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Methane (CH4) is the primary constituent of natural gas and a significant contributor to global climate change, accounting for 11% of all U.S. greenhouse gas emissions. With the advent of hydraulic fracturing technology, production of natural gas from shale gas reserves has increased by 35% from 2005 to 2013. Fugitive CH4 emissions attributed to venting or leakage across the life cycle of natural gas systems have also increased, making the climate benefits ascribed to natural gas questionable when compared to oil and coal. This dissertation reports the results of three studies that improve our knowledge of the environmental and political ramifications of continued investment in and consumption of natural gas fuels. Using bottom-up flux chamber techniques we made direct measurements of CH4 emissions from 100 natural gas leaks in cast iron distribution mains within Metro Boston, MA in order to assess the nature of the distribution of gas leak size and constrain estimates of fugitive CH4 emissions across leak-prone urban distribution infrastructure. We find that the distribution of leak size is skewed, a small fraction of ‘superemitter’ leaks contribute disproportionate CH4 emissions, and CH4 flux at leak sites is not an indicator of safety. Next, we use the lens of urban natural gas infrastructure systems and apply an ecological analytical framework to identify dysfunctions in and opportunities for coordinated urban infrastructure management in Boston, MA. We find that there are real physical and fiscal constraints to retrofitting and expanding aging, urban infrastructure in U.S. cities. Achieving sustainable, resilient urban infrastructure requires active participation by all stakeholders as well as coordination within and between stakeholder groups. Finally, we introduce the term ‘unleakable carbon’ to refer to the uncombusted carbon-based gases associated with fossil fuel systems and demonstrate that in particular the unleakable carbon associated with natural gas constitutes a potentially large and heretofore unrecognized factor in estimating usable portions of Earth’s fossil fuel reserves. We demonstrate that unless unleakable carbon is curtailed, roughly 80 – 100% of our global natural gas reserves must remain underground if we hope to limit warming to 2 °C from 2010 to 2050.

[EN] Climate change, a resultant effect of greenhouse gas emissions, is a worldwide concern because its continuation is having significant impacts on people, natural resources and economic conditions around the world. The root cause of this recent past and projected climate change is now recognised to be the warming potential of a number of greenhouse gases that, by absorbing terrestrial infrared radiation, raise the temperature of the troposphere and with it, global surface temperatures. The major greenhouse gases are water vapour, carbon dioxide, methane, nitrous oxide and fluorinated gases. While carbon dioxide receives the most attention as a factor which causes global warming, methane also cause significant radiative forcing. Methane is only second to carbon dioxide in its contribution to global warming and its emissions are caused by both natural and anthropogenic actions. Human activities such as intensive livestock farming are the primary cause of the increased methane concentrations in the atmosphere, being ruminants the animals which create large amounts of methane via fermentation of feeds in the rumen. During this physiological digestive process, hydrogen is released by some microbes during fermentation of forage and is used by methanogenic Archaea (methanogens) to convert carbon dioxide to methane, which is released through eructation, normal respiration and small quantities as flatus. Rumen fermentation of cattle contributes the most towards the greenhouse effect through methane emission followed by sheep, goats and buffalos, respectively. Several techniques have been developed to quantify methane emissions from ruminants - indirect calorimetry, sulphur hexafluoride tracer technique and in vitro gas production technique - and some strategies for reduction of methane emissions from the rumen have been described - defaunation treatment, vaccine and dietary composition -. The initial topics of this research were: design the experiments with goats because there are not many reports about methane emissions in these animals; investigate the influence of dietary composition (carbohydrates) as a strategy for reduction methane emissions from the rumen; and use the indirect calorimetry as method to quantify methane production. Consequently, three experiments were performed. Murciano-Granadina goats during mid or late lactation were used. Diets were mixed rations that differed in the inclusion of cereal or fibrous by-products. The effect of diet was studied on milk yield, digestibility, rumen parameters, energy partitioning, carbon and nitrogen balance, substrate oxidation and methane productions. In the first experiment, gas exchange was measured using a face mask which was fixed to the head of the goat by a rubber band; a sample of exhaled gas was stored in a gas collection bag which was connected to an analyzer, and it measured the concentration of O2, CO2 and CH4 from the air. This first experiment replaces corn grain with beet pulp and the amount of methane recovered was 19.6 and 29.7 g/day, respectively. In the other two experiments, gas exchange was measured by a head box designed for small ruminants where the goat introduced the whole head and a specific software automatically recorded concentrations of O2, CO2 and CH4 from the exhaled air continuously throughout the day. The second experiment involved two diets with high and low level of starch and no differences were found on methane emission (28.5 g/day). The experiment number three replaces ingredient by ingredient like in the experiment number one. Here, barley grain was replaced with orange pulp or soybean hulls and no differences were found, with an average methane production value of 41 g/day. The metabolizable energy intake during the three experiments was 1279 kJ/kg of BW0.75 and day on average, and the efficiency use of metabolizable energy intake for milk production was 0.6. / [ES] El cambio climático es una preocupación de ámbito mundial debido a que su perpetuación en el tiempo está teniendo un impacto significativo sobre las personas, los recursos naturales y las condiciones económicas de todo el mundo. La causa fundamental de este fenómeno es el potencial de calentamiento de una serie de gases de efecto invernadero que, mediante la absorción de la radiación infrarroja terrestre, elevan la temperatura de la troposfera y, con ella, las temperaturas superficiales de la Tierra. Los principales gases de efecto invernadero son el vapor de agua, el dióxido de carbono, el metano, el óxido nitroso y los gases fluorados. El metano, después del dióxido de carbono, es el gas que más repercusión tiene sobre el calentamiento global y sus emisiones son causadas tanto por acciones naturales como humanas. Actividades antropogénicas tales como la ganadería intensiva son la principal causa de aumento de las concentraciones de metano en la atmósfera, siendo los rumiantes los animales que mayores cantidades de metano generan a través de la fermentación de alimentos que se produce en el rumen. Las emisiones de metano del ganado vacuno son las que principalmente contribuyen al efecto invernadero seguido de las ovejas, las cabras y los búfalos, respectivamente. Se han descrito diferentes técnicas para medir las emisiones de metano de los rumiantes - la calorimetría indirecta, la técnica del marcador con hexafluoruro de azufre y la técnica de producción de gas in vitro - y, además, se han mencionado algunas estrategias para reducir las emisiones de metano - la defaunación, las vacunas y la composición de la dieta -. Los puntos clave de esta Tesis fueron: diseñar los experimentos con cabras, debido a que no hay muchas investigaciones sobre emisiones de metano en estos animales; estudiar la influencia de la composición de la dieta (hidratos de carbono) como una posible estrategia para la reducción de las emisiones de metano del rumen; y utilizar la calorimetría indirecta como método para cuantificar la producción de metano. Se realizaron tres experimentos. Se utilizaron cabras de la raza Murciano-Granadina en mitad o final de la lactación. Las dietas eran raciones mixtas que diferían en la inclusión de cereal o subproductos fibrosos. El efecto de la dieta se estudió en la producción de leche, la digestibilidad, los parámetros del rumen, la partición de energía, el balance de carbono y nitrógeno, la oxidación de nutrientes y las producciones de metano. En el primer experimento, el intercambio de gases se midió utilizando una mascarilla que se fijó a la cabeza de la cabra con una goma; se almacenó una muestra de gas exhalado en una bolsa de recogida de gas que estaba conectada a un analizador, y se midió la concentración de O2, CO2 y CH4 del aire. En este primer experimento se reemplazó el grano de maíz con pulpa de remolacha y la cantidad de metano recuperado fue del 19,6 y 29,7 g/día, respectivamente. En los otros dos experimentos, el intercambio de gases se midió mediante una urna o cajón diseñado para pequeños rumiantes, donde la cabra introducía toda la cabeza y un programa informático grababa automáticamente las concentraciones de O2, CO2 y CH4 del aire exhalado de forma continua a lo largo del día. El segundo experimento consistió en dos dietas con alto y bajo nivel de almidón y no se encontraron diferencias en la emisión de metano (28,5 g/día). En el tercer experimento se sustituyó ingrediente por ingrediente como en el experimento número uno. El grano de cebada se sustituyó por pulpa de naranja o cascarilla de soja y tampoco se encontraron diferencias, con un valor promedio de la producción de metano de 41 g/día. La energía metabolizable ingerida durante los tres experimentos fue de 1279 kJ/kg de peso metabólico (PV0.75) y día de promedio, y la eficiencia de utilización de la energía metabolizable ingerida para la producción de leche fue de / [CAT] El canvi climàtic és una preocupació d'àmbit mundial ja que la seua perpetuació en el temps està tenint un impacte significatiu sobre les persones, els recursos naturals i les condicions econòmiques de tot el món. La causa fonamental d'aquest fenòmen és el potencial d'escalfament d'una sèrie de gasos d'efecte hivernacle que, mitjançant l'absorció de la radiació infraroja terrestre, eleven la temperatura de la troposfera i, amb ella, les temperatures superficials de la Terra. Els principals gasos d'efecte hivernacle són el vapor d'aigua, el diòxid de carboni, el metà, l'òxid nitrós i els gasos fluorats. El metà, després del diòxid de carboni, és el gas que més repercussió té sobre l'escalfament global i les seues emissions són causades tant per accions naturals com humanes. Activitats antropogèniques com ara la ramaderia intensiva són la principal causa d'augment de les concentracions de metà a l'atmosfera, sent els remugants els animals que més quantitats de metà generen a través de la fermentació d'aliments que es produeix al rumen. Les emissions de metà dels bovins són les que principalment contribueixen a l'efecte hivernacle seguit de les ovelles, les cabres i els búfals, respectivament. S'han descrit diferents tècniques per mesurar les emissions de metà dels remugants - la calorimetria indirecta, la tècnica del marcador amb hexafluorur de sofre i la tècnica de producció de gas in vitro - i, a més, s'han esmentat algunes estratègies per reduir les emissions de metà - la defaunació, les vacunes i la composició de la dieta -. Els punts clau d'aquesta Tesi van ser: dissenyar els experiments amb cabres, pel fet que no hi ha moltes investigacions sobre emissions de metà en aquests animals; estudiar la influència de la composició de la dieta (hidrats de carboni) com una possible estratègia per a la reducció de les emissions de metà del rumen; i utilitzar la calorimetria indirecta com a mètode per quantificar la producció de metà. Es van realitzar tres experiments. S'utilitzaren cabres de la raça Murciano-Granadina a la meitat o final de la lactació. Les dietes eren racions mixtes que diferien en la inclusió de cereal o subproductes fibrosos. L'efecte de la dieta es va estudiar en la producció de llet, la digestibilitat, els paràmetres del rumen, la partició d'energia, el balanç de carboni i nitrogen, l'oxidació de nutrients i les produccions de metà. En el primer experiment, l'intercanvi de gasos es va mesurar utilitzant una màscara que es va fixar al cap de la cabra amb una goma; es va emmagatzemar una mostra de gas exhalat en una bossa de recollida de gas que estava connectada a un analitzador, i es va mesurar la concentració d'O2, CO2 i CH4 de l'aire. En aquest primer experiment es va reemplaçar el gra de blat de moro amb polpa de remolatxa i la quantitat de metà recuperat va ser del 19,6 i 29,7 g/dia, respectivament. En els altres dos experiments, l'intercanvi de gasos es va mesurar mitjançant una urna o calaix dissenyat per a petits remugants, on la cabra introduïa tot el cap i un programa informàtic gravava automàticament les concentracions d'O2, CO2 i CH4 de l'aire exhalat de forma contínua al llarg del dia. El segon experiment va consistir en dues dietes amb alt i baix nivell de midó i no es van trobar diferències en l'emissió de metà (28,5 g/dia). En el tercer experiment es va substituir ingredient per ingredient com en l'experiment número u. El gra d'ordi es va substituir per polpa de taronja o pellofa de soja i tampoc es van trobar diferències, amb un valor mitjà de la producció de metà de 41 g/dia. L'energia metabolitzable ingerida durant els tres experiments va ser de 1279 kJ/kg de pes metabòlic (PV0.75) i dia de mitjana, i l'eficiència d'utilització de l'energia metabolitzable ingerida per a la producció de llet va ser de 0,6. / Ibáñez Sanchis, C. (2015). INFLUENCE OF NUTRITION ON METHANE GAS PRODUCTION IN MURCIANO-GRANADINA GOATS [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/59389 / TESIS

Cattle are responsible for greenhouse gas emissions such as carbon dioxide, methane and nitrous oxide. In particular, the cow-calf phase of production accounts for approximately 80 percent of the total beef production system greenhouse gas emissions. Tannins are chemical compounds found in certain forages and they have the potential to help reduce these negative environmental impacts. Thus, given that the cow-calf phase often relies on feeding hay, feeding tannin-containing hays may represent a significant mitigation practice. With my MS program, I sought to explore whether tannin-containing hays fed to mother cows and heifers influence methane and nitrogen emissions relative to feeding traditional legume and grass hays . I found that “non-traditional” hays such as cicer milkvetch and tannin-containing hays such as sainfoin, birdsfoot trefoil and small burnet can help mitigate greenhouse gas and nitrogen emissions produced from heifers and mature cows. Therefore, these hays could be used to feed cattle during the fall and winter to help create a more environmentally friendly cow-calf phase of beef production.

Peatlands cover 3% of the earth's surface, with approximately 110 to 130 million hectares in Canada and are important in terms of the long-term sequestration of atmospheric carbon. In contrast to their removal of CO2 from the atmosphere, peatlands represent 15 to 30% of the total methane emissions to the atmosphere with Canadian wetlands emitting approximately 0.1 to 1 x 1010 g yr^-1. Drainage and harvesting of peatlands generally reduces CH4 emissions to the atmosphere and increases CO2 emissions by up to 400%. However, recent studies have suggested that drained peatlands may represent a larger source of atmospheric CH4 than undisturbed peatlands. In the first part of this study, potential CH4 production and oxidation was determined from natural, harvested and recently restored peat. Total depth integrated CH4 production decreased with time post harvest where CH4 production at 2-yr > 7-yr > 20-yr cutover peat. This decrease in CH4 production was a result of a decreased source of labile carbon, a decrease in the methanogenic population, and an increase in the concentration of alternative electron acceptors. Restoration has altered CH4 production processes so that total depth integrated CH4 production was 2-yr > 7-yr >RESTORED> 20-yr cutover peat. Depth dependent trends in potential CH4 oxidation and production from each peat were dependent on the water table position while substrate quality was the main difference production values between the Lac St. Jean and Bois-des-Bel peat. Comparison of CH4 fluxes over the four field seasons showed restored site bare peat and mosses did not play a significant role in CH4 emissions from the peatland. However, the overall CH4 function of the peatland was directly related to the increase in CH4 emissions from vascular vegetation, remnant ditches and newly constructed ponds which were directly attributed to an increase in labile carbon for methanogenesis provided by vegetation. CH4 fluxes from ditches and ponds suggest that these features are the largest sources of CH4 from the peatland. However, when weighting the fluxes to the areal extent of each feature, ditches become secondary to vascular vegetation in total CH4 emissions while the ponds had a minimal impact on the amount of CH4 emitted from the peatland. Furthermore, ebullition from ditches and ponds was insignificant in comparison to the diffusive fluxes. When comparing CH4 emissions from this site to natural peatland systems (~10 g CH4 m^-2 a^-1), it is evident that the site is still a much smaller source of CH4 and that the carbon and CH4 process are still changing as the pool of labile carbon increases (develops). Vegetation succession is still occurring and more time and monitoring is needed in order to determine if this site will return to similar CH4 functions as natural peatlands. / Thesis / Master of Science (MSc)

Natural gas is currently an attractive substitute for diesel fuel in the Heavy-Duty (HD) diesel transportation sector. This is primarily attributed to its cost effectiveness, but also its ability to reduce the amount of CO2 and harmful engine pollutants emitted into the atmosphere. Lean-burn dual-fuel engines substitute natural gas in place of diesel but typically suffer from high engine-out methane (CH4) emissions, particularly under low load operation. In response to this issue, this work set out to improve upon the efficiency and emissions of a lean-burn dual-fuel combustion system in an HD diesel/natural gas engine. Thermodynamic experimental engine testing was performed at various steady-state operating points in order to identify the most effective methods and technologies for improving emissions and efficiency. Low Temperature Combustion (LTC) along with several valvetrain and injection strategies were evaluated for benefits, with special attention paid to low load operating conditions. LTC was proven to be a useful method for decreasing methane emissions while simultaneously improving engine efficiency. The benefits of LTC were a function of load with the greatest advantages experienced under medium load operation. Additionally, the low load strategies tested were determined to be effective techniques for reducing methane emissions and could possibly extend the dual-fuel operating regime to lighter load conditions. Overall, no operating condition tested throughout the engine map resulted in a brake engine-out methane emissions level of less than 0.5 g/kWh at gas substitutions greater than approximately 75%. It is suggested that the limits of this particular lean-burn dual-fuel design were reached, and that it would likely require improvements to either the combustion system or exhaust after-treatment if Euro VI emissions levels for methane were to be achieved.

Conventional production of meat products from ruminant animals in the United States requires inputs including the cultivation and nitrogen fertilization of annual grains such as corn and barley, and transportation of cattle and grain to feedlots. Consumers have concerns about the impact of feedlot conditions on animal health, and about the implications of pharmaceutical inputs such as growth hormones and antibiotics on the environment and human health. These concerns have led to a growing interest in pasturefinished meat production by consumers. Such smaller-scale livestock production systems can be healthier and lower-stress for animals, are integrated into local food systems and are more transparent to consumers, and have higher potential profitability for producers than traditional ruminant production methods. There is a strong market for pasture-finished beef products, and prices for naturally or organically raised beef have remained well above feedlot-produced product prices. There is also concern about the impact of ruminant production on the environment, including air and water pollution from feedlot production and greenhouse gasses that are emitted from ruminant animals during feed digestion. This thesis project explored the potential of a beef production system based on perennial legumes, including the non-bloating legume birdsfoot trefoil (BFT; Lotus corniculatus L.) for producing meat products from cattle while reducing concentrate feeding and methane production. The condensed tannins that are produced by BFT bind proteins in the rumen but allow them to be digested in the abomasum and intestines, which in turn leads to better utilization of forage nutrients during the finishing period and higher gains or milk production. The higher digestibility of legumes compared with grasses reduces methane emissions in cattle both through higher digestibility of the forage and through direct impacts on methanogens operating in the rumen. As reported in this thesis, steers finished on BFT gained significantly more weight per day than steers fed another perennial forage legume, cicer milkvetch, but did not gain as rapidly as feedlot-fed steers. At the end of summer grazing, the blood plasma of pasture-fed steers was lower in saturated and omega-6 fatty acids and higher in transvaccenic and omega-3 fatty acids than the blood plasma of feedlot-fed steers. When beef cows grazed grass and legume pastures, enteric methane emissions were lower on the legume pastures than the grass pasture. These results demonstrate that, compared with other feed sources, perennial legume pastures used for cattle production can improve cattle gains and reduce environmental impacts.

Methane is a potent greenhouse gas with a global warming potential 21 times that of carbon dioxide. Globally, ruminants are the main anthropogenic contributors to methane release to the atmosphere. Methane is produced in the gastrointestinal tract of ruminants, mostly within the rumen by methanogenic archaea. However, methane production represents a loss of 2 to 12% of dietary gross energy for the animal, which could otherwise be available for growth or milk production. Therefore, mitigation of methane production by ruminants could produce both economic and environmental benefits, with more sustainable and energy efficient livestock, and offering a promising way of slowing global warming. Despite extensive research undertaken to find ways of reducing methane emissions from ruminants, progress has been relatively limited. Furthermore, there is still a lack of studies linking rumen microbiology and ruminant nutrition and production. The central purpose of this research was to investigate feed additives to reduce methane emissions and to understand associated changes that occur in the rumen microbiota. For the first experiment (Chapter 2), biochar was evaluated as an antimethanogenic compound for beef cattle. The in vitro gas production technique was used to study the effects of biochar on rumen fermentation and methane production. Overall, methane production was reduced by 5% by the addition of biochar compounds (10 g/kg of substrate). The observed reduction in methane produced was not associated with a change in volatile fatty acid profile suggesting biochar primarily inhibited fermentation. Ammonia concentration was significantly reduced with biochar inclusion. Because different biochars had different effects on methane production, further investigation of relationships between the physicochemical properties of biochars and antimethanogenic effects are necessary. However, due to the small reduction in methane production recorded, research with biochar was discontinued. Encapsulated nitrate was then explored as an antimethanogenic additive and as an alternative non-protein nitrogen source to urea (Chapter 3). The effect of using encapsulated nitrate as a replacement for urea or dietary protein, plus the addition of inorganic sulphur, on enteric methane emissions, nutrient digestibility, nitrogen utilization and microbial protein synthesis from crossbred beef steers were studied. In addition, nitrate toxicity and eating behaviour were investigated. The inclusion of encapsulated nitrate reduced methane production compared to urea and a true protein source, with no adverse effects on rumen fermentation or nitrogen metabolism and no effects with the inclusion of elemental sulphur. The level of addition of encapsulated nitrate (14.3 g nitrate /kg DM) and the time of adaptation chosen for this study (14 days) were adequate to avoid nitrate toxicity. Finally, the effects of adding nitrate inclusion to different basal diets on rumen microbial populations and relationships of these populations with methane production were investigated (Chapter 4). The V4 hypervariable regions of the bacterial and archaea 16S rRNA genes were amplified and sequenced. Effects on microbial population induced by nitrate were dependant on the basal diet but nitrate altered specific archaeal and bacterial OTUs consistently between studies. A direct and strong correlation between some archaea taxonomic groups and OTUs with methane production was observed.

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