O uso de técnicas miniaturizadas de preparo de amostra vem se tornando uma tendência cada vez mais crescente em química analítica. Dentre elas o MEPS (Microextraction by a Packed Sorbent) apresenta grande potencial por poder ser acoplado on-line, sem grandes modificações, à cromatografia gasosa e líquida, não necessitando de grande quantidade de tempo para análise e seu cartucho sorvente ser reutilizável. O uso de MEPS, foi mais explorado até o presente momento na análise de fármacos em fluídos biológicos; dessa forma existe um pequeno número de publicações que exploram o uso dessa técnica na determinação de agrotóxicos em matrizes de alimentos. Por esse motivo, o presente trabalho teve como objetivo a avaliação do uso dessa técnica na determinação de seis agrotóxicos utilizados no cultivo da cana-de-açúcar (tebutiurom, carbofurano, atrazina, metribuzim, ametrina e bifentrina) em amostras de garapa. Para o desenvolvimento desse estudo foram verificadas dentre as variáveis pH, força iônica, solvente de eluição e volume do solvente de eluição, quais poderiam afetar o desempenho da técnica em diferentes fases extratoras, empregando nessa etapa de otimização planejamento fatorial fracionário 24-1. As fases avaliadas foram C18 Chromabond e HLB Oasis, assim como sistemas comercialmente disponíveis com as fases C18, C8, SAX, SCX e SIL. Durante essa etapa foi realizado um estudo inicial do uso do grafeno como material sorvente em MEPS, considerando as propriedades que esse material apresenta para atuar como adsorvente em técnicas de preparo de amostra. Contudo, o uso do grafeno apresentou entupimento no cartucho de sorção, problema ainda em avaliação. A fase C18 Chromabond foi a que apresentou os melhores resultados, sendo a escolhida para otimização dos parâmetros envolvidos na etapa de extração por MEPS. Os parâmetros otimizados por planejamento fatorial 23 foram os ciclos de: aspiração da amostra, lavagem e eluição. O método desenvolvido foi validado baseado nos critérios exigidos pelo MAPA e apresentou seletividade, linearidade e os limites de quantificação variaram de 2-10 μg/L. A recuperação foi adequada para todos os analitos (71,7-106,9%), assim como a precisão intra e inter-dia que apresentou coeficientes de variação (CV) menores que 16%. O método desenvolvido foi aplicado em quatro amostras reais de garapa de diferentes regiões. / The use of miniaturized techniques in sample preparation has becoming a growing trend in analytical chemistry. Among these techniques MEPS (Microextraction by a Packed Sorbent) presents a great potential affording on-line coupling, without much modification to gas and liquid chromatography systems, in addition it does not require large analyses time and the sorbent cartridge is reusable. MEPS utilization has been explored mainly for drugs analyses in biological fluids, existing limited number of publications that apply this technique for pesticides analyses in food sample matrix. For this reason the goal of present work was the evaluation of MEPS in the analyses of six pesticides used in sugarcane cultivation (tebuthiuron, carbofuran, atrazine, metribuzine, ametryn and bifenthrin) in sugarcane juice samples. During the method development several variables were evaluated including pH, ionic strength, elution solvent and solvent volume, to determine which ones could affect the technique perform in different sorbent phases. For this optimization step, fractional factorial design 24-1 was utilized. Phases evaluated included C18 Chromabond and HLB Oasis, and also commercially available system containg C18, C8, SAX, SCX e SIL. During this step, it was also carried out an initial study employing graphene in a MEPS system; Tanking into account the properties that this material presents to act as adsorbent in sample preparation techniques. However the graphene showed obstruction problems in the sorption cartridge, whose solution is under way. The phase C18 Chromabond showed better results, and was chosen to MEPS parameters optimization. MEPs parameters optimized by full factorial desing 23 were the following cycles: sample aspiration, washing and elution. The method, was validated based upon the MAPA requirements and showed good selectivity, linearity an quantifications limits ranging from 2-10 μg/L. Recovery was satisfactory for all pesticides (71,7-106,9%), intra- and inter-day precision were satisfactory and showed coefficients of variation (CV) less than 16%. Hence, the developed method was applied to the analysis of four real samples of sugarcane juice obtained from different regions.

New technologies, such as an efficient vapor-compression evaporator, a stationary lime kiln (SLK), and the MixAlco process, compelled us to re-evaluate methods for producing sugar from cane. These technologies allow more water and lime to be used, and they add more value to bagasse. Extracting and preserving the sugars, and lime pretreating the bagasse to enhance biodigestibility, all at the same time in a pile, was demonstrated to be unfeasible; therefore, sugar extraction must occur before lime treating the bagasse. Sugar extraction should occur countercurrently by lixiviation, where liquid moves in stages opposite to the soaked bagasse (megasse), which is conveyed by screw-press conveyors that gently squeeze the fiber in each stage, improving extraction. The performance of a pilot-scale screw-press conveyor was tested for dewatering capabilities and power consumption. The unoptimized equipment decreased megasse moisture from 96 to 89%. Simulation of the process suggested that eight stages are necessary to achieve 98% recovery from typical sugarcane. The cumulative power for the screw-press conveyor system was 17.0±2.1 hp•h/ton dry fiber. Thin raw juice preserved with lime for several months showed no sucrose degradation and no quality deterioration, except for reducing sugar destruction. The lime loading needed for 1-year preservation is 0.20 g Ca(OH)2/g sucrose. Shorter times require less lime. After preservation, the juice was carbonated and filtered, and the resulting sludge pelletized. Due to their high organic content, the pellets were too weak for calcination temperatures used in the SLK. The organics must be decreased prior to pelletization and sodium must be supplemented as a binding agent. Long-term lime pretreatment of bagasse showed two delignification phases: bulk (rapid) and residual (slow). These were modeled by two simultaneous first-order reactions. Treatments with air purging and higher temperatures (50 – 57oC) delignified more effectively, especially during the residual phase, thus yielding higher cellulase-enzyme digestibilities after 2 – 8 weeks of treatment. At temperatures > 60oC, pure oxygen purging is preferred. Fresh bagasse was of better quality than old bagasse. Treatment with NaOH yielded a larger bulk delignification phase than Ca(OH)2. Long-term lime pulping of bagasse was unsuitable for copy-quality paper, but it was appropriate for strawboard and other filler applications.