A recomendação de doses de nitrogênio (N) para a cana-de-açúcar (Saccharum spp.) com base em testes de solo é essencial para o aumento da sustentabilidade desse agroecossistema. Além disso, pouco se conhece sobre as reações do N orgânico dissolvido (NOD) na zona de transição palha-solo nos canaviais. A influência das formas minerais de N (N-NH4+ e N-NO3-) na mineralização de carbono (C) nessa região transitória também é desconhecida. Desse modo, os objetivos do estudo foram: i) correlacionar diversos métodos para a predição do N mineralizável do solo com parâmetros de resposta da cana-de-açúcar ao N; ii) quantificar os processos de mineralização de C e sorção de compostos do NOD aplicados em palha e solo (ambos amostrados na zona de transição); e iii) determinar a mineralização C e o conteúdo de N mineral em palha e solo de cana-de-açúcar (provenientes da zona de transição) pela adição de 14C-glicose associada ou não à fontes minerais de N. Entre 2006 e 2013 foram instalados 21 experimentos de curva de resposta da cana-de-açúcar ao N no Estado de São Paulo, Brasil, para correlacionar métodos de natureza biológica, química, microbiológica e isotópica (15N), com a produtividade de colmos (PCC) e extração de N (ENC) no tratamento controle, produção relativa da cultura (PRC) e com a dose de N necessária para obtenção de 90% da PRC (DN 90% PRC). As amostragens de solo foram realizadas nas camadas de 0-20 e 20-40 cm. Foram detectadas fracas correlações entre a incubação anaeróbia e a PCC, e o N extraível por KCl a quente por 4 h e o N extraível por tampão fosfato-borato a pH 11,2 com a ENC. Os métodos não se correlacionaram com a PRC e a DN 90% PRC. Nenhum método é recomendado no ajuste de doses de N para aplicação em soqueiras de cana-de-açúcar no Estado de São Paulo. Para o estudo das reações do NOD e do N mineral, amostras de palha e solo foram coletadas na região de transição entre os dois materiais, em dois sítios experimentais localizados no Estado de São Paulo. A mineralização de C e sorção de mistura de aminoácidos, peptídeos, ureia e proteína (todos marcados em 14C) foi determinada pela aplicação dos compostos em palha e solo. A mineralização de C e conteúdo de N mineral pela adição de 14C-glicose com ou sem as formas de N mineral (N-NH4+ e N-NO3-) também foi avaliada. Existem diferenças acentuadas entre a palha e solo relacionadas à dinâmica do NOD, perfil da comunidade microbiana e imobilização de N. Em geral, o conteúdo de 14C restante dos compostos do NOD foi maior no solo em relação à palha. Os peptídeos e a ureia apresentaram rápida mineralização de C, enquanto que a sorção da proteína foi maior no solo em comparação com a palha. A associação da 14C-glicose com N-NO3- resultou em maior mineralização de 14C na palha de ambos os sítios. Ocorreu intensa imobilização de N-NH4+, sobretudo no resíduo de cana-de-açúcar. / Recommendation of nitrogen (N) rates for sugarcane (Saccharum spp.) based upon soil testing is essential for increasing the sustainability of this agroecosystem. In addition, little is known about the dynamics of dissolved organic nitrogen (DON) in the straw-soil transition zone in sugarcane fields. The influence of mineral N forms in the carbon (C) mineralization in this transitional region is also unknown. Thus, the objectives of this study were: i) correlate several methods to predict the soil mineralizable N with sugarcane N response parameters; ii) quantifying the C mineralization and sorption processes of DON compounds applied to straw and soil (both sampled in the transition zone); and iii) determine the C mineralization and mineral N content in straw and soil (from the transition zone) by addition of 14C-glucose with or without mineral sources of N. Between 2006 and 2013, 21 sugarcane N response trials were performed in the State of São Paulo, Brazil, to correlate biological, chemical, microbiological and isotopic (15N) methods with stalks yield (SYC) and total N uptake (NUC) in the control treatment, relative stalks yield (RSY) and the N rate required to achieve 90% of the RSY (NR 90% RSY). Soil sampling was performed at 0-20 and 20-40 cm depths. Weak correlations were detected between anaerobic incubation and the SYC, and the hot KCl extractable N and phosphate-borate buffer at pH 11.2 extractable N with NUC. Methods did not correlate with RSY and the NR 90% RSY. No method is recommended for adjusting N fertilizer rates for application on sugarcane ratoons in the state of São Paulo, Brazil. To study the reactions of DON and mineral N, straw and soil samples were collected in the transition region between the two materials, in two experimental sites located in the State of São Paulo. The C mineralization and sorption of 14C-labelled amino acids mix, peptides, urea and protein was performed by addition of the compounds in straw and soil. The C mineralization and mineral N content by the addition of 14C-glucose with or without mineral N forms (NH4+-N and NO3--N) was also checked. There are marked differences between straw and soil regarding to the DON dynamics, microbial community profile and N immobilization. In general, the 14C remaining of the applied DON compounds in the soil was higher when compared to the straw. Peptides and urea had a rapid C mineralization, while the protein sorption was higher in the soil than the straw. The use of 14C-glucose with NO3--N intensified 14C mineralization in the straw of both sites. There was an intense immobilization of NH4+-N, mainly in the sugarcane residue.

Return liquor from thermal hydrolysis process (THP) can significantly add to the nitrogen load of a wastewater treatment plant (WWTP) and introduce UV quenching substances to the wastewater stream when recycled. While there are mature technologies in place to handle the inorganic nitrogen produced due to the thermal pretreatment, organic nitrogen remains a parameter of concern for utilities employing THP pretreatment. The impact of operating conditions of the THP on dissolved organic nitrogen (DON) and UV absorbance in return liquor was investigated. Operating conditions studied were (1) operating temperature (2) solids retention time (SRT) in the anaerobic digester (3) THP flash pressure (4) the effect of co-digestion of sewage sludge with food waste and, (5) polymer conditioning. Operating temperature and polymer dose had the most significant impact on DON and UV quenching. It was found that an increase in operating temperature resulted in an increase in DON, which was primarily contributed by the hydrophilic fraction. An increase in temperature also resulted in increased UV254 absorbance. However, this trend was not linear and the increase was more pronounced when the temperature was increased from 150 C to 170 C. Increasing flash pressure from 25 psi to 45 psi did not have a significant impact on the return liquor. However, increasing the flash pressure to 75 psi increased the DON and UV254 absorbing compounds. Co-digesting the sludge with food waste resulted in a slight increase in DON and a decrease in dissolved organic carbon (DOC) and UV quenching compounds. Increasing the SRT from 10 days to 15 days resulted in a slight decrease in DON but did not have any impact on UV254 absorbance. Overall, it can be concluded that optimizing operating conditions of thermal hydrolysis process can result in decreased DON and UV quenching compounds in the recycle stream. / Master of Science

Many Best Management Practices (BMPs) have been developed to reduce excessive nutrients in stormwater runoff and mitigate harmful algal blooms in downstream receiving water bodies. This study demonstrates a new BMP by comparing two green sorption media (i.e., specialty adsorbents) for nutrient removal in cascade upflow biofiltration systems operated in parallel. The proposed filtration technology can control hydraulic gradients, prevent clogging and settlements, and increase hydraulic loading while removing more nutrients in an integrated physicochemical and microbiological treatment process. The two green sorption media being tested in this study include zero-valent-iron and perlite-based green sorption media (ZIPGEM) and biochar, iron, and perlite-integrated green sorption media (BIPGEM). BIPGEM or ZIPGEM was installed in two identical upflow bioreactors operated in sequence within each biofiltration system compared mainly for nitrate removal at three influent conditions for process reliability assessment. In addition, kinetics studies were conducted and analyzed to improve the understanding of reactor design. Dissolved organic nitrogen was monitored by using FT-ICR MS (Fourier transform ion cyclotron resonance mass spectrometer) whereas population dynamics of nitrifiers and denitrifiers were quantified by using RT-PCR (real time polymerase chain reaction). The process reliability was compared and confirmed based on the nitrate removal efficiencies, microbial population, and oxidation-reduction potential variations across the two biofiltration systems with different green sorption media. Results indicated that ZIPGEM performed slightly better than BIPGEM and the two identical upflow bioreactors operated in sequence within each biofiltration system exhibited steady operation with higher hydraulic loading relative to the downflow settings in the literature.

Studies were conducted to evaluate the impact of landfill leachate discharge on the operation of waste water treatment plants (WWTPs). Two aspects of interferences were found: one is UV quenching substances, which are bio-refractory and able to penetrate the biological treatment processes, consequently interfere the UV disinfection in WWTPs. The other one is organic nitrogen, which can pass the nitrification-denitrification process and contribute to the effluent total nitrogen (TN). Also, treatability study was conducted for landfill gas (LFG) condensate. In a laboratory study, leachate samples were fractionated into humic acids (HA), fulvic acids (FA) and Hydrophilic (Hpi) fractions, the specific UV254 absorbance (SUVA254) of the three fractions follows: HA > FA > Hpi. However, the overall UV254 absorbance of the Hpi fraction was important because there was more hydrophilic organic matter than humic or fulvic acids. It was found that the size distribution of the three fractions follows: HA > FA > Hpi. This indicates that membrane separation following biological treatment is a promising technology for the removal of humic substances from landfill leachates. Leachate samples treated in this manner could usually meet the UV transmittance requirement of the POTWs. Also, nitrogen species in landfill leachates under various stabilization states were investigated. Although the effect of landfill stabilization state on the characteristics of organic matter and ammonia is well documented, there are few investigations into the landfill leachate organic nitrogen under different stabilization stages. Ammonia was found to leach out slower than organic matter and can maintain a constant level within the first a couple of years (< 10 years). The concentration and biodegradability of organic nitrogen were found to decrease with landfill age. A size distribution study showed that most of organic nitrogen in landfill leachates is < 1 kDa. The protein concentration was analyzed and showed a strong correlation with the organic nitrogen. Different slopes of regression curves of untreated and treated leachates indicate that protein is more biodegradable than the other organic nitrogen species in landfill leachates. XAD-8 resin was employed to isolate the hydrophilic fraction of leachate samples, hydrophilic organic nitrogen was found to be more biodegradable/bioavailable than the hydrophobic fractions. Furthermore, biological and physical-chemical treatment methods were applied to a landfill biogas (LFG) condensate to explore the feasible treatment alternatives for organic contaminant and arsenic removal efficiency. Sequencing batch reactor (SBR) showed effectiveness for the degradation of organic matter, even in an environment containing high levels of arsenic. This indicated a relatively low toxicity of organic arsenic as compared to inorganic arsenic. However, for arsenic removal, oxidation-coagulation, including biological oxidation, conventional oxidation and advanced oxidation followed by ferric salt coagulation, and carbon adsorption were not effective for what is believed to be tri-methyl arsenic. Among these, advanced oxidation-coagulation showed the best treatment efficiency (15.1% removal). Only reverse osmosis (RO) could reduce the arsenic concentration to an acceptable level to meet discharge limits. These results implied high stability and low toxicity of organic arsenic. / Ph. D.

Espécies nitrogenadas vem sendo adicionadas ao meio ambiente de forma intensa desde o desenvolvimento do processo Haber-Bosch para transformação de N2 em NH3, alterando significativamente o ciclo biogeoquímico do nitrogênio no ambiente. Uma vez na atmosfera, o nitrogênio reativo é depositado de volta à superfície da Terra por processos de deposição úmida e seca. A importância de levar em conta as formas orgânicas de nitrogênio para estimar a deposição de nitrogênio atmosférico pela chuva (úmida) já é conhecida, no entanto, ainda há poucos trabalhos que avaliam essa fração devido às dificuldades e incertezas impostas pelos métodos analíticos disponíveis. Este trabalho traz o desenvolvimento de um novo método, simples e de baixo custo, para a determinação de nitrogênio orgânico (N-org) em água de chuva utilizando o processo foto-Fenton e um foto-reator construído de forma artesanal. Por meio da adição de solução de Fenton (50 µmol L-1 Fe2+ e 2 mmol L-1 H2O2) e 90 min de radiação UV (85 °C) foi possível obter em média 106 ± 8% de recuperação de nitrogênio para soluções contendo 50 µmol N L-1 das moléculas modelos: ureia, serina, glicina e histidina. No caso da arginina, 90 min de radiação foi suficiente para degradar soluções contendo 10 µmol N L-1. O reator comercial se mostrou mais eficiente na degradação dos compostos testados (30 min), no entanto, com um tempo de 75 min, o reator artesanal atingiu os mesmos resultados. Com o uso de 0,2 g L-1 TiO2 e 120 min de radiação UV, também foi possível obter resultados satisfatórios. Porém, esse método possuiu valores de branco elevados, havendo necessidade de filtrar as amostras irradiadas antes da análise, adicionando tempo e custo ao procedimento analítico. O método desenvolvido utilizando foto-Fenton foi aplicado para a determinação de N-org em amostras de água de chuva coletadas na cidade de Ribeirão Preto (SP) de 2013 a 2017. A concentração de N-org variou de 3,5 a 195 µmol N L-1 com concentração média ponderada pelo volume (MPV) de 17,7 ± 1,0 µmol N L-1 (n=236). Essa média foi maior que aquelas obtidas em água de chuva de várias partes do mundo, podendo ser atribuída a elevada queima de biomassa na região de estudo. As concentrações de aminoácidos livres dissolvidos (AA) representaram em média 15 ± 12% (n=144) em relação à fração orgânica de nitrogênio na chuva, enquanto as concentrações de ureia foram próximas ou inferiores ao limite de quantificação do método (0,5 µmol N L-1). Considerando toda série temporal iniciada no mesmo sítio amostral desde 2005, as concentrações MPV calculadas para os íons NH4+ foi de 22,2 ± 1,1 µmol L-1 (n=460), NO3- de 13,3 ± 0,6 µmol L-1 (n=466), sendo que a concentração de NO2- foi irrelevante. Foram obtidas concentrações significativamente mais elevadas (teste-t, P=0,05) de NH4+, NO3-, N-org e AA no período de safra da cana (seco) com relação à entressafra (chuvoso), para todos os anos avaliados. Apesar da colheita manual da cana ter sido drasticamente reduzida, o fato de manter a mesma tendência sazonal desde 2005, demonstra que a prática da queima de biomassa ainda é intensa na região. O uso de fogo para manejo na área rural ainda é comum, além de haver grandes áreas queimadas de forma acidental. A deposição úmida de nitrogênio (N-org + NH4+ + NO3-) para Ribeirão Preto foi de 10,5 kg (N) ha-1 ano-1, sendo que a fração orgânica representou 33% dessa deposição, demonstrando a importância de se determinar N-org para melhor estimar os fluxos atmosféricos de deposição. A massa estimada de nitrogênio depositada pela chuva é cerca de 16% do nitrogênio aplicado por meio de fertilizantes em culturas de cana. Somando as deposições de nitrogênio pelo material particulado, pela fase gasosa, e úmida, esta última representa 71% do fluxo atmosférico de nitrogênio. Nesse contexto, a fração orgânica corresponde a 24% da deposição total, sendo que este valor ainda pode estar sendo subestimado, pois as concentrações de N-org no material particulado não foram determinadas. A simplicidade e exatidão do método aqui proposto pode facilitar a aquisição de dados de N-org na chuva de outras partes do mundo, melhorando assim o conhecimento sobre o ciclo biogeoquímico global do nitrogênio. / Nitrogen species have been intensively added to the environment since the development of Haber-Bosch process for N2 transformation to NH3, significantly altering the biogeochemical cycle of nitrogen. Once in the atmosphere, reactive nitrogen is deposited back to the Earth\'s surface by wet and dry deposition processes. The importance of taking into account the organic forms of nitrogen to estimate atmospheric nitrogen deposition by rain is already known. However, few studies evaluated this fraction due to the difficulties and uncertainties imposed by the available analytical methods. This work presents the development of a new, simple and low-cost method for the determination of organic nitrogen (N-org) in rainwater using photo-Fenton process and a homemade photo-reactor. By adding Fenton solution (50 mol L-1 Fe2+ and 2 mmol L-1 H2O2) and keeping the reaction under UV radiation for 90 min (85 °C), it was possible to obtain an average of 106 ± 8% nitrogen recovery for solutions containing 50 mol N L-1 of the model molecules: urea, serine, glycine and histidine. In the case of arginine, 90 min of radiation was sufficient to degrade solutions containing 10 mol N L-1. A commercial reactor showed to be more efficient in degradation of the tested compounds (30 min). However, with a time of 75 min, the homemade reactor achieved the same results. With 0.2 g L-1 TiO2 and 120 min of UV radiation, it was also possible to obtain satisfactory results. Nevertheless, this method had high blank values, and filtration of irradiated samples before the analysis was necessary, which increased time and cost to the analytical procedure. The developed method using photo-Fenton was applied to determine N-org in rainwater samples collected in Ribeirão Preto city (SP) from 2013 to 2017. N-org concentrations ranged from 3.5 to 195 mol N L-1 with a volume-weighted mean concentration (VWM) of 17.7 ± 1.0 mol N L-1 (n = 236). This value was higher than those reported for rainwater from different parts of the world, and this fact can be attributed to the high biomass burning in the study region. Dissolved free amino acids (AA) mean concentrations represented 15 ± 12% (n = 144) of the organic nitrogen fraction in rain, while urea concentrations were close to or below the limit of quantification of the method (0.5 mol N L-1). Considering all temporal series, initiated in 2005 at the same sampling site, the VWM concentration calculated for NH4+ ions was 22.2 ± 1.1 mol L-1 (n = 460) and for NO3- was 13.3 ± 0.6 mol L-1 (n = 466), while NO2- mean concentration was irrelevant. Significantly higher concentrations (t-test, P = 0.05) of NH4+, NO3-, N-org and AA were obtained during the harvest period (dry season) in relation to the non-harvest one (rainy season), for all evaluated years. Although manual harvesting was drastically reduced, the fact that the same seasonal trend has been maintained since 2005 demonstrates that the practice of biomass burning is still intense in the region. In rural area, using fire for land management is still common, in addition to large areas burned by unintentional fires. Nitrogen deposition (N-org + NH4+ + NO3-) in Ribeirão Preto was 10.5 kg (N) ha-1 year-1, and the organic fraction represented 33% of this deposition, demonstrating the importance of determining N-org to better estimate the atmospheric deposition fluxes. The estimated mass of nitrogen deposited by rain represents approximately 16% of the nitrogen introduced by fertilizers in sugarcane crops. Summing up the nitrogen deposition by particulate matter, by gas phase, and by rain, the latter represents 71% of the atmospheric nitrogen flux. In this context, the organic fraction corresponds to 24% of the total deposition, and this value may still be underestimated, since N-org concentrations in particulate matter were not determined. The simplicity and accuracy of the method proposed here may facilitate acquisition of N-org data in rainwater from other parts of the world, thus improving the knowledge on the global biogeochemical cycle of nitrogen.

No description available.

Espécies nitrogenadas vem sendo adicionadas ao meio ambiente de forma intensa desde o desenvolvimento do processo Haber-Bosch para transformação de N2 em NH3, alterando significativamente o ciclo biogeoquímico do nitrogênio no ambiente. Uma vez na atmosfera, o nitrogênio reativo é depositado de volta à superfície da Terra por processos de deposição úmida e seca. A importância de levar em conta as formas orgânicas de nitrogênio para estimar a deposição de nitrogênio atmosférico pela chuva (úmida) já é conhecida, no entanto, ainda há poucos trabalhos que avaliam essa fração devido às dificuldades e incertezas impostas pelos métodos analíticos disponíveis. Este trabalho traz o desenvolvimento de um novo método, simples e de baixo custo, para a determinação de nitrogênio orgânico (N-org) em água de chuva utilizando o processo foto-Fenton e um foto-reator construído de forma artesanal. Por meio da adição de solução de Fenton (50 µmol L-1 Fe2+ e 2 mmol L-1 H2O2) e 90 min de radiação UV (85 °C) foi possível obter em média 106 ± 8% de recuperação de nitrogênio para soluções contendo 50 µmol N L-1 das moléculas modelos: ureia, serina, glicina e histidina. No caso da arginina, 90 min de radiação foi suficiente para degradar soluções contendo 10 µmol N L-1. O reator comercial se mostrou mais eficiente na degradação dos compostos testados (30 min), no entanto, com um tempo de 75 min, o reator artesanal atingiu os mesmos resultados. Com o uso de 0,2 g L-1 TiO2 e 120 min de radiação UV, também foi possível obter resultados satisfatórios. Porém, esse método possuiu valores de branco elevados, havendo necessidade de filtrar as amostras irradiadas antes da análise, adicionando tempo e custo ao procedimento analítico. O método desenvolvido utilizando foto-Fenton foi aplicado para a determinação de N-org em amostras de água de chuva coletadas na cidade de Ribeirão Preto (SP) de 2013 a 2017. A concentração de N-org variou de 3,5 a 195 µmol N L-1 com concentração média ponderada pelo volume (MPV) de 17,7 ± 1,0 µmol N L-1 (n=236). Essa média foi maior que aquelas obtidas em água de chuva de várias partes do mundo, podendo ser atribuída a elevada queima de biomassa na região de estudo. As concentrações de aminoácidos livres dissolvidos (AA) representaram em média 15 ± 12% (n=144) em relação à fração orgânica de nitrogênio na chuva, enquanto as concentrações de ureia foram próximas ou inferiores ao limite de quantificação do método (0,5 µmol N L-1). Considerando toda série temporal iniciada no mesmo sítio amostral desde 2005, as concentrações MPV calculadas para os íons NH4+ foi de 22,2 ± 1,1 µmol L-1 (n=460), NO3- de 13,3 ± 0,6 µmol L-1 (n=466), sendo que a concentração de NO2- foi irrelevante. Foram obtidas concentrações significativamente mais elevadas (teste-t, P=0,05) de NH4+, NO3-, N-org e AA no período de safra da cana (seco) com relação à entressafra (chuvoso), para todos os anos avaliados. Apesar da colheita manual da cana ter sido drasticamente reduzida, o fato de manter a mesma tendência sazonal desde 2005, demonstra que a prática da queima de biomassa ainda é intensa na região. O uso de fogo para manejo na área rural ainda é comum, além de haver grandes áreas queimadas de forma acidental. A deposição úmida de nitrogênio (N-org + NH4+ + NO3-) para Ribeirão Preto foi de 10,5 kg (N) ha-1 ano-1, sendo que a fração orgânica representou 33% dessa deposição, demonstrando a importância de se determinar N-org para melhor estimar os fluxos atmosféricos de deposição. A massa estimada de nitrogênio depositada pela chuva é cerca de 16% do nitrogênio aplicado por meio de fertilizantes em culturas de cana. Somando as deposições de nitrogênio pelo material particulado, pela fase gasosa, e úmida, esta última representa 71% do fluxo atmosférico de nitrogênio. Nesse contexto, a fração orgânica corresponde a 24% da deposição total, sendo que este valor ainda pode estar sendo subestimado, pois as concentrações de N-org no material particulado não foram determinadas. A simplicidade e exatidão do método aqui proposto pode facilitar a aquisição de dados de N-org na chuva de outras partes do mundo, melhorando assim o conhecimento sobre o ciclo biogeoquímico global do nitrogênio. / Nitrogen species have been intensively added to the environment since the development of Haber-Bosch process for N2 transformation to NH3, significantly altering the biogeochemical cycle of nitrogen. Once in the atmosphere, reactive nitrogen is deposited back to the Earth\'s surface by wet and dry deposition processes. The importance of taking into account the organic forms of nitrogen to estimate atmospheric nitrogen deposition by rain is already known. However, few studies evaluated this fraction due to the difficulties and uncertainties imposed by the available analytical methods. This work presents the development of a new, simple and low-cost method for the determination of organic nitrogen (N-org) in rainwater using photo-Fenton process and a homemade photo-reactor. By adding Fenton solution (50 mol L-1 Fe2+ and 2 mmol L-1 H2O2) and keeping the reaction under UV radiation for 90 min (85 °C), it was possible to obtain an average of 106 ± 8% nitrogen recovery for solutions containing 50 mol N L-1 of the model molecules: urea, serine, glycine and histidine. In the case of arginine, 90 min of radiation was sufficient to degrade solutions containing 10 mol N L-1. A commercial reactor showed to be more efficient in degradation of the tested compounds (30 min). However, with a time of 75 min, the homemade reactor achieved the same results. With 0.2 g L-1 TiO2 and 120 min of UV radiation, it was also possible to obtain satisfactory results. Nevertheless, this method had high blank values, and filtration of irradiated samples before the analysis was necessary, which increased time and cost to the analytical procedure. The developed method using photo-Fenton was applied to determine N-org in rainwater samples collected in Ribeirão Preto city (SP) from 2013 to 2017. N-org concentrations ranged from 3.5 to 195 mol N L-1 with a volume-weighted mean concentration (VWM) of 17.7 ± 1.0 mol N L-1 (n = 236). This value was higher than those reported for rainwater from different parts of the world, and this fact can be attributed to the high biomass burning in the study region. Dissolved free amino acids (AA) mean concentrations represented 15 ± 12% (n = 144) of the organic nitrogen fraction in rain, while urea concentrations were close to or below the limit of quantification of the method (0.5 mol N L-1). Considering all temporal series, initiated in 2005 at the same sampling site, the VWM concentration calculated for NH4+ ions was 22.2 ± 1.1 mol L-1 (n = 460) and for NO3- was 13.3 ± 0.6 mol L-1 (n = 466), while NO2- mean concentration was irrelevant. Significantly higher concentrations (t-test, P = 0.05) of NH4+, NO3-, N-org and AA were obtained during the harvest period (dry season) in relation to the non-harvest one (rainy season), for all evaluated years. Although manual harvesting was drastically reduced, the fact that the same seasonal trend has been maintained since 2005 demonstrates that the practice of biomass burning is still intense in the region. In rural area, using fire for land management is still common, in addition to large areas burned by unintentional fires. Nitrogen deposition (N-org + NH4+ + NO3-) in Ribeirão Preto was 10.5 kg (N) ha-1 year-1, and the organic fraction represented 33% of this deposition, demonstrating the importance of determining N-org to better estimate the atmospheric deposition fluxes. The estimated mass of nitrogen deposited by rain represents approximately 16% of the nitrogen introduced by fertilizers in sugarcane crops. Summing up the nitrogen deposition by particulate matter, by gas phase, and by rain, the latter represents 71% of the atmospheric nitrogen flux. In this context, the organic fraction corresponds to 24% of the total deposition, and this value may still be underestimated, since N-org concentrations in particulate matter were not determined. The simplicity and accuracy of the method proposed here may facilitate acquisition of N-org data in rainwater from other parts of the world, thus improving the knowledge on the global biogeochemical cycle of nitrogen.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-05-23T15:29:24Z No. of bitstreams: 1 PATRICIA A DE SOUZA_TESE DOUTORADO__GEOQUÍMICA UFF.pdf: 3232130 bytes, checksum: 1d90cf082dcb5a35552bfb02f10beaf7 (MD5) / Made available in DSpace on 2017-05-23T15:29:24Z (GMT). No. of bitstreams: 1 PATRICIA A DE SOUZA_TESE DOUTORADO__GEOQUÍMICA UFF.pdf: 3232130 bytes, checksum: 1d90cf082dcb5a35552bfb02f10beaf7 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Fundação de Amparo a Pesquisa do Rio de Janeiro / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / As regiões tropicais estão sofrendo mudanças na quantidade e na forma de N depositado como um resultado da poluição urbana. As origens e os sorvedouros desses poluentes têm sido pouco estudados. Neste trabalho foram examinadas as entradas atmosféricas de N em regiões costeiras urbanas e em áreas montanhosas de Floresta Atlântica (400 m e 1000 m acima do mar) no estado do Rio de Janeiro, de agosto de 2008 a agosto de 2009. Concentrações de nitrogênio total dissolvido (NTD), nitrogênio inorgânico dissolvido (NID= NH4++ NO3-+ O2-) e ureia foram medidos na precipitação total em todos os locais de amostragem, bem como na transprecipitação - água que atravessa o dossel da floresta - em locais de uma floresta submontana. Nitrogênio total dissolvido foi analisado pelo método de oxidação por perssulfato de potássio. Amônio (NH4+) e nitrito (NO2-) foram determinados pelos métodos espectrofotométricos de Azul de Indofenol e diazotação, respectivamente. Nitrato (NO3-) foi analisado pelo método espectrofotométrico após o método de redução de cádmio em amostras de transprecipitação. Em amostras de precipitação total, NO3- foi analisado por método cromatógrafo. Ureia foi determinada pelo método spectrofotométrico de diacetilmonoxima. Nitrogênio orgânico dissolvido (NOD) foi calculado como a diferença entre NTD e NID. As concentrações anuais médias ponderadas pelo volume de todas as espécies foram maiores nas áreas costeiras urbanas que no nos locais de floresta, com NOD compreendendo respectivamente, 32 a 56% e 26 a 32% das concentrações de NTD na precipitação total. A deposição total de NTD variou 12,1 a 17,2 kg N ha-1 ano - 1 e tenderam a decrescer com o aumento da distância da região costeira urbana. O fluxo de NTD na transprecipitação na floresta submontana, 34,4 kg N ha-1 ano-1, foi duas vezes maior que a deposição de NTD na precipitação total, com NOD compreendendo 61% do total de N depositado no solo da floresta. A magnitude e a qualidade do NOD foram ainda mudadas durante a passagem através do dossel da floresta; ureia compreendeu 27% do NOD na transprecipitação comparado com o total de 100% na precipitação total. Apesar das diferenças sazonais da entrada da água precipitada, nenhuma diferença sazonal significativa foi encontrada na deposição de N na precipitação total e na transprecipitação entre os períodos seco e de chuvas. Este estudo mostra que NOD é um importante, e ainda pouco estudado, componente da deposição de NTD, compreendendo um terço a mais que a metade do N depositado na chuva e na transprecipitação. Além disso, o aumento da p oluição de N em áreas de expansão urbana nos trópicos poderá impactar a ciclagem de nutrientes nos ecossistemas adjacentes. Neste local de floresta Atlântica submontana o fluxo de N na transprecipitação foi 3 - 7 vezes maior que a carga critica empírica para florestas tropical e subtropical húmidas. / Tropical regions are currently experiencing changes in the qua ntity and form of N deposition as a result of urban and industrial pollution. The sources and sinks for these pollutants have, to date, been little s tudied. In this work were examined atmospheric N inputs to coastal urban region and montane (400 m and 10 00 m) Atlantic Forest sites in Rio de Janeiro state, from August 2008 to August 2009. Concentrations of t otal dissolved nitrogen ( NTD ), dissolved inorganic nitrogen ( NID = NH 4 + + NO 3 - + NO 2 - ) and urea were measured in bulk precipitation at all sampling si tes, as well as canopy throughfall - rainwater that has passed through the forest canopy - in the lower montane forest plot. Total dissolved nitrogen was analized by oxidation with potassium persulphate. Ammonium (NH 4 + ) and nitrite (NO 2 - ) were determined b y Indophenol Blue and by diazotization spectrophotometric methods , respectively . Nitrate (NO 3 - ) was analyzed by cadmium reduction follow ed by spectrophotometric method after cadmium reduction column method for throughfall samples. In bulk deposition sample s, NO 3 - was analized by chromatographer method . Urea was determined spectrophotometrically by diacetilmonoxime method. Dissolved organic nitrogen (DON) was calculated as the difference between TDN and DIN. Annual volume - weighted mean bulk concentrations of all species were higher at the coastal urban than montane forest s sites, with DON accounting for 32 to 56% and 26 to 32%, respectively, of the TDN concentration in precipitation. Bulk deposition of TDN ranged 12.1 to 17.2 kg N ha - 1 yr - 1 and tended to dec rease with increasing distance from the coastal urban region. In the lower montane forest, t hroughfall TDN flux, 34.3 kg N ha - 1 yr - 1 , was over 2 - fold higher than bulk TDN deposition, and DON comprised 61% of the total N deposited to forest soil. The qual ity of DON also changed upon passage through the forest canopy; urea comprised 27% of DON in throughfall compared to up to 100% in bulk precipitation. Despite marked seasonal differences in water input, significant differences in bulk or throughfall N dep osition between wet and dry seasons were not detected. Our findings show that DON is an important, yet understudied, component of TDN deposition, comprising one - third to greater than one - half of the N deposited in rainfall and throughfall. Further, incre asing N pollution in expanding urban areas in the tropics could impact N cycling in adjacent ecosystems. In this lower montane Atlantic Forest site, the total throughfall N flux was 3 - 7 fold higher than the empirical critical load for tropical and subtrop ical humid forests

The emerging evidence of preferential accumulation and long residence time of proteinaceous compounds in soil are counter to the traditional view that their structure is readily broken down through microbial activity. The shift in thinking of their residence time is, however, heavily influenced by physical and chemical protections in soil, representing an important change for understanding global biogeochemical carbon and nitrogen cycling. We investigated the accumulation patterns of proteinogenic amino acids for a long term (thousands of years) related to their sources and sinks. We found clear patterns of change in the amino acids in a 4000 year-chronosequence adjacent to Lake Michigan, USA (Michigan chronosequence) and they were tightly related to the shifts in their biological sources, namely aboveground vegetative community (r2=0.66, p<0.0001) and belowground microbial community (r2=0.71, p<0.0001). Results also showed great variations of approximately 49% between seasons (summer and winter). Moreover, seasonal dynamic patterns (22% variations) of the amino acids in soil mineral associated fraction were rather counter to the conceptual view that it represents a slow soil organic pool with long residence times. The amino acids enriched in the mineral associated fraction, (e.g., positively charged, aromatic, and sulfur containing amino acids), tended to preferentially accumulate in whole soil pool during the 4000 years of ecosystem development. Their interaction with soil minerals, therefore, may play a critical role in the long-term sink and selective accumulation of proteinaceous compounds with some degree of the displacement. This was further confirmed by another chronosequence system near Haast River, New Zealand, which is geologically separated and climatically- and ecologically- different from the Michigan chronosequence. Common trends between two chronosequences suggested that either polar interactions or redox reactions may be relatively more important in the mineral interaction of amino acids than non-polar interactions. The consistency of results at two disparate locations in the southern and northern hemispheres is strong evidence that the processes of pedogenesis and ecosystem development are parsimonious and predictable. Our research demonstrated fundamental understanding of behavior of proteinaceous compounds at the molecular species level, and further provided their partitioning mechanisms associated with soil components. / Ph. D.