Formulações a base de dispersões oleosas de conídios aéreos de fungos entomopatogênicos apresentam diversas vantagens em comparação à aplicação de produtos não formulados; entretanto, a complexidade e a falta de compreensão dos fatores que influenciam a persistência desse tipo de formulação fazem com que ainda seja pouco utilizada. O efeito de diferentes níveis de secagem de conídios, tipo de óleo, métodos de extração, estabilidade de blastosporos, compatibilidade de surfactantes e adição de aditivos foram avaliados para o desenvolvimento de micopesticidas formulados em óleo. Os melhores resultados obtidos com os conídios em óleo foram avaliados quanto à proteção conferida à radiação UV e a eficiência das formulações na mortalidade de Tenebrio molitor. Zeolita foi a argila mais eficiente na manutenção da viabilidade de blastosporos de M. anisopliae e B. bassiana, e apesar de resultados promissores a estabilidade desses propágulos foi muito inferior a de conídios aéreos. Vinte surfactantes foram avaliados quanto a inocuidade aos conídios, em dois ensaios, culminando com a seleção dos quatro mais compatíveis, dois deles E5 e E7, avaliados nos experimentos posteriores demonstraram bom potencial para compor a formulação como agentes emulsionantes. Dois aditivos foram avaliados na formulação e respostas distintas foram observadas. O A1 foi altamente incompatível, enquanto diferentes concentrações de A2 (1, 3 e 5%) incrementaram a sobrevivência dos conídios em até sete vezes. As vantagens da presença do A2 ficaram evidentes também em combinações de óleo com os quatro emulsionantes selecionados. As dispersões oleosas proporcionaram sobrevivência até sete vezes superior para conídios expostos a radiação UV em relação a conídios não formulados e dois experimentos comprovaram que as formulações oleosas testadas foram mais eficientes no controle de insetos, com reduções de até 2,3 vezes no tempo de sobrevivência de insetos. Os 12 bioensaios com mais de 20.000 leituras de viabilidade descritos neste trabalho permitiram um melhor entendimento dos fatores críticos que afetam a vida de prateleira de conídios, e indicam procedimentos que podem ser utilizados para melhorar a estabilidade de micopesticidas formulados em óleo. / Oil-based formulations of aerial conidia of entomopatogenic fungi have several advantages compared to the use of unformulated products; however, the complexity and lack of understanding of the factors that influence the persistence of this type of formulation make it still not widely used. The effect of different levels of drying conidia, oil type, extraction methods, blastospores stability, compatibility of surfactants and addition of additives were evaluated for the development of a mycopesticide oil formulation. The best results obtained with aerial conidia were evaluated regarding the protection against UV radiation and the efficacy of the formulations to control Tenebrio molitor. Zeolita was the most compatible clay in maintaining the viability of blastospores of M. anisopliae and B. bassiana, and despite promising results in the stability, the shelf life of these propagules was much lower than aerial conidia. Twenty surfactants were evaluated for safety to conidia in two trials resulting in the selection of the four most compatible, two of them E5 and E8, were evaluated in subsequent experiments demonstrating good potential as emulsifiers in oil-based formulations. Two additives were evaluated in the formulation and distinct responses were observed. A1 was highly toxic to the fungi, while different concentrations of A2 increased the survival of the conidia up to seven times. The advantages of A2 were evident also in combinations of oil with the four selected emulsifiers. Oil-based formulation provided survival up to seven times higher for conidia exposed to simulated UV radiation compared to unformulated conidia, and two experiments showed that oil formulations were more efficient in the insect control, with reductions of up to 2.3 times on the survival time of insects. Twelve bioassays and over 20.000 viability readings described in this work, allowed a better understanding of the critical factors that affect the shelf-life of conidia, and indicate methods that can be used to improve the stability of mycopesticides in oil-based formulations.

Os derramamentos de petróleo são consequência inevitável e indesejável da produção e transporte do petróleo e seus derivados. A maioria desses derramamentos são relativamente pequenos, mas alguns deles são grandes o suficiente para causar significativo impacto ambiental. Nessas situações, os modelos computacionais são ferramentas importantes para estimar a trajetória, dimensionamento e comportamento do óleo derramado no ambiente marinho, sendo determinantes na elaboração de planos de ação e trabalho das equipes de resposta. O transporte e destino de óleo offshore derramado são regidos majoritariamente, no curto período, por processos de transporte e de transformação físico-químicos e no longo período por processos de degradação biológica, de acordo com as condições ambientais locais (oceânicas e atmosféricas). Os principais processos que atuam sobre as manchas de óleo offshore incluem, no curto período, advecção, difusão turbulenta, espalhamento superficial, evaporação, dissolução, emulsificação, sedimentação e a interação de mancha de óleo com a linha da costa. O STFM (Spill, Transport and Fate Model) foi o modelo computacional desenvolvido nesse trabalho. Os algoritmos foram desenvolvidos com base em formulações físico-químicas propostas na literatura, sendo testadas as proposições de diversos autores e selecionadas as equações que apresentaram melhores resultado para integrar o conjunto físico-químico que compõe o STFM. Os resultados do trabalho mostraram que o STFM apresentou desempenho superior aos demais modelos testados na descrição do espalhamento e difusão dando mais estabilidade à mancha por utilizar a derivação de Dodge para a proposta de espalhamento de Fay e substituir o método usual de Randon Walk por Randon Flight (avançado no tempo) na forma canônica dada por Lynch. O algoritmo do STFM também traz outra evolução importante ao incluir um modelo de evaporação baseado nas equações empíricas de Fingas, substituindo as atuais parametrizações baseadas no ADIOS2 e nos métodos de pseudocomponentes. / Oil and its by-products spills are an inevitable and undesirable consequence of their production and transportation. Even though these spills are relatively small, some of them are large enough to cause significant environmental impact. Taken this into account, the computational models are important tools to estimate the trajectory, dimensioning and behavior of the oil spilled in the marine environment, being also determinants to elaborate action plans for response teams work. The transportation and fate of oil spills are governed in the short term by physical-chemical transport and transformation processes and in the long term by biological degradation processes, according to local environmental conditions (oceanic and atmospheric). The main processes that act on offshore oil spills include, in the short term, advection, turbulent diffusion, surface scattering, evaporation, dissolution, emulsification, sedimentation and the interaction of oil slick according to the coast line. The Spill, Transport and Fate Model (STFM) was the computational model developed in this work. The algorithms were developed based on physicochemical formulations proposed in literature, being the propositions of several authors tested and the equations which presented the best results were selected to integrate the physical-chemical set that makes up the STFM. The STFM results presented superior performance, giving more stability to the stain, compared to the other models tested in the scattering and diffusion description, by using the Dodge derivation for the Fay spreading proposal and by replacing the usual \"Randon Walk\" method by \"Randon Flight\" (advanced in time) in the canonical form given by Lynch. The STFM algorithm also brings forward another important evolution by including an evaporation model based on Fingas empirical equations, replacing the current parameterizations based on ADIOS2 and pseudo component methods.

Os derramamentos de petróleo são consequência inevitável e indesejável da produção e transporte do petróleo e seus derivados. A maioria desses derramamentos são relativamente pequenos, mas alguns deles são grandes o suficiente para causar significativo impacto ambiental. Nessas situações, os modelos computacionais são ferramentas importantes para estimar a trajetória, dimensionamento e comportamento do óleo derramado no ambiente marinho, sendo determinantes na elaboração de planos de ação e trabalho das equipes de resposta. O transporte e destino de óleo offshore derramado são regidos majoritariamente, no curto período, por processos de transporte e de transformação físico-químicos e no longo período por processos de degradação biológica, de acordo com as condições ambientais locais (oceânicas e atmosféricas). Os principais processos que atuam sobre as manchas de óleo offshore incluem, no curto período, advecção, difusão turbulenta, espalhamento superficial, evaporação, dissolução, emulsificação, sedimentação e a interação de mancha de óleo com a linha da costa. O STFM (Spill, Transport and Fate Model) foi o modelo computacional desenvolvido nesse trabalho. Os algoritmos foram desenvolvidos com base em formulações físico-químicas propostas na literatura, sendo testadas as proposições de diversos autores e selecionadas as equações que apresentaram melhores resultado para integrar o conjunto físico-químico que compõe o STFM. Os resultados do trabalho mostraram que o STFM apresentou desempenho superior aos demais modelos testados na descrição do espalhamento e difusão dando mais estabilidade à mancha por utilizar a derivação de Dodge para a proposta de espalhamento de Fay e substituir o método usual de Randon Walk por Randon Flight (avançado no tempo) na forma canônica dada por Lynch. O algoritmo do STFM também traz outra evolução importante ao incluir um modelo de evaporação baseado nas equações empíricas de Fingas, substituindo as atuais parametrizações baseadas no ADIOS2 e nos métodos de pseudocomponentes. / Oil and its by-products spills are an inevitable and undesirable consequence of their production and transportation. Even though these spills are relatively small, some of them are large enough to cause significant environmental impact. Taken this into account, the computational models are important tools to estimate the trajectory, dimensioning and behavior of the oil spilled in the marine environment, being also determinants to elaborate action plans for response teams work. The transportation and fate of oil spills are governed in the short term by physical-chemical transport and transformation processes and in the long term by biological degradation processes, according to local environmental conditions (oceanic and atmospheric). The main processes that act on offshore oil spills include, in the short term, advection, turbulent diffusion, surface scattering, evaporation, dissolution, emulsification, sedimentation and the interaction of oil slick according to the coast line. The Spill, Transport and Fate Model (STFM) was the computational model developed in this work. The algorithms were developed based on physicochemical formulations proposed in literature, being the propositions of several authors tested and the equations which presented the best results were selected to integrate the physical-chemical set that makes up the STFM. The STFM results presented superior performance, giving more stability to the stain, compared to the other models tested in the scattering and diffusion description, by using the Dodge derivation for the Fay spreading proposal and by replacing the usual \"Randon Walk\" method by \"Randon Flight\" (advanced in time) in the canonical form given by Lynch. The STFM algorithm also brings forward another important evolution by including an evaporation model based on Fingas empirical equations, replacing the current parameterizations based on ADIOS2 and pseudo component methods.

Formulações a base de dispersões oleosas de conídios aéreos de fungos entomopatogênicos apresentam diversas vantagens em comparação à aplicação de produtos não formulados; entretanto, a complexidade e a falta de compreensão dos fatores que influenciam a persistência desse tipo de formulação fazem com que ainda seja pouco utilizada. O efeito de diferentes níveis de secagem de conídios, tipo de óleo, métodos de extração, estabilidade de blastosporos, compatibilidade de surfactantes e adição de aditivos foram avaliados para o desenvolvimento de micopesticidas formulados em óleo. Os melhores resultados obtidos com os conídios em óleo foram avaliados quanto à proteção conferida à radiação UV e a eficiência das formulações na mortalidade de Tenebrio molitor. Zeolita foi a argila mais eficiente na manutenção da viabilidade de blastosporos de M. anisopliae e B. bassiana, e apesar de resultados promissores a estabilidade desses propágulos foi muito inferior a de conídios aéreos. Vinte surfactantes foram avaliados quanto a inocuidade aos conídios, em dois ensaios, culminando com a seleção dos quatro mais compatíveis, dois deles E5 e E7, avaliados nos experimentos posteriores demonstraram bom potencial para compor a formulação como agentes emulsionantes. Dois aditivos foram avaliados na formulação e respostas distintas foram observadas. O A1 foi altamente incompatível, enquanto diferentes concentrações de A2 (1, 3 e 5%) incrementaram a sobrevivência dos conídios em até sete vezes. As vantagens da presença do A2 ficaram evidentes também em combinações de óleo com os quatro emulsionantes selecionados. As dispersões oleosas proporcionaram sobrevivência até sete vezes superior para conídios expostos a radiação UV em relação a conídios não formulados e dois experimentos comprovaram que as formulações oleosas testadas foram mais eficientes no controle de insetos, com reduções de até 2,3 vezes no tempo de sobrevivência de insetos. Os 12 bioensaios com mais de 20.000 leituras de viabilidade descritos neste trabalho permitiram um melhor entendimento dos fatores críticos que afetam a vida de prateleira de conídios, e indicam procedimentos que podem ser utilizados para melhorar a estabilidade de micopesticidas formulados em óleo. / Oil-based formulations of aerial conidia of entomopatogenic fungi have several advantages compared to the use of unformulated products; however, the complexity and lack of understanding of the factors that influence the persistence of this type of formulation make it still not widely used. The effect of different levels of drying conidia, oil type, extraction methods, blastospores stability, compatibility of surfactants and addition of additives were evaluated for the development of a mycopesticide oil formulation. The best results obtained with aerial conidia were evaluated regarding the protection against UV radiation and the efficacy of the formulations to control Tenebrio molitor. Zeolita was the most compatible clay in maintaining the viability of blastospores of M. anisopliae and B. bassiana, and despite promising results in the stability, the shelf life of these propagules was much lower than aerial conidia. Twenty surfactants were evaluated for safety to conidia in two trials resulting in the selection of the four most compatible, two of them E5 and E8, were evaluated in subsequent experiments demonstrating good potential as emulsifiers in oil-based formulations. Two additives were evaluated in the formulation and distinct responses were observed. A1 was highly toxic to the fungi, while different concentrations of A2 increased the survival of the conidia up to seven times. The advantages of A2 were evident also in combinations of oil with the four selected emulsifiers. Oil-based formulation provided survival up to seven times higher for conidia exposed to simulated UV radiation compared to unformulated conidia, and two experiments showed that oil formulations were more efficient in the insect control, with reductions of up to 2.3 times on the survival time of insects. Twelve bioassays and over 20.000 viability readings described in this work, allowed a better understanding of the critical factors that affect the shelf-life of conidia, and indicate methods that can be used to improve the stability of mycopesticides in oil-based formulations.

Agitated dispersions of one liquid in another immiscible liquid are widely used in chemical industry in operations such as liquid-liquid extraction, suspension polymerisation, and blending of polymers. When holdup of the dispersed phase is increased, in an effort to increase the productivity, at a critical holdup, the dispersed phase catastrophically becomes the continuous phase and vice versa. This phenomenon is known as phase inversion. Although the inversion phenomenon has been studied off and on over the past few decades, the mechanism of phase inversion (PI) has yet not become clear. These studies have however brought out many interesting aspects of PI, besides unravelling the effect of physical and operational variables on PL Experiments show that oil-in-water (o/w) and water-in-oil (w/o) dispersions behave very differently, e.g water drops in w/o dispersions contain oil droplets in them, but oil drops in o/w dispersions contain none, dispersed phase hold up at which inversion occurs increases with agitation speed for w/o dispersions but decreases for o/w dispersions. A common feature of both types of dispersions however is that as agitation speed is increased to high values, inversion holdups reach a constant value. A further increase in agitation speed does not change inversion hold up. Although this finding was first reported a long time ago, the implications it may have not received any attentions. In fact, the work reported in the literature since then does not even mention it. The present work shows that this finding has profound implications. Starting with the finding that at high agitation speed inversion hold up does not change with agitation speed, the present work shows that inversion hold up also does not change with agitator diameter, type of agitator and vessel diameter. In these experiments, carried out in agitated vessel, energy was introduced as a point source. The experiments carried out with turbulent flow in annular region of two coaxial cylinders, inner one rotating, in which energy is introduced nearly uniformly throughout the system, show that the inversion holdup remains unchanged. These results indicate that constant values of inversion holdups for a given liquid-liquid systems (o/w and w/o) are properties of the liquid-liquid systems alone, independent of geometrical and operational parameters. A new hypothesis is proposed to explain the new findings. Phase inversion is considered to occur as a result of imbalance between breakup and coalescence of drops. Electrolytes, which affect only coalescence of drops, were therefore added to the system to investigate the effect of altering coalescence of drops on phase inversion. The experiments performed in the presence of electrolyte KI at various concentrations indicate that addition of electrolyte increases the inversion holdup for both o/w and w/o dispersions for three types of systems: non polar-water, polar-water and immiscible organic-organic. Higher the concentration of electrolyte used, higher was the holdup required for phase inversion. These findings indicate that while the addition of electrolyte increases coalescence of drops in lean dispersions, it has exactly opposite effect on imbalance of breakage and coalescence of drops at high holdups near phase inversion point. The opposite effect of electrolytes in lean and concentrated dispersions could be explained qualitatively, but only in part in the light of a new theory, involving multi-particle interactions. The phase inversion phenomenon is quantified in a simple manner by testing the breakage and coalescence rate expressions available in literature. It has been found that, equilibrium drop size (where breakage and coalescence events are in dynamic equilibrium) approaches infinity near phase inversion holdup which is not an ex perimentally observed fact. To capture the catastrophic nature of phase inversion, two steady state approach is proposed. The two steady states namely the stable steady state and unstable steady state, are achieved by modifying the expression for coalescence frequency on the basis of (i) shear coalescence mechanism and, (ii) recognising the fact that at high dispersed phase holdup the droplets are already in contact with each other at all times and hence rendering the second order coales cence process to a first order one. Using two steady states approach, catastrophic phase inversion is shown to occur at finite drop size.