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

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

The aim of this study was to understand the link beween greenhouse gasses emissions (CH4 and N2O) microbial activity and nutrient content in soil from different types of soil in Svalbard. Warming can cause release of large amounts of carbon and nitrogen in form of greenhouse gasses from soil into the atmosphere. This might strengthen the greenhouse effect and thus global climate change. We measured release of greenhouse gases from soil. At the same time, soil sampling was conducted at five different localities in August in the years 2014 and 2015. Soils were found to have low nutrient content and unfavourable C/N ratio to support vegetation growth. Areas were not a significant source of emissions of greenhouse gasses from soil to the atmosphere.

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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.

O Pantanal é a maior área úmida do planeta e considerada uma das maiores fontes naturais de gases de efeito estufa (GEE). A sub-região da Nhecolândia, um dos maiores ecossistemas do Pantanal, possui o sistema lêntico mais diverso, onde lagoas de água doce coexistem com salinas, apesar das condições climáticas regionais não explicarem totalmente esta alta salinidade. As salinas são permanentes e funcionam de maneira diversa, sendo assim, subdivididas em tipologias verde e preta. As salinas verdes e pretas diferem tanto pela composição e funcionamento biogeoquímico, quanto pela abundância de espécies extremófilas. Tal distinção pode afetar o balanço regional de GEE, e assim, reduzir a confiabilidade das estimativas regionais das emissões gasosas. As estimativas de emissões de GEE obtidas anteriormente no Pantanal representaram principalmente ecossistemas de água doce, desconsiderando, portanto, a transferência de massa a partir das lagoas salinas. As lagoas de água doce, porém, podem ser permanentes ou temporárias, dependo da intensidade das inundações anuais. Estas lagoas concentram grande quantidade de matéria orgânica e vegetação aquática que aumenta este aporte orgânico. Devido a diversidade química das águas superiores na Nhecolândia, buscou-se quantificar os fluxos de GEE em lagoas salinas dos tipos verde e preta, e lagoas de água doce. O monitoramento destes corpos d\'água ocorreram nas duas estações climáticas comuns do Pantanal, seca e úmida, quando as alterações climáticas e químicas das águas são marcantes. Deste modo, foi possível retratar o efeito das variáveis abióticas sobre o balanço de massa no sistema água-atmosfera da segunda maior sub-região pantaneira. Duas metodologias distintas foram utilizadas para indicar a variabilidade espacial entre lagoas análogas, como as salinas, e variações específicas em cada lagoa. Os resultados indicaram que houve grande variabilidade espaço-temporal na dinâmica dos GEE entre os ecossistemas estudados, de maneira que, uma mesma lagoa que atuou como fonte em uma estação, comportou-se como sumidouro em outro período. Houve intensa variabilidade espacial, ainda, entre salinas de mesma tipologia, quando no mesmo período, umas podem ser fonte e outras sumidouros para determinados gases. As maiores emissões de metano e gás carbônico ocorreram na lagoa de água doce, porém, salinas verdes apresentaram valores próximos na mesma estação. Isto aponta a necessidade de aumentar as amostragens diretas visando incorporar a variabilidade espacial e temporal aos modelos climáticos regionais. As medidas in situ podem, assim, caracterizar as contribuições individuais no sistema lêntico e aumentar a confiança nas estimativas de emissões gasosas atribuídas ao Pantanal. / The Pantanal is the largest wetland on the planet and considered one of the largest natural sources of greenhouse gases (GHG). The sub-region of Nhecolândia, one of the largest ecosystems in the Pantanal, has the most diverse lentic system, where freshwater lagoons coexist with saline, although regional climatic conditions do not fully explain this high salinity. The salinas are permanent and function in a different way, being thus subdivided into green and black typologies. The green and black salinas differ as much by the composition and biogeochemical functioning, as by the abundance of extremófilas species. Such a distinction may affect the regional GHG balance sheet, and thus reduce the reliability of regional estimates of gaseous emissions. Estimates of GHG emissions previously obtained in the Pantanal represented mainly freshwater ecosystems, thus disregarding the mass transfer from saline lagoons. Freshwater ponds, however, can be permanent or temporary depending on the intensity of annual floods. These ponds concentrate a great amount of organic matter and aquatic vegetation that increases this organic contribution. Due to the chemical diversity of the upper waters in Nhecolândia, it was sought to quantify GHG flows in saline lagoons of the green and black types, and freshwater lagoons. The monitoring of these bodies of water occurred in the two common wetland climate seasons, when the climatic and chemical changes of the waters are remarkable. In this way, it was possible to portray the effect of the abiotic variables on the mass balance in the water-atmosphere system of the second largest sub-region of the Pantanal. Two different methodologies were used to indicate the spatial variability between analogous lagoons, such as salinas, and specific variations in each lagoon. The results indicated that there was great space-time variability in the GHG dynamics among the studied ecosystems, so that the same lagoon that acted as a source in one season, behaved as a sink in another period. There was intense spatial variability, also, between salinas of the same typology, when in the same period, some can be source and other sinks for certain gases. The highest emissions of methane and carbon dioxide occurred in the freshwater lagoon, however, green salinas presented close values in the same season. This points to the need to increase direct sampling to incorporate spatial and temporal variability into regional climate models. In situ measurements can thus characterize individual contributions in the lentic system and increase confidence in the gaseous emissions estimates attributed to the Pantanal.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2018-02-27T15:18:48Z No. of bitstreams: 1 Guimaraes GP 2005.pdf: 1398079 bytes, checksum: 2001454348415a2dbc540e659a2f4498 (MD5) / Made available in DSpace on 2018-02-27T15:18:48Z (GMT). No. of bitstreams: 1 Guimaraes GP 2005.pdf: 1398079 bytes, checksum: 2001454348415a2dbc540e659a2f4498 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Em ambientes marinhos, a química do nitrogênio é controlada por reações redox, mediadas pelo fitoplâncton e por bactérias, que produzem gases trocados com a atmosfera devido ao desequilíbrio entre as concentrações do ar e do mar. Os dois principais gases de nitrogênio envolvidos neste processo são a amônia (NH3) e o óxido nitroso (N2O). O NH3 é a base dominante na atmosfera, possuindo grande importância como neutralizador dos ácidos presentes no ar. O N2O é um importante gás traço na atmosfera e absorve radiação infravermelha contribuindo para o efeito estufa, além de estar associado a diminuição de O3 na estratosfera. Na Baía de Guanabara cerca de 7,8 milhões de habitantes geram esgotos domésticos, que são lançados diretamente nas suas águas gerando elevadas concentrações de nitrogênio inorgânico, levando a acreditar que esta é uma importante fonte de NH3 e N2O para a atmosfera. Neste trabalho foi realizada uma estimativa preliminar dos fluxos de NH3 e N2O na interface ar-mar da Baía de Guanabara em dois tipos de abordagem: espacial e temporal. Para a abordagem espacial foram coletadas 37 amostras entre os dias 05 e 07 de abril de 2004. Para a abordagem temporal, foram coletadas amostras semanais em 10 praias da cidade do Rio de Janeiro, durante o período de julho de 2003 e fevereiro de 2004 (macrotemporal, n = 267), e amostras de 3 em 3 horas em um ponto central durante 9 a 12 de fevereiro de 2004 (microtemporal, n = 25). Em todas as análises a temperatura, salinidade e pH foram medidos in situ e o nitrogênio amoniacal analisado através do método do indofenol. Apenas na abordagem espacial foram analisados nitrito, nitrato (métodos espectrofotométricos) e N2O por cromatografia gasosa com ECD. Os fluxos foram calculados baseado no modelo de duas camadas (two-layer model) adotando concentrações atmosféricas de 1 e 5 μg m-3 para NH3 e de 325 ppb para N2O. Os fluxos de NH3 na interface ar-mar variaram de –31 a 3486 μg N m-2 h-1. Considerando as maiores concentrações na atmosfera (5 μg NH3 m-3), 92% dos fluxos na abordagem espacial, 68% na macrotemporal e 20% na microtemporal indicaram emissão de NH3 para a atmosfera. Os fluxos de N2O variaram entre -46 e 2123 ng N m-2 h-1 (média 306 ± 495 ng N m-2 h-1), dos quais 89% representaram emissão para a atmosfera. Foi verificada uma alta correlação do N2O com o nitrito (r=0,84) indicando que provavelmente o processo dominante de produção de N2O nas águas superficiais da Baía de Guanabara é a nitrificação. Todos os dados indicam uma maior contribuição orgânica no setor oeste da Baía de Gaunabara, contribuindo com altos fluxos de NH3 e N2O para a atmosfera. / In the marine environment, the chemistry of nitrogen is controlled by redox reactions, mediated by phytoplankton and bacteria, that produce gases exchanged with the atmosphere due to the desequilibrium between the concentrations of air and sea. The two main gases of nitrogen involved in this process are ammonia (NH3) and nitrous oxide (N2O). NH3 is the dominant base in the atmosphere and has great importance as neutralizer of the acids in the air. N2O is a trace gas that absorbs infrared radiation contributing to global warming and to ozone depletion in the stratosphere. Around Guanabara Bay about 7.8 million of habitants release domestic sewage directly in to the water elevating the concentrations of inorganic nitrogen, which leads us to believe that this is an important source of NH3 and N2O to atmosphere. A preliminary estimate of the fluxes of NH3 and N2O in the air-sea interface of Guanabara Bay were made using two approachs: spatial and temporal. For the spatial approach 37 samples were collected from 5 to 7 April 2004. For the temporal approach weekly samples were collected at 10 beaches of the city of Rio de Janeiro, during the period of July 2003 and February 2004 (macro temporal, n = 267), and samples in intervals of 3 hours in a central point from 9 to 12 February 2004 (micro temporal, n = 25). The temperature, salinity and pH were measured in situ and the ammoniacal nitrogen analyzed by the indophenol method. Only in the spatial approach were analyzed the nitrite, nitrate (spectrophotometer methods) and N2O by gaseous chromatography with ECD. The fluxes were calculated based on the two-lawyer model adopting atmospheric concentrations of 1 and 5 μg m-3 for NH3 and 325 ppb for N2O. The fluxes of NH3 in the air-sea interface varied from –31 to 3486 μg N m-2 h-1. Considering the greatest concentrations adopted in air (5 μg NH3 m-3), 92% of the fluxes in the spatial, 68% of macro temporal and 20% of micro temporal approaches indicated emission of NH3 to the atmosphere. The fluxes of N2O varied between –6 and 2123 ng N m-2 h-1, of which 89% indicated emission to the air. A high correlation of N2O with nitrite (r=0.84) was verified indicating that probably the dominant process of production of N2O in the surface waters of Guanabara Bay is nitrification. All data indicate a greater organic contribution in the West sector of Guanabara Bay, contributing with high fluxes of NH3 and N2O to the atmosphere.

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2017-10-27T12:46:47Z No. of bitstreams: 0 / Made available in DSpace on 2017-10-27T12:46:47Z (GMT). No. of bitstreams: 0 / Leishmaniose é uma zoonose desenvolvida por protozoários do gênero Leishmania. A doença se manifesta sob a forma visceral e cutânea cujo tratamento apresenta diversas limitações como alto custo, elevada toxicidade dos fármacos e altos índices de recidiva. A leishmaniose cutânea abrange lesões destrutivas e ulceradas que podem evoluir para condições mais graves culminando em óbito dos hospedeiros acometidos. Tratamentos alternativos tem sido implementados com a finalidade de proporcionar acessibilidade financeira e menores efeitos colaterais aos pacientes. A terapia fotodinâmica se insere nesse contexto devido à praticidade, custo reduzido, mínima toxicidade e sem relatos de resistência descritos na literatura. O objetivo desse trabalho foi avaliar os efeitos da terapia fotodinâmica em leishmaniose cutânea induzida em camundongos BALB/c infectados com leishmaniose cutânea. A otimização da PDT também foi avaliada pela administração de doadores de óxido nítrico (S-nitroso-MSA) encapsulados em nanopartículas de quitosana (CSNPs), já que esse composto é altamente reativo e potencialmente tóxico para o parasito. Camundongos BALB/c foram infectados no membro posterior esquerdo com 1.106 promastigotas de Leishmania (L) amazonensis que expressam o gene da luciferase e acompanhados por 4 semanas até o surgimento da lesão. Após esse período, os animais foram distribuídos em 6 grupos (n=4): Controle (não tratado), PDT1 (submetidos à uma sessão de PDT), PDT2 (duas sessões ), PDT1NPNO e PDT2NPNO (uma sessão e duas sessões de PDT em associação com S-nitroso-MSACPNPS, respectivamente), e NPNO (somente S-nitroso-MSA-CP NPS). A segunda sessão foi realizada 24 h após a primeira. A PDT foi efetuada usando um diodo emissor de luz (LED, λ=660 ± 22 nm) e azul de metileno (100 μM), com densidade de energia de 150 J/cm2. O progresso da doença foi avaliado por meio do tamanho da lesão e escala de dor utilizando um paquímetro e filamentos von Frey, respectivamente. A carga parasitária foi quantificada por intermédio do bioimageamento nas primeiras 96 h após o tratamento e nas 4 semanas seguintes. Os resultados obtidos demonstraram redução na carga parasitária durante o período experimental, com exceção do grupo PDT1NPNO. Houve redução parasitária significante em 72 h e 96 h para os grupos PDT2, PDT2NPNO e NPNO. A maior redução da lesão foi observada para o grupo PDT2 bem como menor sensibilidade ao estímulo doloroso. Nossos resultados indicam efeitos benéficos da PDT em duas sessões, sugerindo que pode ter ocorrido modulação do processo inflamatório. Entretanto, o uso das nanopartículas nas condições utilizadas nesse experimento não foi capaz de otimizar a eficiência da PDT nos animais infectados com Leishmania (L) amazonensis. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-02-09T16:06:33Z No. of bitstreams: 1 TESEDOUTORADO_ANA PAULA DA SILVA_2016.pdf: 3643578 bytes, checksum: aee17ef8cffb8a82bfd826eb5c41ddac (MD5) / Made available in DSpace on 2017-02-09T16:06:33Z (GMT). No. of bitstreams: 1 TESEDOUTORADO_ANA PAULA DA SILVA_2016.pdf: 3643578 bytes, checksum: aee17ef8cffb8a82bfd826eb5c41ddac (MD5) / Coordenação de Aperfeiçoamento de Pessoal Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica, Niterói, RJ. / O Óxido nitroso (N2O) é um importante gás do efeito estufa que contribui para as mudanças climáticas globais através do aquecimento radiativo e depleção do ozônio estratosférico. Segundo o IPCC a concentração atmosférica de N2O aumenta a taxas de 0,2 a 0,3% anualmente, e aumentou do período pré-industrial de 270 ppb para 329 ppb em 2016. A emissão deste gás por solos resulta principalmente dos processos de nitrificação e desnitrificação. O melhor conhecimento da contribuição de cada processo poderá ajudar a prever e mitigar as emissões de N2O por solos. Os métodos atuais para a investigação das taxas brutas de nitrificação e desnitrificação envolvem aplicação de inibidores químicos e/ou marcadores isotópicos 15N, os quais alteram a composição da atmosfera do solo. Neste trabalho a teoria do método da separação barométrica de processos (BaPS) foi utilizada para quantificar as taxas brutas de nitrificação e desnitrificação através de medidas de variações da pressão do ar num sistema hermético e isotérmico sem aplicação de inibidores ou marcadores químicos. Câmaras para incubação do solo equipadas com sensores de pressão, temperatura, O2 e CO2 foram construídas e amostras de solo de uma região que emite altos fluxos de óxido nitroso localizada em Jardim Catarina em São Gonçalo (RJ) foram selecionadas para o estudo dos processos de produção do gás. O fluxo in situ foi medido e o resultado médio foi de 25 ngN2O-Ncm-2h-1. A alta emissão de N2O in situ foi observada após período de alagamento da área de amostragem pelas águas poluídas do Rio Alcântara. O método BaPS foi utilizado para determinar as taxas de respiração do solo, nitrificação bruta e desnitrificação em experimentos no laboratório. Os resultados mostraram que as taxas brutas de desnitrificação foram sempre maiores que as taxas brutas de nitrificação e que os maiores fluxos de N2O gerados estão associados ao processo de desnitrificação. / climate change through radiative warming and the depletion of stratospheric ozone. According to the IPCC, the concentration of N2O atmospheric increases at rates of 0.2 to 0.3% annually, and increased had risen from the pre-industrial period from 270 ppb to 324 ppb by 2011. Its emission from soils results mainly from denitrification and nitrification process. A better knowledge of the contribution of each process should help to predict and mitigate N2O emissions by soils. Current methods for investigation of gross nitrification and denitrification rates involve N tracers and acetylene inhibition techniques These methods have the disadvantage of introducing labeled material into soil or changing the composition of soil atmosphere. In this work, the barometric process separation technique (BaPS) was applied to quantify gross nitrification and denitrification rates by measuring air pressure variations in a hermetic and isothermal system without the application of chemical inhibitors or markers. Soil incubation chambers equipped with pressure, temperature, O2 and CO2 sensors were constructed and soil samples from a region known to emit high nitrous oxide flows located in Jardim Catarina, São Gonçalo (RJ) were selected for this study. In situ flow was measured and the mean result resulted in 25 ngN2O-Ncm-2h-1. The high N2O emission in situ was observed after a period of flooding in the polluted waters of the Alcântara River. The BaPS method was used to determine the rates of soil respiration, gross nitrification and denitrification. The results showed that the gross denitrification rate was always greater than nitrification and that the higher N2O fluxes generated are associated with the denitrification process

This thesis links papers reporting field measurements, modelling studies and reviews of greenhouse gas (GHG) emissions and their abatement from agriculture, in particular from livestock production. The aims of the work were to: quantify GHG emissions from litter-based farmyard manures; evaluate means by which GHG emissions from agricultural production may be abated; assess synergies and conflicts between the abatement of other N pollutants on emissions of nitrous oxide (N2O); analyse two records of soil temperature from 1976-2010 from Wolverhampton (UK) and Vienna (Austria). Agricultural emissions of GHGs are not readily abated by ‘end of pipe’ technologies. Large decreases in agricultural GHG emissions may require changes in the production and consumption of food that could have unwelcome impacts on both consumers and producers. However, identifying and prioritizing both modes and locations of production, together with utilizing inputs, such as N fertilizer and livestock feeds, more efficiently can reduce GHG emissions while maintaining outputs. For example, GHG emissions from livestock production may be lessened by increasing the longevity of dairy cows, thereby decreasing the proportion of unproductive replacement animals in the dairy herd. Sourcing a larger proportion of calves from the dairy herd would decrease emissions of GHGs from beef production. The distance between the region of food production to that of consumption has relatively little impact on total GHG emissions per tonne of food product. Due to greater productivity or lesser energy inputs, importing some foods produced in other parts of the world may decrease GHG emissions per tonne compared with UK production, despite the additional emissions arising from long-distance transport. Manure application techniques to abate ammonia (NH3) emissions do not axiomatically increase emissions of N2O and may decrease them. Soil temperature measurements from 1976 to 2010 were consistent with the warming trends reported over the last 40 years.