aktivierung von Methan an defekten MgO-Oberflächen wurde innerhalb eines Cluster-Ansatzes untersucht und durch periodische Berechnungen mittels periodic slab models verifiziert. Die Ergebnisse wurden mit vorhandenen experimentellen Daten verglichen. / This work presents a detailed quantum chemical (mostly DFT) study of H abstraction from methane by MgO and Li doped MgO. It is motivated by the UniCat effort to understand the oxidative coupling of methane (OCM). Based on the hypothesis that an Li+O•– species is responsible for the H abstraction step in OCM small cationic MgO and Li doped MgO clusters (which model O•– sites) were investigated. Because we were interested in real gas phase model systems the global minimum structures of (MgO)n+ and LiO(MgO)n-1 clusters were first determined (by means of genetic algorithm) and then used in subsequent reactivity studies. To check if there are any structural differences between neutral and cationic MgO clusters the neutral species were studied as well. After structure determination, the activation of methane by the O•– radical sites was investigated. The small cluster sizes enabled to study the reaction in detail and to compare different methods of calculations. The results were verified by comparison with more realistic models that mimic Li doped MgO surface, like non-embedded and embedded clusters and slab models. However, unexpected results for the Li+O•– sites led to the consideration of additional types of sites in MgO that may be active for OCM – such as low-coordinated O2- sites, O vacancies with different charge and impurity defects. In particular morphological defects and different types of F centers were investigated. Methane activation by defective MgO surface was studied by a cluster approach and then followed by periodic calculations on periodic slab models. The results were compared to existing experimental data.

Automatische Melksysteme (AMS) gelten als jüngste Innovation auf dem Gebiet der Melktechnik und weisen im Vergleich mit konventionellen Melkständen eine Reihe von Besonderheiten auf. Um die Kühe zum freiwilligen und regelmäßigen Besuch des Melksystems anzuhalten, sind optimale mikroklimatische Bedingungen in der Melkbox notwendig. Die Analyse der mikroklimatischen Bedingungen in AMS erfolgte in einem Betrieb mit zwei parallel arbeitenden AMS und 110 melkenden Kühen. Dabei wurden die Parameter Luftqualität in der Melkbox und im Stall, Geräuschbelastung innerhalb der Melkbox während des Melkens sowie Verschmutzungsgrad und Keimgehalt an relevanten Punkten des AMS untersucht. Um die jahreszeitlichen Einflüsse auf das Stallklima zu kennzeichnen erfolgten die Untersuchungen im März 2002, Juni 2002 sowie Januar 2003. Eine besondere mikroklimatische Situation in der Melkbox konnte in den Analysen für die Stallluftparameter Kohlendioxid und Methan festgestellt werden. Dabei wurden erhöhte Konzentrationen immer dann beobachtet, wenn sich eine Kuh in der Melkbox befand. Die Bauweise des AMS im Kopfbereich der Melkbox konnte als entscheidender Grund für die hohen Konzentrationen der Gase ermittelt werden, da dadurch der Luftaustausch mit der Umgebung behindert wird. Die Geräuschkulisse für die Kühe innerhalb der Melkbox erwies sich während der Eutervorbereitung als besonders belastend, da der Schallpegel hier am höchsten war und gleichzeitig eine Frequenzverschiebung in den höherfrequenten Bereich festzustellen war. Ein erster Ansatz der Beschreibung der hygienischen Zustände in einem AMS erfolgte mit Hilfe von digitalen Bildern, welche an den Schnittstellen zwischen Tier, Endprodukt und Technik gemacht wurden. Der visuell wahrnehmbare Verschmutzungsgrad ließ sich in Beziehung zu gleichzeitig erfassten Tupferproben und darin isolierten Keimen setzen. Eine Verbesserung bzw. Anpassung der mikroklimatischen Situation innerhalb von AMS erscheint als notwendig, um eine ausreichende Motivation der Kühe zum Besuch der Melkbox zu erreichen. / Automatic milking systems (AMS) are considered as the most recent innovation in the area of milking technology. In comparison with conventional milking parlour they show a set of specific characteristics. Optimal microclimatic conditions in the milking box are necessary to motivate the cows to visit the milking system voluntarily and regularly. The analysis of the microclimatic conditions in AMS took place on a farm with two AMS working parallel and 110 lactating cows. The parameters examined were: the air quality in the milking box and in the barn, the noise load within the milking box during milking as well as the degree of pollution and the germ load at relevant points of the AMS. To mark the seasonal influences on the climate within the barn, the investigations took place in March 2002, June 2002 as well as January 2003. A special microclimatic situation in the milking box was noticed in the analyses for the barn air parameters carbon dioxide and methane. Whenever a cow was in the milking box, increased concentrations were observed. The construction method of the AMS in the head area of the milking box was determined as main reason for the high concentrations of gases, since this impedes the interchange of air with the environment. The sound load for the cows within the milking box was particularly heavy during the preparation of the udder. The sound level was highest during the cleaning of the udder and the frequencies shifted into the higher range. The description of the hygienic conditions in an AMS was first approached by means of digital pictures, which were made at the interfaces between animal, final product and technology. The visually perceptible degree of pollution could be set in relation to Dab RPR, which were taken at the same time like the digital pictures, and isolated germs therein. An improvement and/or an adjustment of the microclimatic situation within AMS appears necessary in order to achieve a sufficient motivation of the cows to go into the milking box.

In den Pflanzenzellwänden befindliche Polysaccharide stehen dem Prozess nur bedingt als Energiequelle zur Verfügung, da diese in einem Komplex mit Lignin verknüpft sind. Um diese Substanzen für den Biogasprozess verfügbar zu machen und demnach den Substratumsatz bzw. die Prozesseffizienz zu erhöhen, sind geeignete Stoffe oder Techniken einzusetzen bzw. zu entwickeln. In dieser Arbeit wurde zielführend der Einsatz von unterschiedlichen Enzympräparaten in drei verschiedenen Prozessstufen bei ausgewählten Energiepflanzen mit variierender Häcksellänge untersucht. Anhand von Enzymaktivitätsbestimmungen konnten Enzympräparate für die einzelnen Stufen selektiert werden. Die ausgewählten Enzyme wurden einzeln oder in Mischung während der Silierung, direkt vor dem Biogasprozess sowie während des Biogasprozesses zum Substrat dotiert und dieses nach der jeweiligen Vorbehandlung in Batch-Gärtests vergoren. Neben der Biogas- und Methanausbeute wurde zur Bewertung der Enzymleistung der Abbau an Lignocellulose sowie die Freisetzung an niedermolekularen Kohlenhydraten ermittelt. Zusätzlich wurde das Quellen der Lignocellulose mit Hilfe eines Wasserzusatzes in Form einer Vorhydrolyse als Vorbehandlungsmethode mit allgemein positivem Ergebnis geprüft. Das Ziel der verbesserten Substratumsetzung bei Mais und Roggen und folglich einer Erhöhung der Biogasproduktion wurde durch den Zusatz ausgewählter Enzympräparate erreicht. Es konnten Grundlagen bezüglich der Wirkung von Enzymen in Biogasprozessen geschaffen werden, anhand derer deutlich wurde, dass besonders die enzymatische Behandlung in den der Methanisierung vorgelagerten Prozessstufen weiterzuentwickeln ist. / Polysaccharides of plant cell walls are of limited digestibility due to their cross-linking to lignin. In order to make the molecules available for the biogas process and thus increase the substrate utilization and process efficiency appropriate substances or techniques are needed. It was therefore the aim of this work to investigate the effects of different enzyme preparations in three digestion process stages. Selected energy plants with varying degrees of particle sizes (chopping lengths) were used as digester feedstock. Enzyme preparations for the different process stages were chosen by enzyme assays. The selected enzymes were added to the feedstock during the ensiling, directly before the biogas process or during the biogas process separate or in mixtures. Pre-treated substrates were subsequently digested in batch fermentation tests. Beside the biogas and methane yield the degradation degree of lignocellulose and the release of low molecular carbohydrates were investigated for evaluating the enzyme performance. Additionally, the swelling of lignocellulose caused by addition of water in a pre-hydrolysis process was examined as a method of pre-treatment, with generally positive results. The aim of an improved substrate conversion of maize and rye and thus an enhanced biogas production by enzymatic pretreatments was achieved. Scientific fundamentals regarding the impact of enzymes on biogas processes were established. Enzymatic pretreatments in process steps before methanation showed potential for further developments.

University, Diss., 2005--Heidelberg.

Clean post-discharge nitrogen plasma and nitrogen plasma with different traces have been focus of scientists for more than 50 years and there were published many articles on theme active discharge, post-discharge, processes and reactions. It is possible to create kinetic models from all these information and then calculate concentrations of elements in atomic form. This diploma thesis is focused on measuring of concentration of atomic nitrogen for different conditions (decay time, pressure, admixture). The titration method by nitric oxide in post-discharge was used to determinate of concentration of atomic nitrogen. All experimental results were obtained by the optical emission spectroscopy. Optical emission spectra were taken in the range of 300-600 nm. DC discharge was created in a quartz tube in a flowing regime. The flowing regime was chosen for this experiment because of better time resolution of decay time, order in milliseconds. Decay time was in the range of 16 – 82 ms for individual experiments. Nitrogen flow was 400 mln/min. Nitrogen oxide flow was in the range of 0-10 mln/min and it was added at the selected post-discharge time. Trace of methane was 0,006 % of the whole volume. Total gas pressure was set on values from 500 to 4000 Pa. The output of discharge was set on constant value of current 150 mA and the output has changed according to the amount of pressure. Nitrogen first positive, second positive and first negative spectral systems, NO spectral system and NO2* spectral system were recognized in all measured spectra. Absolute concentration of atomic nitrogen was specified by the method of titration of NO. Traces of methane increase dissociation of molecular nitrogen and therefore increase the concentration of atomic nitrogen. This thesis brings new results into longtime research of moon Titan and new results into study of processes in nitrogen-methane plasma.

Die Konzentrationen der Treibhausgase (THG) Kohlendioxid (CO2), Methan (CH4) und Lachgas (N2O) haben ein Niveau erreicht, welches mit sehr hoher Wahrscheinlichkeit seit 800.000 Jahren nicht vorgekommen ist (Stocker et al. 2013).

Methane (CH4) source of Greenhouse Gases should be considered; CH4 is formed by composting under anaerobic conditions. Using microbial Methane oxidation is a solution with low cost and effective. In this study, 27 bio-filters and 18 laboratory-scale bioreactors were used to investigate the potential for CH4 removal in biogas. The CH4, Dinitrogen monoxide (N2O) and Carbon dioxide (CO2) concentrations at the inlet and outlet of the air purifier were measured by gas chromatography. The results showed that the CH4 concentration decreased in experiments while the CO2 and N2O content increased in all experiments. An experiment was conducted with 1 kg of biofilter material with the input of 800 ppm CH4 contained in a 5-liter flask for 49 hours containing. The results also showed that the CH4 concentration decreased by 71% after 20 hours and N2O was formed in the reactor. / Mê-tan (CH4) là nguồn khí gây nên hiệu ứng nhà kính cần được quan tâm, khí CH4 được sinh ra trong quá trình ủ vi sinh trong điều kiện kị khí. Một giải pháp với chi phí thấp là sử dụng vi sinh vật oxy hóa khí CH4 cố định trên giá thể là vật liệu sử dụng trong thiết bị lọc sinh học. Trong nghiên cứu này, 27 thiết bị lọc sinh học trên thực tế và 19 bình lọc tại phòng thí nghiệm đã được sử dụng nhằm mục đích khảo sát khả năng loại bỏ CH4 có trong khí sinh học. Nồng độ khí CH4, N2O và CO2 ở đầu vào và đầu ra bể lọc khí được đo đạc bằng phương pháp sắc ký khí. Kết quả cho thấy nồng độ khí CH4 giảm sau khi qua hệ thống lọc sinh học ở một số bình, trong khi nồng độ khí CO2 và N2O lại tăng lên ở tất cả các bình. Khi khảo sát khả năng oxi hóa CH4 ở nồng độ 800 ppm của 1kg vật liệu thiết bị lọc sinh học chứa trong bình phản ứng thể tích 5L với thời gian 49 giờ. Kết quả cho thấy nồng nồng độ CH4 giảm 71% sau 20 giờ. Tuy nhiên, N2O đã được ghi nhận có hình thành trong bình phản ứng đó.

Im Laborversuch konnte der positive Einfluss einer thermobarischen Vorbehandlung auf die Hydrolysier- und Vergärbarkeit von Rinderfestmist und Rindergülle nachgewiesen werden. Die Laborergebnisse wurden innerhalb eines theoretischen Modells in den Praxismaßstab übertragen, um den Einfluss auf Treibhausgasemissionen, Energiebilanz und Ökonomie zu bewerten. Die Vorbehandlungstemperaturen im Labor lagen zwischen 140 und 220°C in Schritten von 20 K und einer Vorbehandlungszeit von jeweils 5 Minuten. Die höchste Methanmehr¬ausbeute von 58 % konnte bei einer Temperatur von 180°C ermittelt werden. Das Auftreten von Inhibitoren und nicht vergärbaren Bestandteilen führte bei einer Aufbereitungstemperatur von 220°C zu Methanausbeuten, die geringer waren als die des unaufbereiteten Einsatzstoffes. In einer erweiterten Analyse konnte ein funktioneller Zusammenhang zwischen der Methanausbeute nach 30 Tagen und der Methanbildungsrate und -ausbeute während der Beschleunigungsphase gezeigt werden. Mittels einer Regressionsanalyse der so ermittelten Werte wurde nachgewiesen, dass die optimale Aufbereitungstemperatur 164°C ist und die minimale größer als 115°C zu sein hat. Treibhausgasemissionen und Energiebilanz wurden im Rahmen einer Ökobilanz nach ISO 14044 (2006) ermittelt, sowie eine Kosten-Nutzen-Analyse durchgeführt. Dazu wurde eine Anlage zur thermobarischen Vorbehandlung entwickelt und innerhalb eines Modells in eine Biogasanlage integriert. Weiterhin wurde in diesem Modell Maissilage durch Rinderfestmist und / oder Rindergülle als Einsatzstoff ersetzt. Rinderfestmist, ein Einsatzstoff mit hohem organischen Trockenmassegehalt, der ohne Vorbehandlung nicht einsetzbar wäre, erreichte eine energetische Amortisationszeit von 9 Monaten, eine Vermeidung in Höhe der während der Herstellung emittierten Treibhausgase innerhalb von 3 Monaten und eine ökonomische Amortisationszeit von 3 Jahren 3 Monaten, wohingegen Rindergülle keine positiven Effekte zeigte. / Hydrolysis and digestibility of cattle waste as feedstock for anaerobic digestion were improved by thermobarical treatment in lab-scale experiments. The effects of this improvement on greenhouse gas emissions, energy balance and economic benefit was assessed in a full-scale model application. Thermobarical treatment temperatures in lab-scale experiments were 140 to 220°C in 20 K steps for a 5-minute duration. Methane yields could be increased by up to 58 % at a treatment temperature of 180°C. At 220°C, the abundance of inhibitors and other non-digestible substances led to lower methane yields than those obtained from untreated material. In an extended analysis, it could be demonstrated that there is a functional correlation between the methane yields after 30 days and the formation rate and methane yield in the acceleration phase. It could be proved in a regression of these correlation values that the optimum treatment temperature is 164°C and that the minimum treatment temperature should be above 115°C. The theoretical application of a full-scale model was used for assessing energy balance and greenhouse gas emissions following an LCA approach according to ISO 14044 (2006) as well as economy. A model device for thermobarical treatment has been suggested for and theoretically integrated in a biogas plant. The assessment considered the replacement of maize silage as feedstock with liquid and / or solid cattle waste. The integration of thermobarical pretreatment is beneficial for raw material with high organic dry matter content that needs pretreatment to be suitable for anaerobic digestion: Solid cattle waste revealed very short payback times, e.g. 9 months for energy, 3 months for greenhouse gases, and 3 years 3 months for economic amortization, whereas, in contrast, liquid cattle waste did not perform positive replacement effects in this analysis.