N2O chemisorption technique for copper dispersion determination was developed and optimized for accurate and reproducible results. With this technique, the bulk oxidation of pre-reduced catalyst can be prevented by N2O decomposition at low temperature (30oC). Only surface copper atoms are oxidized. The amount of freshly oxidized surface coppers is determined from H2-back-titration of fixed oxygen.The impact of temperature and time of exposure during oxidation was studied. Measurements made at higher temperature (60oC) resulted in overestimation of copper dispersion due to oxygen diffusion into the bulk and sub-layers. Much longer exposure time may also have an impact on copper dispersion estimation.For accurate results and good precision, it is recommended to work under mild conditions (isothermal oxidation at 30oC for 45 min.The developed method was successfully applied to fresh and spent catalyst. As expected, the copper dispersion for fresh catalyst was significantly higher than copper dispersion for spent catalyst.

A field experiment was carried out in Ontario, Canada to compare independently measured soil N2O profile concentration and surface N2O flux measurements overwinter and at spring thaw, to estimate the soil N2O content accumulation overwinter, and to estimate the magnitude of the contribution of the physical release of trapped N2O to surface fluxes at spring thaw. Gas samples at various depths were taken and N2O concentrations determined, soil profile gaseous N2O content was calculated by estimating the air-filled pore-space from soil condition measurements, and soil aqueous N2O content was calculated using liquid water content measurements and applying Henry’s Law. Soil N2O content was found to reach a maximum of ~25 mg N2O m-2, and by comparing changes in soil N2O content to surface fluxes measured using the micrometeorological flux-gradient technique, the physical release of previously produced N2O was estimated to contribute up to 47% of spring thaw N2O surface fluxes.

Agriculture management including tillage and crop residues impact the functioning of soil microbiota. Soil microbiota cycle nutrients, with greenhouse gases being a byproduct within the cycle. The main objectives of this thesis were to 1) assess tillage and corn residue impact on N-cycling soil microorganisms and N2O emissions in situ (Chapter 3); and 2) evaluate N-cycling soil microorganisms in situ relative to N2O flux during a spring thaw cycle (Chapter 4). In situ sampling addresses how changing field conditions influence soil bacterial processes. Results indicated tillage and removal of corn residue declined soil microbial abundance and increased N2O emissions. These responses were dependent on local environmental conditions; moisture, carbon and nitrogen availability. The spring thaw study highlighted N-cycling microorganisms were present and active over the spring thaw event, and delayed nosZ denitrifier activity was related to the timing of significant N2O emission events, suggesting new evidence of de novo denitrification. / Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA) and Natural Science and Engineering Research Council (NSERC)

Studies have shown that including perennial forages in cropping rotations can increase soil carbon (C) and lower nitrous oxide (N2O) emissions when compared to continuous annual cropping. Research is needed to evaluate the inclusion of a perennial forage in an annual crop rotation on net carbon dioxide (CO2) and N2O fluxes, natural and agronomic drivers of seasonal greenhouse gases (GHGs), and the possibility of using forages as a C sequestration-CO2 mitigation tool. A long-term field experiment site to determine GHG budgets for Red River Valley cropping systems in Manitoba, Canada was used. The site consisted of four plots with the same annual rotation management history. A perennial legume, alfalfa, was grown in 2008 and 2009 on two plots and spring wheat and industrial oilseed-rapeseed grown on the other two plots in 2008 and 2009, respectively. Nitrous oxide and CO2 fluxes were measured continuously using the flux gradient micrometeorological method. For the net study period, the perennial phase sequestered twice the atmospheric CO2 (2070 kg C ha-1) compared to the annual crops. The annual rotation emitted 3.5 times more N2O than the perennial legume phase. When accounting for harvest C removals and considering GHGs in CO2-equivalent (eq.), the perennial legume phase was a net sink of 5440 kg CO2-eq. ha-1 and the annual rotation was a net source of 4500 kg CO2-eq. ha-1 for the two year study period. Information gathered will help bridge missing data gaps in national emission trends and enhance development of Canadian GHG mitigation models.

Studies have shown that including perennial forages in cropping rotations can increase soil carbon (C) and lower nitrous oxide (N2O) emissions when compared to continuous annual cropping. Research is needed to evaluate the inclusion of a perennial forage in an annual crop rotation on net carbon dioxide (CO2) and N2O fluxes, natural and agronomic drivers of seasonal greenhouse gases (GHGs), and the possibility of using forages as a C sequestration-CO2 mitigation tool. A long-term field experiment site to determine GHG budgets for Red River Valley cropping systems in Manitoba, Canada was used. The site consisted of four plots with the same annual rotation management history. A perennial legume, alfalfa, was grown in 2008 and 2009 on two plots and spring wheat and industrial oilseed-rapeseed grown on the other two plots in 2008 and 2009, respectively. Nitrous oxide and CO2 fluxes were measured continuously using the flux gradient micrometeorological method. For the net study period, the perennial phase sequestered twice the atmospheric CO2 (2070 kg C ha-1) compared to the annual crops. The annual rotation emitted 3.5 times more N2O than the perennial legume phase. When accounting for harvest C removals and considering GHGs in CO2-equivalent (eq.), the perennial legume phase was a net sink of 5440 kg CO2-eq. ha-1 and the annual rotation was a net source of 4500 kg CO2-eq. ha-1 for the two year study period. Information gathered will help bridge missing data gaps in national emission trends and enhance development of Canadian GHG mitigation models.

Dinitrous oxide (N2O) is a potent greenhouse gas some 354 times stronger than carbon dioxide (CO2) in the atmosphere. Recent studies show that lake denitrification contributes to a considerable part of the global N2O emissions. Despite this, lake-N2O emissions are not being accounted for in global greenhouse gas modeling because it has not yet been accurately understood and quantified. The aim of this study was to assess how denitrification varies between and within boreal lakes and how it is controlled by nitrate- (NO3) and carbon (C) availability and temperature. Studies on denitrification were performed using the acetylene inhibition technique on sediments from three lakes in northern Sweden (February to August, 2014). Results showed that denitrification was correlated (linear regression, r2=0.71) with NO3 concentrations in the hypolimnion water at ambient conditions and that additions of NO3 up to a concentration of 50 µg NO3-N L-1 increased denitrification. Temperature increased denitrification in all lakes, at all sites except in one lake in July, when nutrient concentrations were at its lowest. The spatial and temporal variation in denitrification was small at ambient conditions (1-3 µmol N2O m-2 h-1)but the variation in the response to nutrient additions and temperature increase was very high. This was in part attributed to differences in dissolved organic C (DOC). These findings have important implications for future denitrification research and how lake-N2O production is included in greenhouse gas modeling and contributes to our knowledge on how northern boreal lakes may respond to enhanced nutrient loadings and global warming.

High nitrous oxide (N2O) emission potential has been identified in hemiboreal forest on drained Histosols. However, the environmental factors regulating the emissions were unclear. To investigate the importance of different factors on the N2O emission, a modeling approach was accomplished, using CoupModel with Monti-Carlo based multi-criteria calibration method. The model was made to represent a forest on drained peat soil in south-west Sweden where data of fluxes combined with soil properties and plant conditions were used. The model outcome was consistent with measurements of abiotic (soil temperature, net radiation, groundwater level and soil moisture) and biotic responses (net ecosystem exchange and soil respiration). Both dynamics and magnitude of N2O emissions were well simulated compared to measurements (8.7 ± 2.1 kg N/ha/year). The performance indicators for an ensemble of accepted simulations of N2O emission dynamics and magnitudes were correlated to calibrated parameters related to soil anaerobic fraction and atmospheric nitrogen deposition (correlation coefficient, r ≥ 0.4). A weak correlation with N2O emission dynamics was also found for biotic responses (r ≥ 0.3). However, the ME of simulated and measured N2O emissions was better correlated to the ME of soil moisture (r = -0.6), and also to the ME of both the soil temperature (r = 0.53) and groundwater level (r = -0.7). Groundwater level (range from -0.8 m to -0.13 m) was identified as the most important environmental factor regulating the N2O emissions for present forest soil. Profile analysis indicated that N2O was mainly produced in the deeper layers (≥ 0.35 m) of the soil profile. The optimum soil moisture for N2O production was around 70%.

The work presented in this thesis was undertaken to explain the differences in output powers and small-signal gain coefficients observed in cw N20 and C02 lasers. To isolate the factors limiting small-signal gain, the dynamics of conventional cw N20 laser discharges were investigated using a tunable diode laser (TDL) operating in the 2120-2350 cm-1 frequency region. Absorption measurements were made with the TDL on more than 10 different vibrational bands, allowing vibrational population distributions in the three normal modes of vibration of N20 to be determined. The vibrational populations follow a Boltzmann distribution, and the v1 and v2 mode temperatures are found to be strongly coupled, and to maintain equilibrium with the background gas temperature under all discharge conditions. It is observed that the v3 mode temperature saturates at high discharge currents. This saturation, which is attributed to electron de-excitation, is determined to be the primary factor limiting small-signal 10-μm gain in the N20 laser and is much more important than N20 dissociation. The maximum small-signal gain coefficients achievable in cw N20 lasers are calculated, and the results of the work indicates the measures that must be taken to optimize small-signal gain in the N20 laser. / Thesis / Master of Science (MSc)

Vários países têm buscado investigar as emissões de gases do efeito estufa (GEE) e amônia (NH3) na atividade animal para melhor compreensão da dinâmica e excesso desses gases na atmosfera. As informações disponíveis na literatura sobre as emissões de GEE e NH3 em aviários são variáveis e incertas devido à diversidade e condições particulares das instalações, bem como das inúmeras diferenças no sistema de criação e das complexas interações observadas nos dejetos dos animais. A caracterização das emissões do setor avícola normalmente é realizada por monitoramento aéreo das concentrações dos gases dentro das instalações de produção. No entanto, alguns métodos adotados são insuficientes devido às interferências de outros gases, razão por que as medições podem não refletir, com exatidão, as emissões reais. Diante dessa complexidade, nesta pesquisa buscou-se aplicar técnicas que apresentam menores interferências, bem como desenvolver um sistema de amostragem para medir diretamente as emissões de N2O, CH4 e NH3 dos dejetos de frangos de corte. No desenvolvimento do método, utilizou-se como referência o princípio da câmara estática fechada e a análise por cromatografia gasosa (CG), para estimar as emissões de GEE. Para quantificação direta das emissões de NH3, adaptou-se um método semiaberto estático, baseado na captura, em meio ácido, do NH3 volatilizado dos dejetos das aves. Adicionalmente, buscou-se monitorar as emissões diárias de NH3, CH4 e N2O dos dejetos dos frangos, considerando o típico manejo de reutilização da cama de frango. Foram propostos modelos empíricos para as predições das emissões de N2O, CH4 e NH3, em função do número de reutilizações da cama, da idade das aves e de propriedades físico-químicas da cama de frango. As emissões acumuladas por quatro ciclos de criação permitiram calcular perdas anuais de 0,14, 0,35, e 72,0 g de N2O, CH4 e NH3 ave-alojada-1 ano-1, respectivamente. Considerando o número de frangos de corte alojados em 2015, a atividade avícola emitiu cerca de 545,1 Gg CO2eq pelo manejo dos dejetos nos aviários, correspondente a 0,04 kg CO2eq por kg de carne. Reduções de 21, 40 e 78% foram observadas nas emissões anuais de N2O, CH4 e NH3, respectivamente, ao utilizar (seis ciclos) a cama somente em um ciclo de criação. Contudo, um balanço de N foi conduzido para contabilizar as entradas e saídas de N na produção de frangos de corte durante os quatro ciclos de criação avaliados. A principal entrada de N no sistema foi pela ração, como entrada secundária, o N via cama de frango, o qual aumentou consideravelmente a cada ciclo de reutilização. Considerando que esta pesquisa apresenta uma metodologia aplicável e inovadora para determinar os fluxos de GEE em galpões abertos no país, os dados serão úteis para o inventário anual brasileiro das emissões de GEE oriundas dos dejetos da avicultura de corte. Os resultados são úteis também para incentivar novas pesquisas que possam avançar no conhecimento de impactos e alternativas de mitigação de GEE na produção de frangos de corte e, adicionalmente, conferir sustentabilidade à produção de carne no Brasil / Many countries have sought to investigate the emissions of GHG and ammonia (NH3) in livestock production to better understand the dynamics and the excess of these gases in the atmosphere. The information available in the literature on GHG emissions and NH3 in poultry houses are variable and uncertain due to the diversity and particular conditions of the facilities, as well as the numerous differences in the authoring system and the complex interactions observed in animal manure. The characterization of emissions from poultry sector is usually performed by monitoring of gas concentrations in the production facilities. However, some of the methods adopted are inadequated due to interference from other gases, thus, the measurements may not accurately reflect the actual emissions. In this context, this research developed a sampling system with lower interference that directly measure the emissions of N2O, CH4 and NH3 of broiler manure. The proposed methodology includes the principle of static chamber, and gas chromatography (GC) analysis to determine GHG emissions. For the direct quantification of NH3 emissions a semi-open static method was adapted based on the capture of volatilized NH3 from manure of broilers, in an acidic solution. In addition, the daily monitoring of NH3, CH4 and N2O emissions from broiler manure considered the reutilization of poultry litter, which is the usual management. Empirical models were proposed in the study to predict emissions of N2O, CH4 and NH3, depending on the number of reuses of the litter, the age of the birds and physicochemical properties of the litter. Cumulative emissions per production four cycle allowed us to calculate an annual loss of 0.14, 0.35 and 72.0 g N2O, CH4, NH3 bird-place-1 year-1, respectively. Considering the number of broilers grown in 2015, the poultry production chain emitted about 545.1 Gg CO2eq derived from poultry manure management, corresponding to 0.04 kg CO2 eq per kg meat. A reduction of 21, 40 and 78% was observed in the annual emissions of N2O, CH4 and NH3, respectively, when the litter is used in only one breeding cycle instead of six cycles. However, an N balance was conducted to account N inputs and outputs in the production of broiler during the four breeding cycles. The main entrance of N in the production system was the ration, as a secondary input, the N via poultry litter, which increased considerably each reuse cycle. This research presents an applicable and innovative methodology for determining GHG flows in open sheds houses in Brazil. The data presented will be useful to the Brazilian annual inventory of GHG emissions derived from poultry manure. Moreover the present data has the potential to prompt new research that might further the knowledge on the impacts and GHG mitigation alternatives in the production of broiler thus enhancing sustainability in meat production in Brazil

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-10-24T17:04:36Z No. of bitstreams: 1 2013 - Selenobaldo Alexinaldo Cabral de Sant'Anna.pdf: 1507873 bytes, checksum: 9bcc529b3a4670b9741f4312862f95c3 (MD5) / Made available in DSpace on 2017-10-24T17:04:42Z (GMT). No. of bitstreams: 1 2013 - Selenobaldo Alexinaldo Cabral de Sant'Anna.pdf: 1507873 bytes, checksum: 9bcc529b3a4670b9741f4312862f95c3 (MD5) Previous issue date: 2013-02-25 / CNPq / The study aimed to evaluate the changes in the soil stocks of C and N under non-burnt sugarcane grown in an area previously with pasture, and to quantify greenhouse gas emissions (N2O and CH4) and ammonia volatilization losses when using fertilizer and vinasse. The study was conducted in an area of a clayey Oxisol (LVef) in Ribeir?o Preto-SP. For the evaluation of C and N it was considered a chronosequence of two sugarcane areas, with 3 and 25 years of cultivation, and areas with pasture and over 30 years secondary forest. The stocks of C and N were estimated for the 0-30 cm and 0-100 cm layers. There was no statistical difference for the depth 0-30 cm, after correction for soil equal mass between forest, pasture and sugarcane of 3 years, which amounted to, respectively, 55.05, 48.85 and 49.96 Mg C ha-1 and 4.27, 3.74 and 3.83 Mg N ha-1. The area under the > 25 years sugarcane, for this depth range, showed statistically lower values of C stocks (46.04 Mg C ha-1) and N (3.45 Mg Nha-1) compared to secondary forest; but these values did not differ from the other two systems of land use. In the 0-100 cm layer, the forest showed a value significantly higher (118.36 Mg C ha-1) than the > 25 years sugarcane (103.25 Mg C ha-1) and the pasture (102.29 Mg C ha-1). The C stock (109.97 Mg C ha-1) in the 3 years sugarcane did not differ from the other systems. The forest and the 3 years sugarcane had higher N stock, respectively 8.52 and 8.02 Mg N ha-1, when compared with the sugarcane > 25 years (7.04 Mg N ha-1), but they were not different from the pasture (7.79 Mg N ha-1), which was not different from the > 25 years sugarcane. For sampling of gases and volatilization losses of NH3, a study was conducted in a completely randomized block design with six treatments: CSP-control without straw, FSP-fertilizer without straw, FCP-fertilizer with straw, CCP-control with straw, VSP-vinasse without straw and VCP-vinasse with straw, with five replications and three sampling periods in the years 2010, 2011 and 2012. The treatments consisted of applying 160 m3 ha-1 equivalent to 59 kg N ha-1 vinasse in 2010, 70 kg N ha-1 in 2011, and 108 kg N ha-1 in 2012, application of urea at a dose of 52 kg N ha-1 in 2010, and 100 kg N ha-1 in 2011 and 2012, and controls. The temporal variation of N2O fluxes in the three years was from 5.12 to 42.49 ?g N2O-N m2 h-1. In 2010 there was no difference among treatments, and in 2011 and 2012 it followed the FSP = FCP > CSP = CCP = VCP = VSP order. The emission factors ranged from 0.01 to 0.4%. The average flow rates of CH4 were negative. The NH3 volatilization losses in the three years of evaluation were less than 15% and 2% for doses of fertilizers and vinasse, respectively. The results suggest that the planting of sugarcane in pastures with low production does not significantly modify the stocks of C and N in the soil, although they reach values below the secondary forest (> 30 years) ones. The usage of nitrogen fertilization induces the production of N2O from the soil; the same tends to occur with vinasse application. Also, even with the maintenance of the straw, the emission levels are too low to be credited to these practices a risk of compromising the ethanol program. / O trabalho teve como objetivo avaliar as mudan?as nos estoques de C e N no solo em ?rea de cana-de-a??car cultivada sem queima em ?rea antes ocupada por pastagem e quantificar as emiss?es de gases (N2O e CH4) e as perdas por volatiliza??o de am?nia do solo pelo uso de fertilizante e vinha?a. O estudo foi realizado em uma ?rea de LATOSSOLO VERMELHO Eutrof?rrico (LVef), textura argilosa, no Munic?pio de Ribeir?o Preto-SP. Para avalia??o dos estoques de C e N foi considerada uma cronossequ?ncia com duas ?reas de cana-de-a??car, uma com mais de 25 anos e outra com 3 anos de cultivo respectivamente, e uma ?rea ocupada com pastagem e outra com floresta secund?ria com mais de 30 anos. Os estoques de C e N foram estimados para as camadas de 0-30 cm e de 0-100 cm. N?o houve diferen?a estat?stica para a profundidade 0-30 cm corrigido para massa igual de terra entre a floresta, pastagem e cana 3 anos, que somaram, respectivamente, 55,05, 48,85 e 49,96 Mg C ha-1 e 4,27, 3,74 e 3,83 Mg N ha-1. A ?rea sob cana > 25 anos para esse intervalo de profundidade apresentou estatisticamente menores valores dos estoques de C (46,04 Mg C ha-1) e N (3,45 Mg N ha-1) em rela??o a floresta secund?ria, por?m esses valores n?o diferiram dos outros dois sistemas de uso do solo. Na camada 0-100 cm a floresta apresentou valor significativamente maior (118,36 Mg C ha-1) do que as ?reas de cana > 25 anos (103,25 Mg C ha-1) e a pastagem (102,29 Mg C ha-1). A ?rea de cana com 3 anos apresentou estoque de C (109,97 Mg C ha-1) que n?o diferiu entre os tr?s outros sistemas. A floresta e a cana com 3 anos apresentaram maiores estoque de N, respectivamente (8,52 e 8,02 Mg N ha-1), comparada com a ?rea de cana > 25 anos (7,04 Mg N ha-1), mas n?o diferente da ?rea de pastagem (7,79 Mg N ha-1), a qual n?o diferenciou da ?rea de cana > 25 anos. Para as amostragens de gases e as perdas por volatiliza??o de NH3 o trabalho foi realizado em delineamento experimental em bloco inteiramente casualizado, com seis tratamentos: CSP - controle sem palha, FSP - fertilizante sem palha, FCP - fertilizante com palha, CCP - controle com palha, VSP - vinha?a sem palha e VCP - vinha?a com palha e com cinco repeti??es e em tr?s per?odos de amostragens correspondentes aos anos de 2010, 2011 e 2012. Os tratamentos consistiram na aplica??o de 160 m3 ha-1 de vinha?a equivalente a 59 kg N ha-1 em 2010, a 70 kg N ha-1 em 2011 e a 108 kg N ha-1 em 2012, aplica??o de ureia na dose de 52 kg N ha-1em 2010 e 100 kg N ha-1 em 2011 e 2012 e controles. A varia??o temporal dos fluxos de N2O nos tr?s anos foi 5,12 a 42,49 ?g N-N2O m2 h-1. Em 2010 n?o houve diferen?a entre tratamentos e em 2011 e 2012 seguiram a ordem FSP = FCP > CSP = CCP = VCP = VSP. Os fatores de emiss?o variaram entre 0,01 e 0,4%. Os fluxos m?dios de CH4 foram negativos. As perdas por volatiliza??o de NH3 nos tr?s anos de avalia??o foram menores que 15% e 2% para as doses de fertilizantes e vinha?a respectivamente. Os resultados sugerem que o plantio da cana-de-a??car em ?reas de pastagens de baixa produ??o n?o modifica significativamente os estoques de C e N do solo, mas alcan?am n?veis inferiores aos da floresta secund?ria (>30 anos). O uso da fertiliza??o nitrogenada induz a produ??o de N2O do solo, assim como tende a ocorrer com a aplica??o da vinha?a, e mesmo com a manuten??o da palhada, os n?veis de emiss?o s?o muito baixos para se atribuir a essas opera??es um risco de comprometimento do programa de etanol.