A mecanização do preparo de amostras minimiza erros sistemáticos, a geração de efluentes e o tempo de análise. Sistemas em fluxo com microbombas solenoide (MPFS) atendem aos requisitos da mecanização de maneira robusta e versátil. Sendo assim, foram desenvolvidos procedimentos analíticos baseados em MPFS e foto-oxidação em linha visando ao fracionamento de fósforo em extratos de alimentos e águas naturais e à determinação de cloreto em águas naturais e urina. Fósforo é um nutriente importante cuja biodisponibilidade depende de sua forma química, tornando importante o fracionamento. O monitoramento de cloreto também é importante porque altas concentrações causam efeitos adversos ao meio ambiente e à saúde. Um MPFS foi proposto para o fracionamento de fósforo solúvel em extratos de alimentos, empregando foto-oxidação em linha do fósforo orgânico a ortofosfato, que foi quantificado pelo método do azul de molibdênio. Foi obtida resposta linear entre 5,0 e 40 mg L-1 para fósforo inorgânico (PI) e orgânico (PO), com limites de detecção de 0,5 e 1,2 mg L-1, respectivamente. Coeficientes de variação foram estimados em 1,2 e 3,6% para PI e PO, respectivamente, com frequência de amostragem de 80 determinações por hora. Por determinação, foram consumidos 380 µg de (NH4)6Mo7O24, 620 µg de ácido ascórbico e 790 µg de K2S2O8, gerando 2,5 mL de efluentes. Os resultados do fracionamento em extratos de alimentos concordaram com os obtidos pelo procedimento de referência (95% de confiança), baseado na digestão nitro-perclórica para a determinação de PO. Um procedimento com MPFS e espectrofotometria de longo caminho óptico foi desenvolvido para o fracionamento de fósforo (inorgânico e orgânico dissolvidos) em águas naturais. A quantificação foi baseada no método do azul de molibdênio, após fotoconversão das espécies a ortofosfato. Resposta linear foi observada entre 10 e 75 µg L-1 P, com limite de detecção de 2,0 µg L-1. Foram obtidos coeficiente de variação de 1,8% e frequência de amostragem de 40 determinações por hora. Por determinação, foram consumidos 160 µg de (NH4)6Mo7O24, 10 µg de SnCl2, 640 de µg K2S2O8 e 10 mg de NaOH, gerando 4,0 mL de efluentes. Os coeficientes angulares das curvas obtidas com 4 tipos diferentes de espécies de PO indicaram conversão quantitativa e os resultados obtidos para amostras de águas de rios foram concordantes com os obtidos pelo procedimento descrito pela AOAC (95% de confiança). Um procedimento limpo foi também desenvolvido para a determinação de cloreto em águas naturais e urina, evitando o uso de reagentes tóxicos. O analito foi foto-oxidado a cloro, que foi determinado por espectrofotometria através da descoloração do alaranjado de metila. Resposta linear foi observada entre 2,0 e 20 mg L-1, com limite de detecção de 0,7 mg L-1. O coeficiente de variação foi estimado em 1,6%, com frequência de amostragem de 75 determinações por hora e consumo de 7,5 µg de corante por determinação. Espécies concomitantes usualmente presentes nas amostras não interferiram mesmo em excesso em relação às concentrações normalmente encontradas. Os resultados das análises das amostras concordaram com os obtidos pelo procedimento de referência (95% de confiança). Os procedimentos propostos são alternativas limpas e rápidas para o fracionamento de fósforo e determinação de cloreto. / Mechanization of sample preparation minimizes systematic errors, waste generation and analysis time. Flow-based systems with solenoid micropumps (MPFS) attain the requirements for mechanization in a versatile and robust way. Therefore, analytical procedures based on MPFS and on-line photo-oxidation were developed aiming phosphorus fractionation in foodstuff and river waters and chloride determination in natural waters and urine. Phosphorus is an important nutrient for plants and animals and its bioavailability depends on its chemical form, making fractionation studies important. Chloride monitoring is relevant because the concentration unbalance leads to environmental and health issues. A MPFS was proposed for the fractionation of water soluble phosphorus in foodstuff, incorporating on-line photo-oxidation of organic phosphorus to phosphate, which was quantified by the spectrophotometric molybdenum blue method. Linear response was observed from 5 to 40 mg L-1 for both inorganic (PI) and organic (PO) phosphorus, with detection limits of 0.5 and 1.2 mg L-1, respectively. Coefficients of variation (n = 20) were estimated as 1.2 and 3.6% for PI and PO, respectively, with a sampling rate of 80 determinations per hour. Per determination, 380 µg of (NH4)6Mo7O24, 620 µg of ascorbic acid and 790 µg of K2S2O8 were consumed, generating 2.5 mL of waste. The results for food extracts agreed with those obtained by the reference procedure (95% confidence level) based on nitro-percloric digestion for PO determination. A MPFS procedure with long pathlength spectrophotometry was developed for phosphorus fractionation (dissolved organic and inorganic) in natural waters. Quantification was also based on the formation of molybdenum blue, after on-line photo-convertion of the organic species to orthophosphate. The analytical response was linear within 10 and 75 µg L-1 with a detection limit of 2.0 µg L-1. Coefficient of variation of 1.8% and sampling rate of 40 determinations per hour were achieved. Per determination, 160 µg of (NH4)6Mo7O24, 10 µg of SnCl2, 640 µg of K2S2O8 and 10 mg of NaOH were consumed, generating 4.0 mL of waste. Slopes of analytical curves obtained for four different PO species agreed with those obtained for orthophosphate, indicating quantitative conversion and the results for five freshwater samples agreed with those obtained by the AOAC reference procedure at 95% confidence level. A green procedure for chloride determination in urine and natural waters was also developed, avoiding hazardous chemicals. The analyte was on-line photo-converted to chlorine which was spectrophotometrically detected by methyl orange discoloration. The analytical response was linear from 2.0 to 20 mg L-1 Cl with a detection limit of 0.7 mg L-1. The coefficient of variation was 1.6% with a sampling rate of 75 determinations per hour, consuming 7.5 µg of the dye per determination. Usual concomitant species did not cause significant interference even in excess in relation to their highest concentration expected in the samples. The results for urine and water samples agreed with those obtained by the reference procedures at the 95% confidence level. The proposed procedures are environmentally friendly and fast alternatives for phosphorus fractionation and chloride determination

Many agricultural fields that have received long-term applications of P often contain levels of P exceeding those required for optimal crop production. Knowledge of the effect of the P remaining in the soil (residual effect) is of great importance for fertilization management. In order to characterize P forms in soils, a wide variety of methods have been proposed. The use of dialysis membrane tubes filled with hydrous ferric oxide (DMT-HFO) has recently been reported as an effective way to characterize P desorption over a long-term in laboratoty studies. However, there is little information on the relationship between kinetics of P release using this new method and plant P uptake. This method consist of a procedure of shaking a sample for a long period of time there by exploiting the whole volume of the soil which is in contrast to the actual plant mode of uptake. This method has also practical limitations in employing it for a routine soil analysis, as it is very expensive and time consuming. The objectives of this study were (i) to study the changes in labile, non-labile and residual P using successive P desorption by DMT-HFO followed by a subsequent fractionation method (combined method) (ii) to assess how the information gained from P desorption kinetic data relates to plant growth at green house and field trials (iii) to investigate the effect of varying shaking time on DMT-HFO extractable P and (iv) to propose a short cut approach to the combined method. The release kinetics of the plots from long term fertilizer trials at the University of Pretoria and Ermelo were studied. P desorption kinetics were described relatively well by a two-component first-order model (R2 = 0.947, 0.918,&0.993 for NPK, MNK,&MNPK treatments respectively). The relative contributions of both the labile pool (SPA) and the less labile pool (SPB) to the total P extracted increased with increased P supply levels. Significant correlations were observed between the rate coefficients and maize grain yield for both soil types. The correlation between the cumulative P extracted and maize yield (r = 0.997**) however was highly significant for Ermelo soils. This method was also used to determine the changes in the different P pools and to relate these P fractions with maize yield. Highly significant correlations were observed between maize grain yield and the different P fractions including total P. In both soil types the contribution of both the labile and non-labile inorganic P fractions in replenishing the solution Pi was significant where as the contributions from the organic fractions were limited. The C/HCl-Pi is the fraction that decreased most in both cases as well. Investigation was carried out to evaluate the effect of varying shaking periods on the extractable DMT-HFO-Pi for UP soils of varying P levels. Four shaking options were applied. Significant difference was observed for the treatment of high P application. Shaking option 2 seemed relatively better than the others since it showed the strongest correlation. Thus for soils with high releasing kinetics and high total P content, provided that the P release from the soil is a rate limiting step, reducing the length of shaking time could shorten the duration one needs to complete the experiment with out influencing the predicting capacity of the methodology. The other objective of this thesis was also to present a short cut method alternative to the combined fractionation method. Comparison of the sum of DMT-HFO-Pi, NaHCO3-Pi, NaOH-Pi, D/HCl-Pi and C/HCl-Pi extracted by a conventional step-by-step method with the sum of DMT-HFO-Pi and a single C/HCl-Pi extraction as a short cut approach for all extraction periods resulted in strong and significant correlations. The C/HCl-Pi fraction extracted by both methods was correlated with maize grain yield and it was found to be highly significant. This study revealed that this short cut approach could be a simplified and economically viable option to study the P dynamics of soils especially for soils where the P pool acting as a source in replenishing the labile portion of P is already identified. The method employed here therefore could act as an analytical tool to approximate successive cropping experiments carried out under green house or field condition. However, data from a wider range of soils is needed to evaluate the universality of this method. More work is also required in relating desorption indices of this method with yield parameters especially at field level. / Thesis (PhD)--University of Pretoria, 2009. / Plant Production and Soil Science / PhD / unrestricted

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2018-11-14T17:13:45Z No. of bitstreams: 1 2013 - Celeste Queiroz Rossi.pdf: 1977299 bytes, checksum: ce171e08be0a2a7e0cf26ac08f9fbd2f (MD5) / Made available in DSpace on 2018-11-14T17:13:45Z (GMT). No. of bitstreams: 1 2013 - Celeste Queiroz Rossi.pdf: 1977299 bytes, checksum: ce171e08be0a2a7e0cf26ac08f9fbd2f (MD5) Previous issue date: 2013-02-26 / CAPES / The accelerated growth of agriculture produces a demand for opening and exploration of new areas. Through government incentives, the migration of sugar cane production reached the Cerrado biome, and this occupation provides a gradual vegetation coverage change. In this context, the aim of this study was to evaluate the effect of sugar cane burning prior to harvesting in the soil organic matter and organic phosphorus in the Goias State Cerrado region. This study was conducted in a chronosequence of 1, 5, 10 and 20 years with straw burning, and application of vinasse in the 20 years area, compared to native vegetation (Cerrado) and pasture areas. The study areas were located in Decal industrial plant in Rio Verde municipality, Goi?s State (Brazil). The soil was classified as an Oxisol with sandy loam texture. Soil samples were taken in pits up to 0.6 m depth. Total organic carbon (TOC), total nitrogen (TN), soil organic matter (SOM) physical and chemical fractionation, and isotopes 13C and 15N were analyzed. Phosphorus chemical fractionation, extracted with NaHCO3, H2SO4 and NaOH, spectroscopic carbon (13C NMR, UV-vis and FTIR) and phosporus (31P NMR) characterization were evaluated. The area with lowest usage time of straw burning had highest Ca and Mg and lowest P and K values. The smallest TOC stocks were observed at the 0-10 cm layer in the sugar cane systems with 1 and 5 years. In general, the highest values of 13C and 15N were observed in the pasture and the lowest values in the Cerrado, with intermediate values in the sugar cane systems. Land use change from Cerrado original vegetation to sugar cane systems resulted in 13C changes, promoting an accumulation of C4 derived carbon plants. Spectroscopic analysis of carbon (13C RMN, UV-vis and infrared) from humic acids carbon showed the same functional groups independent of cane burning harvesting time. At the 0-5 cm depth layer, the aliphatic and carboxylic compounds had the largest contribution compared to the aromatic compounds. The 31P NMR spectroscopy results showed that in the studied areas, the humic acids constitute a readily available source of organic P important for plant uptake, especially in the area that received vinasse. In the areas with 1 and 5 years of harvesting burning sugar cane, the decrease in the accumulation of recalcitrant organic P in the humic acids indicates the usage of the labile-P in the humic substances. / O crescimento acelerado da agricultura gera a necessidade da abertura e explora??o de novas fronteiras agr?colas. Com incentivos governamentais, essa migra??o do setor sucroalcooleiro atingiu o Cerrado, e esta ocupa??o proporciona uma gradativa mudan?a na cobertura vegetal. Neste contexto, o objetivo deste estudo foi avaliar o efeito da queima pr?via para a colheita da cana-de-a??car na mat?ria org?nica e f?sforo org?nico do solo no Cerrado goiano. Foi utilizada uma cronossequ?ncia de 1, 5,10 anos com queima e 20 com queima da palhada e aplica??o de vinha?a, ?rea sob vegeta??o nativa (Cerrado) e pastagem. As ?reas de estudo localizam-se na Usina Decal, em Rio Verde, estado de Goi?s. O solo foi classificado como Latossolo Vermelho Distr?fico de textura franco arenosa. As amostras foram retiradas mediante a abertura de trincheiras at? 60 cm de profundidade. Foram analisados o carbono org?nico total (COT), nitrog?nio total (NT), fracionamento qu?mico e granulom?trico da MOS, 13C e 15N is?topos. A quantifica??o das fra??es de f?sforo foi obtida empregando-se extra??es com NaHCO3, H2SO4 e NaOH, al?m da caracteriza??o espectrosc?pica de carbono (RMN 13C, UV-vis?vel e infravermelho) e f?sforo (RMN 31P). O menor tempo de uso da queima da palhada acarretou em maiores teores de Ca e Mg e menores teores de P e K. Os menores estoques de COT foram verificados na camada de 0-10 cm nos sistemas de cana de 1 e 5 anos. De maneira geral, os maiores valores de 13C e 15N foram verificados na ?rea de pastagem e os menores na ?rea de Cerrado, com valores intermedi?rios para as ?reas de cana. A substitui??o da vegeta??o original de Cerrado para implanta??o de ?reas cultivadas com cana-de-a??car acarretou em mudan?as do 13C, promovendo um ac?mulo de carbono de plantas com ciclo fotossint?tico C4. As an?lises espectrosc?picas de carbono (RMN 13C, UV-v?sivel e infravermelho) dos ?cidos h?micos mostraram os mesmos grupos funcionais independente do tempo de colheita queimada da cana. Na camada de 0-5 cm, a maior contribui??o foi dos compostos alif?ticos e carbox?licos em rela??o aos compostos arom?ticos. Os resultados da espectroscopia de RMN 31P mostram que nas ?reas estudadas os ?cidos h?micos constituem uma reserva importante de P org?nico prontamente dispon?vel e fonte importante para nutri??o das plantas, principalmente na ?rea que recebeu vinha?a. J?, nas ?reas de 1 e 5 anos de cana queimada, a diminui??o do ac?mulo de P org?nico recalcitrante nos ?cidos h?micos indica utiliza??o do P-l?bil das subst?ncias h?micas.

Made available in DSpace on 2016-12-08T15:50:04Z (GMT). No. of bitstreams: 1 PGMS14DA022.pdf: 1661890 bytes, checksum: 3147ca0fadcd842b04a10dab73754a64 (MD5) Previous issue date: 2014-05-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The total content of phosphorus (P) is distributed in the soil forms with different degrees of lability, being the distribution of the forms affected by type soils and soil manegement. The work consisted of three studies, being that the first study quantified the stock of the forms of inorganic and organic P in the surface horizon and in 42 profiles soil of six orders in the Santa Catarina State. After collection, the samples were subjected to chemical fractionation of P Hedley. The soils most weathered had higher stock of P total, while the soils less weathered showed higher levels of labile organic P. In the second study was conducted fractionation analysis of P and P nuclear magnetic resonance (NMR) in soil agroecosystems with high organic matter content. The areas were evaluated in apple orchard, native grass and pine plantation. The results of chemical fractionation and NMR of P, showed that the conversion of natural ecosystems to areas cultivated altered the distribution of P forms in soil, where the fractions organic were reduced in culture without the addition of phosphate fertilizer systems. The third study involved the assessment of forms of P in soils with different clay contents that subjected the applications of liquid swine manure. Soil samples were collected in three regions of Santa Catarina State and subjected to chemical fractionation of P. The results showed that the addition of liquid swine manure for long term increased the content of all forms of P evaluated by fractionation, mainly in inorganic forms, with more accumulated in the topsoil. In soils with sandy texture there accumulation of labile P, and in soils clay there accumulation the of forms lower lability / O conteúdo total de fósforo (P) do solo é distribuido em formas com diferentes graus de labilidade. A distribuição das formas de P podem ser afetadas pelo tipo de solo e o manejo adotado durante seu uso. O trabalho foi composto de três estudos. O primeiro estudo quantificou o estoque das formas de P inorgânicas e orgânicas no horizonte superficial e nos perfis de 42 solos de seis ordens no Estado de Santa Catarina (SC). Após a coleta, as amostras foram submetidas ao fracionamento químico de P de Hedley. No segundo estudo foi realizado o fracionamento químico de P e análise de ressonância magnética nuclear de P (RMN) em amostras de solo de áreas de pomar de maçieira, campo nativo e florestamento de pinus com alto teor de matéria orgânica. O terceiro estudo consistiu na avaliação das formas de P em solos com diferentes teores de argila que foram submetidos a aplicações de dejetos líquidos de suínos. As amostras de solo foram coletadas em três regiões do Estado de SC e submetidas ao fracionamento químico de P. No estudo 1 os solos mais intemperizados apresentaram maiores estoque de P total enquanto os solos menos intemperizados apresentaram maiores teores de P lábil e P orgânico. No segundo estudo os resultados do fracionamento químico e RMN de P mostraram que a conversão de ecossistemas naturais em áreas cultivadas alterou a distribuição das formas de P no solo, onde as frações orgânicas foram reduzidas em sistemas de cultivo sem a adição de fertilizantes fosfatados. Os resultados do terceiro estudo mostraram que a adição de dejetos líquidos de suínos por longo prazo aumentou o teor em todas as formas de P avaliadas pelo fracionamento, principalmente em formas inorgânicas, sendo mais acumulado na camada superficial do solo. Nos solos com textura arenosa houve acúmulo de P principalmente nas frações lábeis e em solos de textura argilosa houve acúmulo de P principalmente em formas de menor labilidade