O presente experimento de laboratório foi realizado no Departamento de Ciência do Solo da ESALQ/USP, em Piracicaba, SP, com o objetivo de avaliar o efeito da presença de diferentes resíduos vegetais na superfície do solo sobre as perdas de amônia por volatilização decorrentes da aplicação de uréia em três doses. Foram utilizadas amostras da camada 0-0,20m de um Nitossolo Vermelho Eutroférrico do município de Piracicaba, SP. Os tratamentos constaram de arranjo fatorial com três repetições envolvendo quatro doses de uréia (0, 60, 120 e 180 mg dm-3 de N), aplicadas na superfície da terra, e quatro formas de cobertura da terra: sem cobertura e com cobertura constituída de fragmentos de folhas de plantas de milho, cana-de-açúcar e amendoim forrageiro, igualmente aplicados na superfície na quantidade de 29g de matéria seca por frasco (equivalente a 5 Mg ha-1). A volatilização de amônia foi avaliada em frascos de plástico de 1,6 L de capacidade, fechados, contendo 0,4 kg de terra umedecida e, para captar a amônia volatilizada, um disco de papel de filtro tratado com 1 mL de H2SO4 de concentração variando de 0,05 a 0,5 mol L-1. Esse disco era substituído diariamente, sendo o ácido remanescente no filtro exposto à amônia, titulado com NaOH 0,02 mol L-1 na presença de indicador bromocresol verde. Ao final do período experimental de 40 dias, amostras da camada superficial (0-0,05m) de terra dos frascos foram coletadas com amostrador especial e submetidas à determinação do pH em CaCl2 0,01 mol L-1. Os picos de máxima perda de amônia por volatilização ocorreram no 3º e no 12º dia após a aplicação da uréia, não havendo efeito dos resíduos culturais sobre a distribuição das perdas ao longo do tempo. As perdas de amônia aumentaram com o aumento da dose de uréia aplicada. Nas terras sem cobertura e naquelas contendo resíduos de milho e de amendoim forrageiro os aumentos foram mais expressivos para as doses menores (60 e 120 mg dm-3 de N-uréia), enquanto nas terras com restos de cana-de-açúcar os maiores aumentos ocorreram para a dose mais alta (180 mg dm-3 de N-uréia). A presença de restos de cultura de amendoim forrageiro na superfície do solo aumentou a quantidade de amônia volatilizada das terras tratadas ou não com uréia, enquanto a de restos de cultura de cana-de-açúcar reduziu a quantidade volatilizada. Os restos de cultura de milho exerceram pouca influência nas perdas de NH3 por volatilização. O pH da camada superficial das terras aumentou em mais de duas unidades com a aplicação de uréia e dos resíduos vegetais. / A laboratory experiment was carried out at the University of São Paulo, Piracicaba campus, Brazil, in order to evaluate how the presence of different plant residues on soil surface will affect ammonia volatilization losses from urea fertilizer applied on soil surface in three rates. Samples from 0-0.2m layer of a ferric Red Latosol located in Piracicaba, State of São Paulo, Brazil, were used in the study. Treatments consisted of a factorial arrangement with three replicates involving four rates of urea (0, 60, 120 and 180 mg dm-1 of N), applied at soil surface and four forms of soil cover: with no cover and with cover consisted of leaf fragments of corn, sugar-cane and peanut plants also applied on the surface at the rate of 29 g of dryed material per flask (equivalent to 5 Mg per hectare). Ammonia volatilization was measured in closed 1.6 L flasks containing 0.4 kg of moistened soil sample and, to capture NH3, a filter paper disk treated with 1 mL of H2SO4 of concentration varying from 0.05 to 0.5 mol L-1. The paper filter was substituted every day and the remaining acid in the exposed filter was titrated with NaOH 0.02 mol L-1 in the presence of bromocresol green. At the end of the experimental period of 40 days, samples of the surface layer (0-0.05 m) of the soil in the flasks were collected using a special sampler and subjected to determination of the pH in CaCl2 0.01 mol L-1. Maximum volatilization occurred at the 3rd and the 12th day of urea application and no influence was observed of the plant residues on the distribution of the losses during the experimental period. Ammonia losses increased with the rate of urea application. For the bare soil samples and for samples covered with corn and peanut residues, these increases were more evident when urea was applied at the smaller rates (60 and 120 mg dm-1 of urea-N), whereas for samples covered with sugar-cane residues, increases were higher when the higher rate (180 mg dm-1 of urea-N) was used. Covering the soil with peanut residues increased the amount of volatilized ammonia in the samples treated and not treated with urea, while covering with sugar-cane residues reduced the volatilization losses. Corn residues showed to have only small influence on ammonia loss. The pH at the surface of the soil samples increased more than two units as the result of urea and plant residues application.

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

La combustion de résidus de biomasse, généralement peu valorisés, pourrait apporter une solution d’approvisionnement intéressante pour la production d’énergie, allégeant la pression sur les ressources forestières. Toutefois, la composition chimique de ces résidus est à l’origine de problèmes techniques autant qu’environnementaux dans les procédés de combustion existants, ce qui limite leur utilisation. Deux de ces problèmes ont été traités dans cette thèse : les émissions de NOX et la quantité de potassium volatilisée lors de la combustion de différents résidus. Des essais de combustion ont été menés dans des réacteurs à l’échelle du laboratoire, sur des granulés de biomasse pure ou en mélange. Contrairement à la volatilisation du potassium, qui est liée à la teneur en différents éléments inorganiques, une relation linéaire forte (R² = 0,98) entre les émissions de NOX et la teneur en azote du combustible a été établie pour les granulés de biomasse pure. Des écarts par rapport à cette relation linéaire ont été observés dans le cas des essais menés sur des granulés de mélange, mettant en relief que la teneur en azote n’est pas le seul paramètre impliqué. Les travaux menés ont ainsi permis d’établir de manière originale que des synergies peuvent exister dans les granulés de mélange de résidus de biomasse, conduisant à des comportements différant de l’additivité directe des comportements des biomasses prises séparément. Ces synergies permettraient d’atténuer les problèmes causés par l’utilisation de ces résidus dans des chaudières en agissant de manière ingénieuse directement sur les propriétés des combustibles sans modification du procédé. / Combustion of biomass residues, which are generally poorly valued, could provide an attractive supply solution for energy production, alleviating pressure on forest resources. However, the chemical composition of these residues is causing both technical and environmental problems in existing combustion processes, which limits their use. Two of these problems have been addressed in this thesis: the amount of volatilized potassium and NOX emissions, when burning different residues. Combustion tests have been conducted in laboratory-scale reactors on pure and mixed biomass pellets. Variations in the amount of volatilized potassium was found to be linked to the content of multiple chemical elements for pure biomass pellets. In the case of NOx emissions, a strong correlation (R² = 0.98) with the nitrogen content of the fuel was found for pure biomass pellets. However, deviations from this linear relationship were observed for trials conducted on mixed biomass pellets, highlighting that the nitrogen content is not the only parameter involved. The work carried out thus made it possible to establish in an original way that synergies can exist in the pellets made of a mixture of biomass residues, leading to beneficial behaviors differing from the direct additivity of the biomass behaviors taken separately. These synergies could allow to mitigate the problems caused by the use of these residues in boilers by ingeniously acting directly on the properties of the fuels without modification of the process.

Submitted by JANAINA MATIAS PEREIRA DA SILVA null (jana.mps@hotmail.com) on 2016-04-29T12:35:20Z No. of bitstreams: 1 Janaina DISSERTAÇÃO FINAL fev com ficha.pdf: 495368 bytes, checksum: 8f0f99954b0a3ecb942b32b395479d4b (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-05-02T18:00:20Z (GMT) No. of bitstreams: 1 silva_jmp_me_bot.pdf: 495368 bytes, checksum: 8f0f99954b0a3ecb942b32b395479d4b (MD5) / Made available in DSpace on 2016-05-02T18:00:20Z (GMT). No. of bitstreams: 1 silva_jmp_me_bot.pdf: 495368 bytes, checksum: 8f0f99954b0a3ecb942b32b395479d4b (MD5) Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A cama de frango é um adubo orgânico cuja principal característica é a concentração de nitrogênio, porém, há uma alta taxa de volatilização de nitrogênio em forma de amônia. No presente estudo, foi possível avaliar a eficiência do gesso agrícola em diminuir as perdas de nitrogênio da cama de frango por volatilização e melhorar sua característica como fertilizante na adubação da cultura do milho. Os ensaios constituíram pela aplicação de gesso agrícola em cama de frangos de corte nos quais, foram empregados doses de 15%, 30% e 45% em relação ao volume de maravalha, e um tratamento controle sem adição de gesso. Durante todo o período de cria, nos três lotes consecutivos de frangos, foram coletadas amostras de amônia volatilizada por meio de sensor durante três períodos do dia a cada sete dias. Uma amostragem da cama foi coletada ao final de cada ciclo para análises químicas. Ao término da cria a cama foi retirada do galpão e aplicada como fertilizante em vasos para o cultivo do milho em casa de vegetação, mantendo os tratamentos inicias combinados com e sem a aplicação de 100mg de nitrogênio/kg da massa de solo, formando um esquema fatorial de quatro tratamentos com duas variáveis (4x2). Após 50 dias de cultivo foram coletadas amostras de solo para análises, observou-se que o gesso foi incapaz de controlar a volatilização de amônia, não diferindo nos teores de nitrogênio inorgânico. Portanto, os tratamentos não incrementaram eficiência em produção de matéria seca do milho, outrora, essas combinações entre cama de frango, gesso e nitrogênio, elevaram a concentração de fósforo e nitrogênio na raiz da cultura. / Poultry litter is organic fertilizer whose major characteristic is the nitrogen concentration, but, there is a high volatization nitrogen rate in the form ammonia. This study, was possible appreciate the phosphorgypsum efficiency to reduce nitrogen losses on poultry litter through volatilization and upgrade characteristic like a fertilizer in the cultivation corn. The testing considered in application phosphogypsum in poultry litter, were employed 15%, 30% and 45% doses compared to wood shaving volume, and control treatment without addition gypsum. While the period creates, three consecutive poultry lots, was collected samples volatilized ammonia by a sensor during three periods in the day each seven days. Was collected sampling bed in every final cycle to chemical analysis, finishing all cycle the bed was removed to be applied as fertilizer inside vase corn cultivation in house vegetation, keeping the treatments initial combination with and without application 100mg nitrogen / kg soil volume, constituted a factorial arrangement of four treatments with two variables (4x2). After 50 days cultivation was collected samples soil to analyze, it was observed that gypsum is unable to control ammonia volatization, not differing inorganic nitrogen. Therefore, treatments was not increase efficiency in production corn dry matter, in the other hand, this combinations between poultry litter, gypsum and nitrogen increased the concentration phosphorus and nitrogen in cultivation root.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The application of pig slurry into the soil can result in losses of nitrogen (N) through volatilization of ammonia (NH3) and the emission of nitrous oxide (N2O), which reduce the efficiency of pig slurry (PS) as source of N to crops, besides adversely affecting the environment, human and animal health. Among strategies under investigation in other countries to mitigate these problems includes the injection of PS in soil and the use of nitrification inhibitors. In Brazil, the research in this area is still in initial stages. Therefore, the aim of this study was to evaluate the efficiency of injecting PS into the soil and the application of nitrification inhibitor dicyandiamide (DCD) in reducing N losses through volatilization of NH3 and N2O emissions in no-till corn. The study was conducted from December 2011 to May 2012 at the Federal University of Santa Maria and the treatments were: T1-control; T2-urea-N + PK; T3-PS surface; T4- PS surface + DCD; T5-injected PS and T6- PS injected + DCD. The dose of DCD (10 kg ha-1) was mixed with PS (50 m3 ha-1) at the time of its application in the field. The application of PS increased emissions of N2O and NH3. Although the strategy of injecting the PS has been efficient in controlling of emissions of NH3, by reducing it to 97,5%, however, it increased N2O emissions by 49,4%, in comparison to the application of PS on soil surface. The application of DCD with PS reduced N2O emissions by 62,0% in surface application and by 69,3% when PS was injected while N loss through volatilization of NH3 was unaffected. The results of this study indicates that injection of pig slurry into the soil under no tillage, combined with the use of the nitrification inhibitor dicyandiamide, is an effective strategy to mitigate the potential pollution of the environment by PS, in addition to preserving the value of fertilizer as source of N to the plants. / A aplicação de dejetos líquidos de suínos no solo pode resultar em perdas de nitrogênio (N) através da volatilização de amônia (NH3) e da emissão de óxido nitroso (N2O), as quais reduzem a eficiência dos dejetos líquidos de suínos (DLS) como fonte de N às culturas, além de impactarem negativamente o ambiente e a saúde humana e animal. Entre as estratégias em estudo em outros países para atenuar esses problemas destacam-se a injeção dos DLS no solo e o uso de inibidores de nitrificação. No Brasil a pesquisa nessa área ainda é incipiente. O objetivo deste trabalho foi avaliar a eficiência da injeção de DLS no solo e do uso do inibidor de nitrificação dicianodiamida (DCD) em reduzir as perdas de N por volatilização de NH3 e as emissões de N2O em plantio direto de milho. O trabalho foi realizado de dezembro de 2011 a maio de 2012 na Universidade Federal de Santa Maria e os tratamentos avaliados foram os seguintes: T1- testemunha; T2- N uréia + PK; T3- DLS em superfície; T4- DLS em superfície + DCD; T5- DLS injetado e T6- DLS injetado + DCD. A dose de DCD (10 kg ha-1) foi misturada à dose de DLS (50 m3 ha-1) no momento da sua aplicação no campo. A aplicação de DLS aumentou as emissões de NH3 e de N2O. Embora a estratégia de injetar os DLS tenha sido eficiente no controle das emissões de NH3, reduzido-as em 97,5%, ela aumentou as emissões de N2O em 49,4%, em relação à aplicação dos DLS na superfície do solo. Contudo, o inibidor de nitrificação (DCD), aplicado junto com os dejetos, reduziu as emissões de N2O em 62,0% na aplicação em superfície e em 69,3% com a injeção no solo, sem afetar a perda de N por volatilização de NH3. Os resultados deste trabalho indicam que a injeção dos dejetos líquidos de suínos no solo em plantio direto, combinada ao uso do inibidor de nitrificação dicianodiamida (DCD), é uma estratégia eficiente para mitigar o potencial poluidor do ambiente pelos DLS, além de preservar o valor fertilizante dos mesmos como fonte de N às culturas.

Made available in DSpace on 2015-03-26T13:53:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-07-26 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The lower NH3 volatilization from urea combined with humicified organic material has been attributed to the formation and adsorption of NH4+ due the high potential acidity and CEC. In this context, an experiment was conducted to evaluate NH3 volatilization from grainy urea or coated with humic acids (HA) and humic substances (HS) synthesized from vegetable charcoal (VC). The synthesis of HA and HS was due to the oxidation from charcoal of eucalyptus with HNO3 4.4 mol L-1 boiled under reflux for 4 hours. The HS were obtained directly by filtration. For the HA and HS achievement, It was solubilized in NaOH 0.5 mol L-1 and the fraction of HA was the one that precipitated until acidification to pH 2.0. It was produced grainy urea and urea coated with 5, 10, 15 and 20 % HA or HS. For the granulation, mixtures of urea (p.a.) and HA or HS were fused in 137 ° C and dripped using a pipette on a metal plate. With the fast cooling of the drops, granules in the form of tablets (4 to 5 mm in diameter) were formed. The commercial grainy urea (1-2 mm) was coated with HA or humic substances, using vegetable oil to promote adhesion. Volatilization of NH3 was evaluated in the laboratory in a closed system with continuous air flow, where 100 mg of N-urea was applied to a 100 cm3 surface of a red-yellow Acrisol (<2 mm). The synthesis income was 327 g kg-1 of HA and 784 g kg-1 of humic substance. The acidity of the carboxylic and phenolic groups was estimated through adjusting multiparameter non-linear potentiometric titration curve and, together, corresponded to the CEC of the HA (4750 mmol c kg-1) and HS (4360 mmol c kg-1), which were 9.5 and 8.7 times higher than the VC. The carboxylic groups were predominant either in the VC as in HA and HS, but the HA had a higher content of carboxylic groups and lower content of phenolic groups than the HS. The presence of carboxylic groups was confirmed by the spectra in the infrared range, showing absorption of stretching and deformation, characteristic of C = O bond with 1703.74 and 1706.88 cm-1 waves to the HA and HS, respectively. The urea fusion did not change the N content, but they ranged on average from 36 to 42 % with the addition of 20 to 5 % HA or HS. The highest volatilization rate occurred between 37 and 41 h after application and this time was little influenced by the proportions of HA and HS. Without the addition of HA and HS, the urea in a tablet shape and the commercial grainy urea provided a total volatilization of 517.4 and 468.8 mg g-1 of N-NH3. The largest reductions in evaporation occur with grainy urea (44.5 %) and coated (28.7 %) with 15 and 20 % HA, respectively. In the grainy urea the proportions of HA and HS provided equivalent reduction in evaporation. / A menor volatilização de NH3 a partir da ureia combinada com material orgânico humificado tem sido atribuída à formação e à adsorção do NH4 + em razão da elevada acidez potencial e CTC. Neste contexto, foi conduzido um experimento para avaliar a volatilização de NH3 a partir da ureia granulada ou revestida com ácidos húmicos (AH) e substâncias húmicas (SH) sintetizadas de carvão vegetal (CV). A síntese dos AH e SH se deu pela oxidação do CV de eucalipto com HNO3 4,4 mol L-1 em ebulição sob refluxo por 4h. As SH foram obtidas diretamente por filtragem. Para obter os AH as SH foram solubilizadas em NaOH 0,5 mol L-1 e a fração AH foi aquela precipitada com a acidificação até pH 2,0. Foi produzida ureia granulada e ureia revestida com 5, 10, 15 e 20 % de AH ou SH. Para a granulação as misturas de ureia (p.a.) com AH ou SH foram fundidas a 137 °C e gotejadas com uma pipeta em uma placa metálica. Com o resfriamento rápido das gotas formaram-se grânulos na forma de pastilhas (4 a 5 mm de diâmetro). A ureia granulada comercial (1 a 2 mm) foi revestida com AH ou SH utilizando-se óleo vegetal para favorecer a aderência. A volatilização de NH3 foi avaliada em laboratório em um sistema fechado com fluxo contínuo de ar, onde 100 mg de N-ureia foi aplicada nas superfície de 100 cm3 de um Argissolo Vermelho- Amarelo (< 2 mm). O rendimento na síntese foi de 327 g kg-1 de AH e 784 g kg-1 de SH. A acidez dos grupos carboxílicos e fenólicos foi estimada por meio do ajuste multiparamétrico não linear da curva de titulação potenciométrica e, em conjunto, corresponderam à CTC dos AH (4.750 mmolc kg-1) e SH (4.360 mmolc kg-1), que foram 9,5 e 8,7 vezes maiores do que a do CV. Os grupos carboxílicos predominaram tanto no CV como nos AH e SH, porém os AH apresentaram maior teor de grupos carboxílicos e menor teor de grupos fenólicos do que as SH. A ocorrência dos grupos carboxílicos foi confirmada pelos espectros na faixa do infravermelho que evidenciaram absorção de estiramento e deformação característica da ligação C=O com 1.703,74 e 1.706,88 cm-1 ondas para os AH e SH, respectivamente. A fusão da ureia não alterou o teor de N, mas estes variaram, em média, de 36 a 42 % com a adição de 20 a 5 % de AH ou SH. A maior taxa de volatilização ocorreu entre 37 e 41 h após a aplicação e este tempo foi pouco influenciado pelas proporções de AH e SH. Sem a adição de AH ou SH a ureia na forma de pastilha e a ureia granulada comercial proporcionaram volatilização total de 517,4 e 468,8 mg g-1 de N-NH3. As maiores reduções na volatilização ocorreram com a ureia granulada (44,5 %) e revestida (28,7 %) com 15 e 20 % de AH, respectivamente. Na ureia granulada as proporções de AH e de SH proporcionaram redução equivalente na volatilização.

Made available in DSpace on 2015-03-26T13:53:30Z (GMT). No. of bitstreams: 1 texto completo.pdf: 485641 bytes, checksum: 8d373d7f31d9cc3806aad98820f5afc7 (MD5) Previous issue date: 2013-04-30 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The fractioned Nitrogen fertilization is a management strategy in which the largest fraction of the dosage is applied in topdressing. In Tillage System (TS), topdressing fertilization efficiency when using urea is compromised by the difficulty of incorporating the fertilizer. Nitrogen fertilization in pre-sowing, during the desiccation of the cover plants is a successful strategy, but in restricted conditions. The experiment aimed to evaluate the nitrogen fertilization in corn pre-sowing under Tillage system, with management of weed plants using pearly or grainy urea. The experiment was held in the experimental field of the Plant Science Department, Federal University of Viçosa during the 2010/2011 crop. The soil of the experimental area was a Red-Yellow Podsol grown for six years in Tillage System. The factors studied were cover plants prior to maize crop (grass Marandú - Brachiaria brizantha, oat - Avena strigosa and weed plants); Nitrogen dose applied at pre-sowing maize with desiccation of cover plants or the topdressing in the V4 stage of corn development (0, 50, 100, 150 and 200 kg ha-1), the application period of 200 kg ah-1 de N in pre-sowing in relation to the desiccation (20 days before, during the desiccation or 20 days after it) and form of urea (PETROBRAS pearly urea - UPP, PETROBRAS granulated urea - UGP and special granulated urea - UTI). These factors were combined in an incomplete factorial according to the Baconian matrix, totaling 29 treatments. Before desiccation, the amount of biomass cover plants was quantified then identified the species of weed plants and determined and content of N in the biomass. The N input through the waste was estimated. In treatment with fractioned application of 200 kg ha-1 N with different Nitrogen fertilizers at respective seasons to desiccation evaluated volatilization of NH3 through static semi-open collectors. The waste of ammonia was expressed regarding the dose of N applied. At the end of the growing cycle of corn (± 70 days after germination) were collected corn plants that have been properly processed for the analysis of the percentage of N. Estimated the amount of N accumulated in shoots of corn and based on these, an estimation of the apparent recovery of N fertilizer, considering or not the N contributed by residues of cover plants. Maize grain productivity was expressed with the grain humidity corrected to 13%. The results showed that nitrogen fertilization 20 days before drying, with weeds still alive provided greater N accumulation in biomass and reduction in C/N ratio. However this has not favored higher mineralization whereas management of weeds through herbicide application was not effective to enable the Nitrogen in the pre-sowing of the Tillage corn. The management of oats as cover crop by herbicide application was more effective to enable the Nitrogen fertilization in the pre-sowing. The special granulated urea was particularly effective for nitrogen fertilization in pre-sowing of maize under TS as management of cover crop through chemical desiccation. / O parcelamento da adubação nitrogenada é a estratégia de manejo em que a maior fração da dose é aplicada na adubação de cobertura. No sistema plantio direto (SPD), pela dificuldade de incorporação do fertilizante, há um comprometimento da eficiência da adubação de cobertura quando se utiliza a ureia. A adubação nitrogenada em pré-semeadura, por ocasião da dessecação da planta de cobertura tem sido uma estratégia de sucesso, mas em restritas condições. O experimento objetivou avaliar a adubação nitrogenada na pré-semeadura do milho em SPD, com manejo das plantas espontâneas utilizando a ureia na forma perolada ou granulada. O experimento foi conduzido no campo experimental do DFT/UFV durante a safra 2010/2011. em um Argissolo Vermelho-Amarelo Câmbico, cultivado há seis anos em SPD. Foram fatores em estudo: planta de cobertura antecessora à cultura do milho (capim Marandú - Brachiaria brizantha, aveia preta - Avena strigosa e as plantas espontâneas); dose de nitrogênio aplicada na pré-semeadura do milho com a dessecação das plantas de cobertura ou em cobertura no estádio V4 de desenvolvimento do milho (0, 50, 100, 150 e 200 kg ha-1), época da aplicação de 200 kg ha-1 de N na pré-semeadura em relação à dessecação (20 dias antes, na dessecação ou 20 dias após) e forma de ureia (ureia perolada PETROBRAS UPP, ureia granulada PETROBRAS UGP e ureia granulada especial UTI). Estes fatores foram combinados em um fatorial incompleto de acordo com a estrutura da matriz Baconiana, totalizando 29 tratamentos. Antes da dessecação quantificou-se a biomassa das plantas de cobertura, identificaram-se as espécies de plantas espontâneas e determinou-se o teor de N na biomassa. Foi estimada a quantidade de N aportada por meio dos resíduos. Em parcelas com aplicação de 200 kg ha-1 com os diferentes fertilizantes nitrogenados nas respectivas épocas em relação à dessecação avaliou-se a volatilização de NH3 por meio de coletores semiaberto estáticos. A perda de amônia foi expressa em relação à dose de N aplicada. Ao final do ciclo vegetativo do milho (±70 dias após a germinação) coletaram-se plantas de milho, que foram processadas para a análise do teor de N. Estimaram-se as quantidades de N acumuladas na parte aérea do milho e com base nestas, estimou-se a recuperação aparente do N dos fertilizantes, considerando ou não o N aportado pelos resíduos das plantas de cobertura. A produtividade do milho foi expressa com a umidade dos grãos corrigida para 13 %. Conclui-se que a adubação nitrogenada 20 dias antes da dessecação, com as plantas espontâneas ainda vivas proporcionou maior acúmulo de N na biomassa e redução na relação C/N. No entanto, isso não favoreceu maior mineralização considerando que manejo das plantas espontâneas por meio da dessecação química não foi eficaz para viabilizar a adubação nitrogenada na pré-semeadura no milho em sistema plantio direto. O manejo da aveia como planta de cobertura por meio da dessecação química foi mais eficaz para viabilizar a adubação nitrogenada na pré-semeadura. A ureia granulada especial foi eficaz para a adubação nitrogenada em pré-semeadura do milho em SPD, como manejo da planta de cobertura por meio da dessecação química.

A contaminação ambiental provocada pelo despejo de resíduos industriais e pela aplicação de agrotóxicos pode resultar no desequilíbrio dos ecossistemas, além de causar danos diretos à saúde humana. No Brasil, existem várias áreas contaminadas com resíduos industriais, tais como o hexaclorobenzeno (HCB), um composto organoclorado usado no passado como fungicida, mas que atualmente tem seu uso proibido devido a sua alta persistência no ambiente e alta capacidade de bioacumulação. Este estudo verificou a possibilidade de remoção de resíduos de HCB do solo contaminado além da possibilidade de contaminação do ar e da água por este composto. Verificou-se: a) o efeito de adição de matéria orgânica, alteração de pH e alagamento da terra sobre a comunidade microbiana e a degradação do HCB; b) a volatilização do HCB e, c) a lixiviação deste composto. A contaminação inicial da terra foi determinada através de extração das amostras de terra contaminada e análise dos extratos por cromatografia gasosa (CG). Alterações das características da terra foram promovidas pela adição de matéria orgânica (bagaço de cana de açúcar ou vermicomposto), adição de Cal ou alagamento das amostras de terra contaminada, além de combinações destes tratamentos. Cada amostra de terra, colocada em frascos de vidro, recebeu uma solução de HCB radiomarcado (14C-HCB). A mineralização do 14C-HCB foi analisada através da captura do CO2 proveniente das amostras de terra por uma solução de hidróxido de potássio e quantificação do 14CO2 por Espectrometria de Cintilação Líquida (ECL). A volatilização do 14C-HCB foi analisada através da captura dos compostos voláteis por lâmina de poliuretano, extração desta lâmina e análise do extrato por ECL, para quantificação dos 14C-compostos voláteis, e por CG, para quantificação dos compostos voláteis (HCB e metabólitos). A formação de 14C-resíduos ligados e de metabólitos do HCB nas amostras de terra foi analisada através da extração destas amostras e posterior análise da terra extraída por ECL e do extrato por CG. Cada amostra de terra também foi analisada quanto à atividade microbiana, medida através da respiração dos microrganismos, e quanto a densidade microbiana, através da metodologia de contagem de unidades formadoras de colônias (UFC) de bactérias e fungos. A mobilidade e a lixiviação do HCB foram estudadas através de percolação de água em tubos de PVC contendo amostras de terra contaminada tratadas com bagaço de cana de açúcar e/ou cal e solução de 14C-HCB, dispostas sobre amostras de terra não contaminada; os tubos foram seccionados e a terra e a água lixiviada foram analisadas por ECL. O período dos estudos foi de 270 dias. A determinação da contaminação inicial da terra indicou a presença do HCB (3400 mg g-1 terra) e dos metabólitos 1,2,4,5 TCB (24 mg g-1 terra), 1,2,3,4 TCB (6 mg g-1 terra) e PCB (267 mg g-1 terra). A volatilização de 14C-compostos ocorreu em todas as amostras, principalmente nas amostras alagadas e com adição de matéria orgânica (29% a 40 %, após 270 dias). O alagamento favoreceu a volatilização provavelmente devido a baixa hidrossolubilidade do HCB e, a presença de matéria orgânica pode ter favorecido a formação de metabólitos mais voláteis através do estímulo à descloração redutiva, que ocorre sob condições de anaerobiose. Entretanto, a descloração redutiva não foi comprovada pois não houve formação nem aumento na concentração de metabólitos do HCB entre os compostos volatilizados. Houve uma diminuição na quantidade de 14C-compostos extraíveis no decorrer do tempo em todas as amostras, mas a concentração de HCB ou de seus metabólitos permaneceu constante independente do tratamento. A atividade e a densidade microbiana foram maiores nas amostras com bagaço de cana de açúcar mas não tiveram efeito sobre a volatilização ou a degradação do HCB. Não ocorreu mineralização ou mobilidade do 14C-HCB na terra contaminada e nem a formação de 14C-resíduos ligados. Portanto, a adição de matéria orgânica, a alteração de pH e o alagamento da terra não se mostraram eficientes para a remoção do HCB de terra contaminada. Além disso, a ocorrência de formação de 14C-compostos voláteis e a ausência de lixiviação do 14C-HCB indicaram que a presença de resíduos de HCB no solo pode levar à contaminação do ar mas não de água subterrânea. / The environmental contamination by industrial wastes and pesticides can cause harmful effects to ecosystem besides direct human health damages. In Brasil, there are several areas contaminated with industrial wastes like the hexachlorobenzene (HCB), a chlorinated organic compound used in the past as fungicide but that has no longer been produced due to its high persistence in the environment and bioaccumulation potential. This study verified the possibility of HCB residues removal from contaminated soil besides the air and water contamination risk. It was verified: a) the effect of organic matter addition, pH change and flooding of the contaminated soil on the microbial community and HCB degradation; b) HCB volatilization and, c) HCB leaching. The initial soil contamination was determined by extraction of contaminated soil samples and analysis of the extract by Gaseous Chromatography (GC). Soil properties changes were promoted by organic material addition (sugar cane bagasse or earthworm humus), lime addition and flooding of the soil samples besides a combination of these treatments. Each soil sample, placed in glass flasks, was treated with radiolabelled HCB solution (14C-HCB). The 14C-HCB mineralization was analyzed by the entrapment of CO2 originated from the soil samples by potassium hydroxide solution and quantification of the 14CO2 by Liquid Scintillation Spectrometry (LSS). The 14C-HCB volatilization was analyzed by the entrapment of the volatiles compounds by a polyurethane lamina, extraction of this lamina and analysis of the extract by LSS, for 14C-volatile compounds quantification, and by GC, for volatile compounds (HCB and metabolites) quantification. The 14C-bound residues and the HCB metabolites of the soil samples were analyzed by the extraction of these samples and further analysis of the extracted soil by LSS and analysis of the extract by GC. Each soil sample was analyzed with regard to its microbial activity by microbial respiration measure and microbial density by the plate count technique. The mobility and leaching of the HCB were studied by water percolation through PVC tubes containing contaminated soil treated with sugar cane bagasse and/or lime and 14C-HCB placed over no contaminated soil; the tubes were cut in sections and the soil and the leached water were analyzed by LSS. All these studies lasted 270 days. The initial soil contamination determination indicated the presence of the HCB (3400 mg g-1 soil) and the metabolites 1,2,4,5 TCB (24 mg g-1 soil), 1,2,3,4 TCB (6 mg g-1 soil) and PCB (267 mg g-1 soil). The volatilization of the 14C-compounds occurred in all the samples, mainly in the flooded samples with organic matter addition (29% to 40% after 270 days). The flooding enhanced the volatilization due the low HCB water-solubility and, the presence of organic material can have favoured the formation of metabolites more volatile than the HCB due to reductive dechlorination that occurs under anaerobic conditions. But the reductive dechlorination occurrence was not proved as there was no formation or increase in metabolite concentration. There was a decrease in 14C-extractable compounds quantity through the time in all the samples but the HCB and metabolites concentrations keep constant independently of the treatment. The microbial activity and density were higher in the samples with sugar cane bagasse but it did not affected the HCB volatilization or degradation. The 14C-HCB mineralization and the 14C-bound residues formation did not occur. The mobility of the 14C-HCB was not observed too. Therefore, the organic material addition, the pH change and the soil flooding were not efficient to HCB removal from the contaminated soil. And, the occurrence of the volatilization of 14C-compounds and the absence of 14C-HCB leaching indicated that the presence of HCB residues in the soil can result in contamination of air but not the ground water.

Master of Science / Department of Agronomy / Gary M. Pierzynski / Soil chemical and physical properties beneath cattle feedlot pens are largely unstudied. This project was conducted to survey select soil chemical and physical properties of soil beneath active open air cattle feedlots. At four cattle feedlots in Kansas, the concentrations of NH4-N, organic-N, organic-C, Cl-, and P were high at the surface and rapidly decreased within 1.00 m. At three of the four feedlots, NO3-N was generally below background concentration (4.1 mg kg-1) while one feedlot had a >75 mg kg-1 increase in the top 1.00 m. Based on feeding data, only a small percent (7.9 to 1.2) of the total N deposited on the surface was found in the top 1.00 m below the pen surface for a range of 25 to 60 years of operation. While in use, these feedlots do not appear to have a high potential for groundwater pollution from NO3-N leaching. However, if they were to become inactive they may pose a severe threat to groundwater quality from organic-N mineralization and NH4-N nitrification. If feedlots were closed and the land could be largely remediated by removing a layer of soil, these feedlots would have an average 48% profile N removed in a 0.25 m thick layer. A chamber, a modified vacuum desiccator, was tested for the investigation of NH3 volatilization from soil in the laboratory. Ammonia volatilization at the soil surface is dependent on air flow, soil and air temperatures, soil water content, pH, the concentrations of NH3 and NH4+ in the air and soil solution, and factors affecting soil temperature including humidity. This chamber was built to control and/or quantify as many of these variables as possible. A technique for quantifying and predicting NH3 volatilization is important because AFOs are one of the largest contributors of NH3 to the atmosphere, which can cause acid precipitation and particulate matter deposition downwind from the operation. The chambers created allowed for repeated measurements with little error and appear to be a feasible, inexpensive apparatus to investigate NH3 volatilization mechanisms. Using synthetic urine as an N source, NH3 volatilization was affected by initial soil moisture content and soil texture and may be affected by initial soil pH. This chamber has promise to provide excellent data to assist the efforts being made to understand and model NH3 volatilization from feedlot pens.

L’activité agricole présente la principale source de contamination de l’atmosphère par les pesticides. Les niveaux de concentration des pesticides dans l’atmosphère méritent une attention particulière de la part de la recherche compte tenu de leurs impacts potentiels sur la population et les écosystèmes. Bien que la volatilisation depuis la plante soit reconnue plus intense et plus rapide que la volatilisation depuis le sol, cette voie de transfert est à ce jour la moins bien renseignée avec peu de modèles disponibles pour sa description. Le manque de connaissances est lié essentiellement à la complexité des interactions entre les processus ayant lieu à la surface de la feuille et qui sont en compétition avec la volatilisation, notamment la pénétration foliaire et la photodégradation. Un système de chambre de volatilisation a été développé afin d’étudier d’une manière simultanée les processus de volatilisation et de pénétration foliaire. Les expérimentations réalisées avec 3 fongicides (époxyconazole, chlorothalonil et fenpropidine) appliqués sur feuilles de blé ont permis une description affinée du processus de pénétration foliaire grâce au protocole d’extraction des feuilles mis en place. Des coefficients de pénétration indispensables à la modélisation du devenir des pesticides à la surface des feuilles ont été calculés ainsi que des relations entre les propriétés physico-chimiques des pesticides et les processus qui contrôlent leur distribution sur et dans la feuille. L’étude expérimentale portant sur le processus de photodégradation a consisté en une irradiation de films de cire simulant les feuilles de blé traités avec des pesticides dans un simulateur solaire Suntest. Les résultats ont démontré que les pertes par photodégradation sont négligeables dans les conditions expérimentales et les pesticides choisis. Le modèle d’échange Sol-Végétation-Atmosphère SURFATM a été adapté aux pesticides selon une approche inspirée du modèle PEARL avec dans un premier temps des coefficients empiriques des processus de pénétration et de photodégradation. L’originalité de ce modèle réside dans sa description mécaniste des conditions micro-météorologiques à l’intérieur du couvert végétal. Ensuite, une approche de distribution des résidus de pesticides dans différents compartiments de la surface foliaire a été définie en se basant sur les résultats expérimentaux, permettant ainsi de prédire la fraction disponible à la volatilisation. La combinaison de cette approche avec les relations déduites entre les propriétés physico-chimiques des pesticides et le processus de pénétration foliaire améliore la généricité du modèle. Par ailleurs, l’effet de la formulation observé expérimentalement a été intégré via des coefficients empiriques permettant ainsi de mieux simuler les flux de volatilisation des produits systémiques. La comparaison entreles sorties du modèles et les résultats expérimentaux recueillis à partir de deux jeux de données acquis sur deux sites différents donne des résultats satisfaisants. Une fois activée la volatilisation depuis le sol, le modèle SURFATM-Pesticides permettra de prédire les émissions vers l’atmosphère de pesticides par volatilisation depuis les parcelles traitées. / The agricultural activity presents the main source of the atmospheric contamination by pesticides. The occurrence of pesticides in the atmosphere concerns the research community due to their potential impacts on population and ecosystems. The volatilization from plants is higher and faster than the volatilization from soil. However, this transfer pathway is difficult to assess with few available models. The lack of knowledge on pesticide volatilization from plants is essentially linked to the complex interactions between processes occurring at the leaf surface and competing with volatilization, such as leaf penetration and photodegradation. A laboratory volatilization chamber was developed in order to study simultaneously the processes of volatilization and leaf penetration of 3 fungicides (epoxyconazole, chlorothalonil and fenpropidine) applied on wheat leaves. These experimentations allowed a refined description of leaf penetration process using a well-defined sequential extraction procedure of leaves. Leaf penetration coefficients, which are necessary to modelling the pesticide fate in plants, were calculated. Moreover relationships between physicochemical properties of pesticides and processes regulating their distribution on and in plant leaves were identified. The experimental study on the photodegradation process consisted in irradiating wax films using simulated solarlight. The results showed that for experimental conditions and pesticides chosen in our study, photodegradation seems to have played a minor role as dissipation process.The soil-vegetation-atmosphere exchange model SURFATM was adapted for pesticides using an approach inspired from the parameterization developed in the PEARL model. The originality of this model resides in its mechanistic description of the micro-meteorological conditions inside the canopy. As a first step the SURFATM-Pesticides model describes leaf penetration and photodegradation processes using empirical coefficients. Then a distribution of pesticide residues in the different compartments of the leaf surface was identified based on the experimental results. This approach allowed the quantification of pesticide fraction on the leaf surface available for volatilization. The combination of this compartmental approach and the identified relationships between physicochemical properties of pesticides and the leaf penetration process improves the genericity of the model. Moreover, the effect of the pesticide formulation in the commercial preparations was integrated in the model via empirical coefficients allowing a better simulation of the volatilization fluxes in the case of systemic pesticides. Comparison of model results and experimental measurements collected from two datasets showed satisfactory results. Once the contribution of soil volatilization has been activated, the SURFATM-Pesticides model will allow us to predict the overall pesticide volatilization at the field scale.