Soil N2O flux is sensitive to soil moisture content and soil temperature, which are in turn sensitive to changes in climate and topography. Thus, N2O flux measurements exhibit a high degree of spatial and temporal variability. Knowing how the spatial distribution of soil N2O flux changes over time in a hummocky, agricultural landscape will identify measurement scales appropriate for estimates of N2O emissions from these types of terrains. As well, little is known about N2O emissions from uncultivated, ephemeral wetlands in agricultural landscapes, but this information is needed for accurate inventories of N2O emissions. The objectives of this study were to describe the spatial and temporal distribution of soil N2O flux in a hummocky agricultural landscape, and to understand how soil water and soil temperature control the spatial and temporal patterns of N2O flux. For a hummocky, agricultural landscape in the Dark Brown soil zone of Saskatchewan, N2O flux and related soil variables were measured along a 128-point transect multiple times over two years and concurrently from a 50 point, stratified design over three years. The spatial and temporal variation in N2O flux followed an event-based / background emission pattern. High flux events were triggered by precipitation events and recession of water from wetlands following spring snowmelt. Days with high mean flux were characterized by highly skewed (reverse J-shaped) distributions. High variance and coherency was observed at cultivated wetland elements during emission events. Strong location-dependent positive relationships were found between soil N2O flux and water-filled pore space or soil temperature, related to specific landscape elements. Background emissions were characterized by random variation or cyclic behavior that ranged in scale from 20 to 60 m. Cumulative emissions were highest from cultivated wetlands and basin centers of uncultivated wetlands, although emissions from cultivated wetlands were much more important to total cumulative emissions on an area basis. The results indicate that models intended to estimate N2O flux from these landscapes cannot rely on a single predictive relationship, but will have to incorporate predictive relationships localized at specific landscape elements depending on the time of year. At certain times predictive relationships cannot be used and up-scaled estimates will have to rely on direct measurement of emissions.

Trots att avloppsreningsverkens primära syfte är att minska människans påverkan på miljön genom att bland annat reducera halten näringsämnen i vattnet bidrar de samtidigt till den ökande växthuseffekten. FN:s klimatpanel pekar ut avloppsreningsverk som en signifikant källa till direkt emission av lustgas och metan och det sker även indirekta emissioner uppströms och nedströms reningsverket. Samtidigt som diskussionen om klimatpåverkan från avloppsreningsverk växer är många recipienter hårt belastade och nu väntas en skärpning av utsläppsvillkoren för att minska tillförseln av näringsämnen till de naturliga vattensystemen. Studier har visat att skärpta utsläppsvillkor ökar klimatpåverkan från avloppsreningsverk. Två miljöproblem, övergödning och klimatförändringar, står mot varandra och måste värderas för att framtidens avloppsrening ska kunna planeras. Syftet var att undersöka hur klimatpåverkan från avloppsreningsverk påverkas av teknikval och utsläppsvillkor. Simuleringsverktyget BioWin användes för att beräkna koldioxidavtryck från Enköpings framtida avloppsreningsverk. Tre olika processtekniker (aktivslamprocessen, membranbioreaktor och aktivslamprocessen med biologisk fosforreduktion) och sju olika utsläppsvillkor studerades. I beräkningarna togs hänsyn till både direkta och indirekta emissioner genom bland annat lustgasproduktion, kemikalieförbrukning och användning av el. Den konventionella aktivslamprocessen orsakade minst koldioxidavtryck medan avtrycket från den moderna membranbioreaktorn var överlägset störst. En skärpning av utsläppsvillkoren för kväve och fosfor gav en ökning av koldioxidavtrycket med upp till 55 % och det var speciellt kvävekravet som styrde ökningen. Då utsläppsvillkoren skärptes ökade avtrycket mest från membranbioreaktorn vilket indikerar att den ur klimatsynpunkt lämpar sig sämre vid skärpta utsläppsvillkor. Lustgasemission stod för den största delen av koldioxidavtrycket. Lustgasemissionen ökade vid skärpta utsläppsvillkor samt då kvävereningen stördes, exempelvis vid låga vattentemperaturer. Fler komponenter bör tas i åtanke vid utvärdering av miljöpåverkan från ett avloppsreningsverk, exempelvis övergödning. Detta skulle göra det möjligt att bedöma den totala miljövinsten, eller förlusten, med att skärpa villkoren. / Although the primary aim for wastewater treatment plants (WWTP) is to minimize the environmental impact by reducing the content of nutrients in the wastewater, they also contribute to the increasing greenhouse effect. The International Panel on Climate Change refer to WWTP:s as a significant source of direct emission of nitrous oxide and methane and indirect emission also occurs upstream and downstream the WWTP. As the discussion about climate impact from WWTP is growing, many recipients are congested and a tightening of the discharge limits is expected in order to reduce the load of nutrients on the natural water systems. Studies have shown that more stringent discharge limits increases the climate impact from WWTP. Two environmental problems, eutrophication and climate change, are facing each other and they must be valued in order for future WWTP to be planned. The aim was to investigate how the climate impact of wastewater treatment plants is affected by choice of technology and discharge limits. The simulation tool BioWin was used to calculate the carbon footprint (CF) from the future WWTP in the town of Enköping. Three different process technologies (activated sludge process, membrane bioreactor and activated sludge process with biological phosphorus removal) and seven different discharge limits were examined. The calculations took into account both direct and indirect emissions from e.g. production of nitrous oxide and use of electricity. The conventional activated sludge process caused the smallest CF, while the modern membrane bioreactor by far caused the largest CF. Tightening of the discharge limits gave an increase of the CF with up to 55 %, and especially the demands on nitrogen governed the increase. More stringent limits increased the CF from the membrane bioreactor the most, which indicates that from an environmental point of view, this technique is less suitable when limits are tightened. Emission of nitrous oxide accounted for the largest part of the CF and this emission increased as the discharge limits were tightened and when the nitrogen treatment was disturbed by, for instance, low water temperatures. More components should be accounted for when environmental impact from WWTP is investigated, e.g. eutrophication. This would make it possible to assess the overall environmental gain, or loss, from tightening of the discharge limits.

Grünland spielt eine große Rolle in der Landnutzung und nimmt ein Drittel der landwirtschaftlich genutzten Fläche von Europa ein. Als Konsequenz der Intensivierung landwirtschaftlicher Bewirtschaftungsmaßnahmen der letzten 60 Jahre nahm die Produktivität des Grünlands zu während die Diversität dieser Systeme abnahm. In Grünland-Ökosystemen spielt Stickstoff (N) eine Schlüsselrolle – N bedingt die Primärproduktion und beeinflusst die Biodiversität. Zudem kann eine steigende N-Verfügbarkeit gasförmige Emissionen, wie z.B. Distickstoffoxid (N2O) und Stickstoffmonoxid (NO) fördern, die eine große Rolle in der Atmosphäre spielen und zur globalen Erwärmung beitragen. Eine höhere Nitratauswaschung (NO3-) aus Böden kann eine Gefahr für die Grundwasserqualität sein. N-Verluste durch Ausgasung von N2O und NO sowie NO3--Auswaschung sind dabei die Folgen der mikrobiellen Prozesse Denitrifikation und Nitrifikation. In dieser Studie haben wir den Effekt von unterschiedlichen Bewirtschaftungsintensitäten und funktioneller Pflanzendiversität auf die N-Verluste und Ökosystemfunktionen untersucht. Die Studie ist Teil des Excellenzclusters „Funktionelle Biodiversitätsforschung“ der Georg-August-Universität Göttingen und wurde durch das Niedersächsische Ministerium für Wissenschaft und Kultur finanziert. Die Studie wurde im Rahmen von zwei interdisziplinären Projekten (BIOMIX & GRASSMAN) von 2008 bis 2010 im Solling, Niedersachsen, Deutschland durchgeführt. Wir untersuchten von Rindern und Schafen beweidetes Grünland (BIOMIX) und gemähtes Grünland mit unterschiedlichen Bewirtschaftungsintensitäten (GRASSMAN). In beiden Projekten wurde die funktionelle Pflanzendiversität durch Herbizide eingestellt. Der Fokus unserer Arbeit lag auf den N-Verlusten (N2O and NO Emissionen, NO3--Auswaschung) und der N Dynamik (Netto und Brutto Mineralisation). In GRASSMAN berechneten wir zusätzlich die N-Nutzungseffizienz und die N-Rückhalteeffizienz auf Ökosystemebene. Dabei ist die N-Nutzungseffizienz das Produkt der Aufnahmeeffizienz (definiert als N-Aufnahme der Pflanze pro verfügbares N) und der N-Nutzungseffizienz auf Pflanzenebene (definiert als Produktivität pro N-Aufnahme der Pflanze). Darüber hinaus berechnen wir N-Rückhalteeffizienz in Böden als einen Index, der das Verhältnis von N-Verlusten zu dem im Grünland verbleibenden N beschreibt. In BIOMIX haben wir die Auswirkung von Beweidung und Pflanzenarten-zusammensetzung auf N2O and NO Emissionen untersucht. Die mit einem Herbizid gegen Dikotyle vorbehandelten Weiden wurden mit Rindern oder Schafen Rotationsweise beweidet. Mittlere N2O Emissionen lagen bei 38.7 µg N2O-N m-2 h-1, mittlere NO Emissionen betrugen 2.4 µg NO-N m-2 h-1. Kumulative NO-N Emissionen waren höher auf den von Schafen beweideten Flächen als auf den von Rindern beweideten Flächen. In einem kontrollierten Applikations-Experiment führte die Behandlung mit Rinderurin zu höheren N2O Emissionen als die Behandlung mit Schafurin. Die Emissionshöchstwerte von 1921 µg N2O-N m-2 h-1 bei Behandlung mit Rinderurin im Vergleich zu 556 µg N2O-N m-2 h-1 bei Schafurin standen im Zusammenhang mit unterschiedlichen N-Einträgen pro Ausscheidung der Tiere. Die Emissionshöchstwerte der mit Dung behandelten Flächen waren im Vergleich mit den jeweiligen Urinbehandlungen viel geringer. Die N2O Emissionsfaktoren betrugen 0.4% für Rinderurin, 0.5% für Schafurin, 0.05% für Rinderdung und 0.09% für Schafdung. Sowohl das Beweidungs-Experiment, als auch das kontrollierte Applikations-Experiment zeigten, dass die Pflanzenartenzusammensetzung auf N-Emissionen im Vergleich zum Einfluss der Weidetierart auf N-Emissionen unbedeutend war. Trotz höherer N-Einträge auf Rinderweiden waren die N-Emissionen aus der Schafbeweidung höher. Wir führten dies auf die gleichmäßigere Verteilung von Schafs-Exkrementen im Vergleich zu Rindern-Exkrementen zurück. In GRASSMAN untersuchten wir die Auswirkungen von unterschiedlichen Bewirtschaftungsregimen (Düngung und Schnittintensität) und Pflanzenarten-zusammensetzung auf die N-Verluste (N2O Emissionen, NO3- Auswaschung) und die N-Dynamik (Netto und Brutto Mineralisation) und kalkulierten die N-Nutzungseffizienz und die N-Rückhalteeffizienz. Ein dreifaktorielles Design mit folgenden Faktoren wurde über einen Zeitraum von zwei Jahren etabliert: Düngung (180 – 30 – 100 kg NPK ha-1 yr-1 und keine Düngung), Schnittintensität (ein- und dreimal pro Jahr) und Pflanzenartenzusammensetzung (eine unbehandelte Kontrolle, eine Dikotyl-erhöhte und eine Monokotyl-erhöhte Grasnarbe). In 2009 wurden die N2O Emissionen erheblich von beiden Bewirtschaftungsfaktoren (Düngung und Schnittintensität) beeinflusst, während in 2010 nur die Düngung die N2O Emissionen beeinflusste. In 2009 wurden NO3- Auswaschungsverluste durch Düngung und in 2010 von beiden Bewirtschaftungsfaktoren (Düngung und Schnittintensität) beeinflusst. Die Netto N-Mineralisation Raten wurden in 2009 nur von der Düngung beeinflusst. In 2010, zeigte nicht nur die Düngung, sondern auch die Schnittintensität einen Einfluss auf die Netto N-Mineralisation Raten. Weder die Bewirtschaftung (Düngung) noch die Pflanzenartenzusammensetzung hatte einen Einfluss auf die Brutto N-Mineralisation. Die N-Nutzungseffizienz wurde vor allem durch die Düngung und als weiterer Faktor durch die Schnittintensität in 2009 beeinflusst, welche 41% bzw. 3% der Varianz erklärten. In 2010 hatte die Düngung mit 24% der erklärten Varianz einen geringeren Effekt auf die N-Nutzungseffizienz, während die Auswirkungen der Schnittintensität (12%) und die Pflanzenartenzusammensetzung (6%) stärker ausgeprägt waren. Die N-Nutzungseffizienz war auf ungedüngten Flächen größer als auf gedüngten, in den dreimal geschnittenen Flächen höher als in den einmal geschnittenen, und in der unbehandelten Kontrolle höher als in der Monokotyl-erhöhte oder Dikotyl-erhöhte Grasnarbe. Düngung verringert die N-Nutzungseffizienz durch die Abnahme in der N-Aufnahmeeffizienz und der N-Nutzungseffizienz auf Pflanzenebene, während die Schnittintensität und die Pflanzenartenzusammensetzung nur durch die N-Aufnahmeeffizienz beeinflusst werden. Die N-Rückhalteeffizienz wurde nur für 2010 berechnet und wurde durch die Düngung und die Pflanzenartenzusammensetzung mit 22% und 17% der erklärten Varianz beeinflusst. N-Rückhalteeffizienz nahm in der Reihenfolge unbehandelte Kontrolle > Dikotyl-erhöhte > Monokotyl-erhöhte Grasnarbe mit einem signifikanten Unterschied zwischen der unbehandelten Kontrolle und der Monokotyl-erhöhten Grasnarbe ab. Die N-Rückhalteeffizienz ist mit dem mikrobiellen Ammonium (NH4+) und der mikrobiellen Biomasse hoch und mit der N-Aufnahme der Pflanzen nur gering korreliert, was die Bedeutung der mikrobiellen N Retention im System Boden-Pflanze unterstreicht. Unsere Ergebnisse zeigen, dass die Bewirtschaftung der wichtigste und bestimmende Faktor der Ökosystemfunktionen eines Grünlands ist. Düngung, Schnittintensität und Beweidung beeinflussen die N-Nutzungseffizienz, die N-Rückhalteeffizienz und die N-Verluste. Die Zusammensetzung der botanischen Grasnarbe hat einen geringen Einfluss auf den N Kreislauf oder die N-Nutzungs- und die N-Rückhalteeffizienz. Wobei die Pflanzenartenzusammensetzung der unbehandelten Kontrolle (~70% Monokotyle und ~30% Dikotyle), die sich unter der extensiven Langzeit-Bewirtschaftung eingestellt hatte, die höchsten Effizienzen zeigte - sowohl eine Erhöhung der Monokotyledonen als auch eine Erhöhung der Dikotyledonen führte zu einer Verringerung der Effizienzen. Darüber hinaus sind N-Nutzungs- und N-Rückhalteeffizienz geeignete Werkzeuge, die sich zur Evaluierung ökologischer Nachhaltigkeit von Pflanzenartenzusammensetzungen und Management-Praktiken im Grünland eignen.

Unintentional nitrogen (N) loss from agroecosystems produces greenhouse gases, induces eutrophication, and is costly for farmers; therefore, adoption of conservation agricultural management practices, such as no-till and cover cropping, has increased. This study assessed N loss via leaching, NH3 volatilization, N2O emissions, and N retention in plant and soil pools of corn conservation agroecosystems across a year. Three systems were evaluated: 1) an unfertilized organic system with cover crops Vicia villosa, Triticum aestivum, or a mix of the two; 2) an organic system with a Vicia cover crop employing three fertilization schemes (0 N, organic N, or a cover crop N-credit approach); 3) a conventional system with a Triticum cover crop and three fertilization techniques (0 N, urea N, or organic N). During cover crop growth, species affected N leaching but gaseous emissions were low across all treatments. During corn growth, cover crop and fertilizer approach affected N loss. Fertilized treatments had greater N loss than unfertilized treatments, and fertilizer type affected gaseous fluxes temporally and in magnitude. Overall, increased N availability did not always indicate greater N loss or yield, suggesting that N conserving management techniques can be employed in conservation agriculture systems without sacrificing yield.

Los suelos de los bosques tropicales desempeñan un papel importante en el clima de la Tierra mediante el intercambio con la atmosfera de grandes cantidades de gases de efecto invernadero (GEI). Sin embargo, esta importante función podría ser alterada por las actividades humanas causando el aumento en la deposición de nutrientes en los ecosistemas terrestres, especialmente en las regiones tropicales. Las causas de cómo el incremento de las cantidades de nutrientes está afectando los flujos de suelo de los GEI de los bosques tropicales es relativamente poco conocida, por ello los monitoreos de nutrientes in situ de los bosques montanos tropicales (BHT) son aún menos comprendidos. Ya que los BHT representan alrededor del 11-21% de la superficie forestal tropical, es de vital importancia predecir y cuantificar los cambios en los flujos de GEI del suelo en respuesta a la adición de nutrientes ya que podrían favorecer la retroalimentación a otros cambios globales. Esta tesis tiene como objetivo cuantificar el impacto de adición moderada de nitrógeno (N) y/o fósforo (P) en los flujos de tres GEI en suelo: dióxido de carbono (CO2), óxido nitroso (N2O) y el metano (CH4), a lo largo de un gradiente altitudinal (1000 m, 2000 m, 3000 m) de los BHT primarios en el sur de Ecuador. Desde hace más de cinco años, se ha medido los flujos de GEI del suelo en un experimento de manipulación de nutrientes (‘NUMEX’, por sus siglas en inglés), con replicas para control, y la adición de N (50 kg N ha-1 año-1), P (10 kg P ha-1 año-1) y N+P. Las mediciones in situ se realizaron mensualmente utilizando cámaras ventiladas estáticas, seguido por un análisis de cromatografía de gases para conseguir una perspectiva más profunda sobre los procesos implicados en el intercambio suelo-atmósfera de GEI. Se realizaron nuevas investigaciones incluyendo el monitoreo de factores básicos de control (i.e. temperatura del suelo, humedad y las concentraciones del N mineral), los diferentes componentes de los flujos de CO2 del suelo, tasas de reciclaje netos de N y fuentes de los flujos de N2O del suelo. Con este propósito, se utilizó la extracción de hojarasca y técnicas de excavación de zanjas (trenching technique), incubación de las muestras in situ (buried bag method) y el etiquetaje de 15N de corto plazo. Los flujos de GEI del suelo en los bosques que estudiados se mostraron en el rango de aceptado de los flujos de gases de otras BHT en elevaciones comparables, excepto para el N2O. Los flujos de N2O, que se derivan principalmente de la des nitrificación, fueron bajos para un TMF lo que se puede atribuir a los ciclos conservativos de N del suelo en nuestros sitios de estudios. Los suelos fueron fuentes de CO2 y N2O (la intensidad del recurso disminuye al aumentar la altitud) y en todas las elevaciones el CH4 es bajo. Encontramos efectos de los nutrientes en todos los flujos de GEI medidos en cada elevación. Las respuestas de los flujos de CO2 del suelo cambian con la duración y el tipo de nutrientes adicionado. En 1000 m, la adición del N no afecta los flujos de CO2 del suelo, mientras que las adiciones de P y N+P disminuyeron los flujos en el primer y cuarto a quinto año. En 2000 m., la adición de N y N+P incrementa los flujos de CO2 en el primer año; a partir de entonces, la adición del N disminuye los flujos mientras que la adición de N + P no mostro ningún efecto la adición de P carece de efectos. En 3000 m, la adición de N además incrementó los flujos de CO2 constantemente; la adición de P y N+P aumentaron los flujos sólo en el primer año a partir de entonces no existió ningún efecto. Los efectos diferenciales de los nutrientes estuvieron relacionados a un estatus del N y P y respuestas variadas de los componentes de la respiración del suelo. Las respuestas de los flujos de N2O y CH4 a la adición de nutrientes mostraron gran variabilidad entre años. Los flujos de N2O no se vieron afectados por la adición de tres a cinco años de N a pesar de las diferencias significativas observadas durante los dos primeros años del mismo experimento. Atribuimos la ausencia de las respuestas en años mas tardíos debido a los contenidos bajos de humedad del suelo en nuestro periodo de monitoreo 2010-2012. En todo el gradiente altitudinal, la adición de P disminuyó los flujos de N2O y las concentraciones de N mineral, presumiblemente debido a que alivió de la limitación del P en la producción primaria neta, lo que aumentó la captación de N a través de las plantas. La adición de N+P además mostró tendencias similares las respuestas a la adición de N solamente, pero con efectos menos fuertes debido a los efectos contrapuestos de la adición de P. Durante los dos primeros años de la adición de nutrientes, los flujos de CH4 no se vieron afectados en ninguna elevación, lo cual atribuimos a la combinación de cantidades moderadas de nutrientes añadidos, la fuerte inmovilización de nutrientes, y la separación de la más alta capacidad de absorción de CH4 en el subsuelo de la superficie del suelo donde se añaden fertilizantes. En el tercer a quinto año, la adición de nutrientes del suelo aumentaron la captación de CH4, aunque los efectos de N y P variaron a lo largo del gradiente altitudinal: en 1000 m, la adición de N y N+P aumentó la captación anual de CH4 a 20-60%; en 2000 m P y N+P incrementaron la captación a 21-50%; y en 3000 m la adición de P y N+P incrementó la captación de CH4 a 34-40%. Estos efectos diferenciales de la adición de nutrientes pueden estar relacionados con el estatus inicial de del suelo y respuesta diferenciales de otros componentes del ecosistema a la adición de nutrientes en cada elevación. Demostramos que los flujos de GEI del suelo y consecuentemente la red potencial de calentamiento global del suelo pueden cambiar considerablemente a lo largo de un gradiente de elevación, siguiendo una tendencia general de disminución con el aumento de la elevación. Los resultados indican además que la elevada deposición de N y P puede afectar los flujos de GEI del suelo en los BHT Andinos, pero las respuestas a los flujos de GEI a la adición de nutrientes depende del estatus inicial de los nutrientes del suelo, la duración de la adición de nutrientes y la variabilidad inter-anual de las condiciones climáticas. Puesto que los efectos de la adición de nutrientes fueron no lineares con el tiempo de exposición y a la par existen complejas interacciones con otros componentes del ecosistema, aún quedan muchas incertidumbres en la predicción exacta de los efectos de la deposición de nutrientes en los flujos de GEI. Sin embargo, ofrecemos los primeros datos sobre los efectos de nutrientes a medio plazo de N, P y N+P en los flujos de los tres principales gases de efecto invernadero del suelo a lo largo de un gradiente altitudinal de los BHT Andina. Nuestros resultados sugieren que la red potencial de calentamiento global de los suelos en todo el gradiente altitudinal podría aumentar ligeramente con la entrada contribución de N, mientras que podría disminuir con el aumento de la contribución de P y N+P.

The increased use of synthetic nitrogen fertilizers since the early 1900s has resulted in greater food production but also problems with nitrogen pollution in freshwaters. Nitrate (NO3-) is a common pollutant in rivers and groundwater in agricultural watersheds; the drinking water limit in Canada is 10 mg N/L. Microbial processing of NO3- and ammonium (NH4+) can produce nitrous oxide (N2O), a potent greenhouse gas responsible for about 5% of the greenhouse effect. Rivers provide a complex environment, where a variety of redox conditions, available substrates and microbial populations can co-exist on small spatial and temporal scales. Therefore, many questions remain about N cycling in river environments. N2O is produced during anoxic microbial NO3- or NO2- reduction to N2 (denitrification) and oxic microbial NH4+ oxidation to NO3- (nitrification). A significant portion (~25%) of global anthropogenic N2O is produced in rivers and estuaries, but mechanisms are not clear and predictability is poor. The United Nations Intergovernmental Panel on Climate Change (IPCC) provides default equations for calculating N2O emission estimates, in which annual NO3- loading to rivers is positively linearly related to N2O emissions. However, it is unclear how sound these linear relationships are and if measured N2O emissions are similar to IPCC estimates. The Grand River watershed is the largest in southern Ontario. Nutrient discharge to the Grand River is high due to extensive agriculture and high urban populations. The river often has a hypoxic water column due to high community respiration in summer. However, although nitrogen pollution is significant, N cycling is not well understood in the river. This thesis shows that NO3- and NH4+ do not typically change on the diel scale, with the exception of two sites downstream of wastewater treatment plants (WWTPs). However, N2O concentration changes dramatically. N2O concentrations are higher at night and lower during the day for most sites, but are reversed at very low-nutrient sites. N2O is therefore a sensitive indicator of changes in N cycling that may not be evident from NO3- and NH4+ concentrations or stable isotope ratios. Additionally, this work shows the importance of having a sampling design that captures diel variability in N2O. Previous work in rivers and streams worldwide focused on the appropriate N2O:NO3- ratio used to predict N2O emissions. In contrast, this thesis shows that there is a significant but very weak relationship between instantaneous N2O emissions and NO3- concentrations. However, there is a much stronger negative exponential relationship between DO and N2O. Annual N2O emissions tripled between 2006 and 2007 but NO3- masses in the river were only 10% higher, likely because river levels were lower and anoxia more prevalent in 2007. This research suggests that the IPCC needs a new conceptual model for N2O-NO3- relationships in rivers. N2O is produced in rivers, partially due to microbial processing of NO3- and NH4+ from WWTP effluent. However, WWTP effluent may also include dissolved N2O and CH4 but this previously had not been directly quantified. It was also unclear if stable isotopic ratios of NH4+, NO3-, N2O and CH4 in WWTP effluent were distinct from river sources and could be used for effluent tracing. N2O emissions from three WWTPs in the Grand River Watershed were measured over 24 hours in summer and winter. N2O emissions were similar to direct emissions from WWTPs but CH4 emissions were about an order of magnitude lower than direct WWTP emissions. This is a previously-ignored source of N2O and CH4 to the atmosphere. While stable isotopic ranges of NO3- and NH4+ were not always distinct from river sources, ??15N-N2O, ??18O-N2O and ??13C-CH4 were distinct, making them potentially useful tracers of WWTP effluent in rivers. N2O isotopic signatures may help determine production and removal processes in rivers, but isotopic effects of the major production pathway, denitrification, have not been characterized for river sediments. This was addressed by preparing anoxic laboratory incubations of river sediment from two sites (non-urban and urban) in the Grand River and measuring stable isotopic effects of N2O production via denitrification. Stable isotopic fractionations were similar to published values but, surprisingly, strongly negatively correlated to production rate, even though NO3- substrate was plentiful. This novel finding suggests that N2O reduction resulting in isotopic effects is more prevalent in high-substrate systems than previously thought, and that N2O reduction may be inhibited by high NO3- or NO2- or by lags in N2O reductase activity in high N2O-production incubations. This could explain why N2O emissions from the Grand River are lower than predicted by IPCC equations, which assume that N2O:(N2O+N2) ratios produced by denitrification are constant. Concern about NO3- export to freshwater lakes and to oceans is growing, but the role of large, eutrophic rivers in removing watershed NO3- loading via denitrification and biotic assimilation is not clear. To understand how much NO3- the Grand River receives, and how much it removes annually, a NO3- isotope mass balance for the Grand River was created. The river denitrified between 0.5% and 17% of incoming NO3-, less than the 50% suggested by the IPCC. This is surprising, as the river is well mixed, has moderate to high NO3- concentrations, experiences hypoxia (promoting denitrification), and has extensive biomass (biofilm and macrophytes) that assimilate N. However, the river???s short residence time (~3 days not counting reservoirs), organic carbon-poor sediment and mineralization of organic matter could contribute to low denitrification rates. These findings suggest that denitrification rates in rivers worldwide could be lower than previously estimated. Although error was high, most ??15N-NO3- values for losses were in the expected range for denitrification and most ??15N-NO3- values for gains were within ranges from tributaries, WWTP effluent and groundwater measured in the watershed. The model suggests that 68% to 83% of N loads to the watershed are lost before entering the Grand River, and 13% is exported to Lake Erie, leaving 5 to 19% lost in the Grand River from a combination of denitrification, assimilation and storage. These findings suggest that large rivers are much less efficient in denitrification than other locations in watersheds such as small streams, ponds, groundwater and riparian zones. They also indicate that agricultural NO3- loading is much higher than WWTP effluent, suggesting that N management strategies should focus on agricultural runoff and groundwater. Given that N2O:NO3- relationships are weak and non-linear in the Grand River, a new conceptual model for N2O:NO3- relationships is presented. First, the Grand River dataset was supplemented with data from high-oxygen streams in southern Ontario. Regression tree analysis shows a weak relationship between NO3- and N2O in these streams with no other factors (temperature, DO, NH4+, TP, DOC, etc.) improving fit. A conceptual model was then created, which posits that N2O emission variability (between and within sites) increases with NO3- concentration when NO3- concentrations are above the threshold for NO3- limitation. The global dataset does not dispute this model, though a NO3- threshold was not clear. The lack of sites with both high NO3- and high N2O may indicate a paucity of research on eutrophic sites. Alternatively, high NO3- may indicate oxic conditions (i.e. little to no denitrification to remove it) which are incompatible with very high N2O emissions. In this case, the conceptual model can be modified such that N2O variability decreases when NO3- > ~ 4 mg N/L. The work also shows that low DO consistently results in high N2O emissions but high temperatures result in a very large range of N2O emissions. This approach allows N2O emissions, which have very high variability and are difficult to predict, to be constrained to likely ranges.

I used a specific inhibitor approach to systematically measure NH4+ oxidation rates through the euphotic zone of three distinct oceanographic regimes. Study sites included Saanich Inlet, a highly productive British Columbia fjord, the Line P oceanographic transect in the NE subarctic pacific, and the Bermuda Atlantic Time-series Study (BATS) station in the oligotrophic, sub-tropical Sargasso Sea. Nitrate uptake rates were also measured at select stations on a number of research cruises. NH4+ oxidation rates were found to proceed throughout the euphotic zone in each of my study regions, and, overall, euphotic zone NH4+ oxidation rates ranged from undetectable to 203 nmol L-1 d-1. A general characterization of the rates observed in each of my study regions shows that euphotic zone NH4+ oxidation rates were typically highest in Saanich Inlet, intermediate along Line P, and lowest at BATS. The observation that NH4+ oxidation occurred throughout the euphotic zone in each of my study regions was in contrast to the traditional assumption of no euphotic zone nitrification, and it should now be considered a ubiquitous process in the euphotic regions of the ocean. Results found that euphotic zone nitrification could have potentially supported, on average, 15, 53 and 79% of the phytoplankton NO3- requirements in Saanich Inlet, and along Line P and at BATS, respectively, and this underscores the need for a major re-evaluation of the new production paradigm. Light, substrate concentrations, and potentially substrate supply rates were all found to play a role in regulating NH4+ oxidation, albeit to varying degrees, and I discuss the influence that each of these variables may have had on controlling NH4+ oxidation rates at regionally specific scales in Chapters 2 (Saanich Inlet), 3 (Line P) and 4 (BATS). Finally, a cross study-region comparison of results showed that the relative degree by which new production estimates were reduced, when euphotic zone nitrification was taken into consideration, decreased exponentially as total NO3- uptake rates increased; the relationship I describe between these two variables may potentially provide a simple and rapid means of estimating the extent to which new production may have been overestimated at regionally specific and global scales. My Line P sampling program also provided me with an opportunity to conduct the first investigation of intermediate depth N2O distributions along the Line P oceanographic transect. My results demonstrated that nitrification is the predominant production pathway for N2O in the NE subarctic Pacific. N2O distributions along Line P were variable, however, and I also consider the role of different transiting water masses and potential far-field denitrification in contributing to this variability. Finally, I estimated sea-to-air fluxes of N2O and based on these results I have demonstrated that the NE subarctic Pacific is a “hotspot” for N2O emissions to the atmosphere. / Graduate

Atmospheric nitrous acid (HONO) is a significant and sometimes dominant OH source at polar region. An improved method of detecting HONO is developed using photo-fragmentation and laser-induced fluorescence (LIF). The detection limit of this method is 2-3 pptv for ten-minute integration time with 35% uncertainty. The abundance of laser-induced fluorescence (LIF) HONO measurements during ANTCI (Antarctic troposphere chemistry investigation) 2003 exceeds the pure gas phase model predictions by a factor of 1.92±0.67, which implies snow emission of HONO. A 1D air-snowpack model of HONO was developed and constrained by observed chemistry and meteology data. The 1D model includes pure gas phase chemical mechanisms, molecular diffusion and mechanical dispersion, windpumping in snow, gas phase to quasi-liquid layer phase HONO transfer and quasi-liquid layer nitrate photolysis. Based on the air-snowpack model, snow emission of HONO is highly likely and will be transported to place of the measurements. The pH, thickness of quasi liquid layer and contineous nitrite measurement are key factors to calibrate and validate the air snowpack model.

Existe uma preocupação mundial com as mudanças climáticas causadas pelo aumento da concentração de gases do efeito estufa (GEE) e consequente acréscimo na temperatura média da superfície terrestre. A queima de combustíveis fósseis é a maior causadora do aquecimento global e responsável por danos à saúde humana. É notável o esforço global em diversificar a matriz mundial de combustíveis líquidos, priorizando a substituição de fontes fósseis por renováveis. Tal substituição reforça a necessidade de avaliações de todas as emissões de GEE na cadeia produtiva da cana-de-açúcar. O Brasil é o maior produtor de etanol proveniente de cana-de-açúcar. Um importante co-produto deste processo produtivo é a vinhaça, sendo produzida em elevadas quantidades e constituída por uma expressiva carga orgânica. Esta é comumente aplicada ao solo por fertirrigação. Apesar de atuar beneficamente no solo, pouco se sabe sobre a capacidade deste co-produto de aumentar as emissões de GEE no solo. Assim, o objetivo foi avaliar o efeito da aplicação da vinhaça nas emissões de N2O e CH4 e na comunidade de bactérias desnitrificantes e metanogênicas do solo. As amostragens de GEE e solo foram em áreas de cana sem queima a partir da aplicação de doses vinhaça (0, 150, 300 e 450 m3 ha-1). O delineamento experimental realizado foi em cinco blocos casualizados, totalizando 25 câmaras de coleta de gases do efeito estufa. Amostras de solo foram coletadas em quatro períodos de amostragem após aplicação de vinhaça (0, 7, 15 e 30 dias), em dois anos consecutivos. Foram analisados os GEE, N2O e CH4, além da abundancia de genes por meio da técnica de qPCR. A fertirrigação via aplicação de vinhaça no solo, nos dois anos, proporcionou aumento nas emissões de N-N2O, principalmente nos primeiros dias após a aplicação. Contudo os fluxos de C-CH4 oscilaram indicando a capacidade do solo de servir ora como fonte ora como sumidouro deste GEE. Os fatores de emissão obtidos para aplicação de N na forma de vinhaça, dose de 300 m3 ha-1, foram de 0,08% para o primeiro ano e 0,07% para o segundo ano. A partir da técnica de qPCR, a abundância dos genes indicou que a introdução deste resíduo ao solo pode aumentar significativamente o total de bactérias no solo e a atividade do gene nosZ, contudo o mesmo não ocorre com o potencial de desnitrificação biológica (gene nirK) e nem com o gene mcrA (redução de CH4). Os resultados demonstram que a aplicação da vinhaça no solo influencia as emissões de GEE, assim como a comunidade microbiana do solo / There is a global concern with climate change caused by increased concentration of greenhouse gases (GHG) and consequent increase in the average temperature of the Earth surface. Fossil fuels burning is the major cause of global warming and it is responsible for damages to human health. Remarkable global efforts in diversifying liquid fuels have been attempted, giving priority to the replacement of fossil fuels to renewables. Such substitution reinforces the need of an evaluation of all GHG emissions in the production chain of sugarcane. Brazil is the largest producer of ethanol with source from sugarcane. An important co-product of the production process is vinasse, which is being produced in large quantities comprising a significant organic load. This is commonly applied over the ground by fertigation. Despite being good for the soil, little is known about the ability of this co-product of increasing GHG emissions. This work aimed to evaluate the effect of the application of vinasse in the emissions of N2O and CH4 and in the soil community of denitrifying and methanogenic bacteria. Sampling of GHG and soil were performed in areas of sugarcane without burning with the application of different vinasse doses (0, 150, 300 and 450 m3 ha-1). The experiment was conducted in five blocks, totaling 25 collection chambers of greenhouse gases. Soil samples were collected in four sampling periods after application of vinasse (0, 7, 15 and 30 days), in two consecutive years. We analyzed the GHG, N2O and CH4, and the abundance of genes by qPCR technique. The fertigation via vinasse application on the ground in two years provided an increase in emissions of N-N2O, especially in the first couple of days after application. However the flow of C-CH4 was variable indicating the ability of the soil to serve either as source or as sink of this GHG. The emission factor obtained for N application in the form of vinasse dose of 300 m3 ha-1 was 0.08% for the first year and 0.07% for the second year. By qPCR technique, the abundance of the genes indicated that the use of this residue to the soil can significantly increase the amount of bacteria in the soil and nosZ gene activity. However it does not occur with the potential for biological denitrification (nirK gene) or with the gene mcrA (reduction of CH4). These results demonstrate that the application of vinasse in the soil influences GHG emissions as well as the soil microbial community

Submitted by Onia Arantes Albuquerque (onia.ufg@gmail.com) on 2018-11-01T15:21:36Z No. of bitstreams: 2 Tese - Yoná Serpa Mascarenhas - 2018.pdf: 2053155 bytes, checksum: 6802041af44b7acb24d35f6fbf64647d (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-11-01T15:44:43Z (GMT) No. of bitstreams: 2 Tese - Yoná Serpa Mascarenhas - 2018.pdf: 2053155 bytes, checksum: 6802041af44b7acb24d35f6fbf64647d (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-11-01T15:44:43Z (GMT). No. of bitstreams: 2 Tese - Yoná Serpa Mascarenhas - 2018.pdf: 2053155 bytes, checksum: 6802041af44b7acb24d35f6fbf64647d (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-05-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The flooded rice crop (Oryza sativa L.) emits both N2O and CH4, which can contribute significantly to total greenhouse gas (GHG) emissions. Application of nitrogen fertilizers is normally necessary to achieve optimum yields, however over application may increase the risks of pollution and N2O and CH4 emissions in flooded rice system. A study in field conditions was carried out at the Palmital Farm, Embrapa Experimental Station Rice and Beans, in Gleysol Haplic, in order to verify the greenhouse gas emissions, the carbon stock and the physical properties of the soil in a system of production of flooded rice in tropical lowlands under different sources and doses of N. The treatments resulted from the factorial combination: (common urea (UC) and protected urea (UP)), and three nitrogen doses (30, 70, 150 kg ha-1) plus the control. Unformed and deformed soil samples were collected at depths 0-5; 5-10; 10-15; 15-20; 20-30; 30-40 and 40-50 cm, to determine the physical properties of the soil. Gas collection was carried out in the 2014/2015 harvest, in the off-season 2015, and in the 2015/2016 harvest. The concentrations of N2O and CH4 were determined by gas chromatography. For the determination of nitrate (NO3-) and ammonium (NH4 +) in the non-flooded period, soil samples were collected, soil solutions were collected in the flooded period, Eh and soil pH were determined. Nitrogen management affected the physical quality of Gleysol Haplic studied, but did not interfere in the productivity of flooded rice. The carbon and total nitrogen stocks decreased as the depth increased in the soil profile, with an increase in the layer of 10-20 cm. The results indicate that N2O fluxes remained low, regardless of applied N rates, when the soil was flooded, but they showed emission peaks in the non-flooded period, especially after precipitation or in the drainage period for the rice harvest. For the CH4 emissions the highest flows occurred at the end of the vegetative stage (growth) of the rice and after drainage when the soil was low aeration. The N2O and CH4 fluxes did not present a linear relation with the NH4 +, Eh and soil pH values. Emissions of N2O and CH4 did not show significant differences between sources and doses of N. Emissions of N2O increased with the incorporation of green manure, while CH4 emissions were potentiated with the incorporation of rice crop residues. The 64 kg ha-1 dose presented the best efficiency of N fertilizer to cultivate BRS Catiana with the lowest emission intensity. / O cultivo de arroz inundado (Oryza sativa L.) emite tanto N2O como CH4, que podem contribuir significativamente para as emissões totais de gases de efeito estufa (GEE) dos sistemas. A aplicação de fertilizantes nitrogenados, normalmente é necessária para atingir ótimos rendimentos, no entanto, aplicação em excesso, pode aumentar os riscos de poluição e de emissões de N2O e CH4 em sistema de arroz irrigado por inundação. Um estudo em condições de campo foi realizado na Fazenda Palmital, Estação Experimental da Embrapa Arroz e Feijão, em Gleissolo Háplico, com o intuito de determinar as emissões de GEE, o estoque de carbono e as propriedades físicas do solo em sistema de produção de arroz irrigado por inundação em várzeas tropicais sob diferentes fontes e doses de N. Os tratamentos resultaram da combinação fatorial: (ureia comum (UC) e ureia protegida (UP)), e três doses nitrogênio (30, 70, 150 kg ha-1), mais a testemunha. Coletaram-se amostras indeformadas e deformadas de solo nas profundidades 0-5; 5-10; 10-15; 15-20; 20-30; 30-40 e 40-50 cm, para determinação das propriedades físicas do solo. As coletas dos gases foram realizadas na safra 2014/2015, na entressafra 2015, e na safra 2015/2016. As concentrações de N2O e CH4 foram determinadas por cromatografia gasosa. Para determinação de nitrato (NO3-) e amônio (NH4+) no período não inundado foram coletadas amostras de solo e no período inundado foram coletadas soluções do solo, das quais também foram determinados o Eh e o pH do solo. O manejo do nitrogênio afetou a qualidade física do Gleissolo Háplico estudado, porém não interferiu na produtividade do arroz irrigado por inundação. Os estoques de carbono (C) e de N total diminuíram com o aumento da profundidade do perfil do solo, com maior incremento na camada 10-20 cm. Os resultados indicam que os fluxos de N2O permaneceram baixos, independentemente das taxas de N aplicadas, quando o solo estava inundado, mas apresentaram picos de emissões no período não inundado, especialmente após precipitações ou após o período de drenagem para a colheita do arroz. Para as emissões de CH4, os maiores fluxos ocorreram no final da fase vegetativa do arroz e após a drenagem, quando o solo se encontrava com baixa aeração. Os fluxos de N2O e CH4 não apresentaram relação linear com os teores de NH4+, Eh e pH do solo. As emissões de N2O e CH4 não apresentaram diferenças significativas entre as fontes e doses de N. As emissões de N2O elevaram-se com a incorporação de adubo verde, enquanto as emissões de CH4 foram potencializadas com a incorporação dos restos culturais do arroz. A dose 64 kg ha-1 apresentou a melhor eficiência de uso de N fertilizante para cultivar BRS Catiana com a menor intensidade de emissão.