Presented diploma thesis is focused on the ecotoxicological evaluation of insecticide mixtures Perfekthion and Bulldock 25 EC and their effective substances, dimethoate and beta-cyfluthrin, respectively. Dimethoate is an organophosphate insecticide while beta-cyfluthrin belongs to pyrethroids. Both mixtures’ target organisms are sucking and biting pests on grain crops, potatoes, vegetables, oilseed rape and ornamental flowers. Their application over large areas and transport in large volumes generates a significant risk of entering the environment. Mixtures and substances were tested on water plant Lemna minor, algae Desmodesmus quadricauda and crustaceans Daphnia magna and Thamnocephalus platyurus. The LC50, EC50, and IC50 values were determined and ecotoxicity of substances and mixtures was evaluated and compared.

The chemical fate and biological impacts of cyfluthrin in aquatic ecosystems were investigated using microcosms (1.9 m^3 concrete tanks) during 1989. Results were compared to a concurrent pesticide registration study using mesocosms (634.7 m^3 earthen ponds). Ten spray drift and five soil runoff simulations were conducted. Pesticide loadings were scaled by system volume, with the same experimental design in ponds and microcosms. Aqueous cyfluthrin concentrations and sediment residue values were generally higher in microcosms, while aqueous half-life was shorter in the smaller systems.

Master of Science / Department of Grain Science and Industry / Bhadriraju Subramanyam / The insecticides, β-cyfluthrin and chlorpyrifos-methyl plus deltamethrin, are approved in the United States for treating empty bin surfaces. Chlorpyrifos-methyl plus deltamethrin and spinosad insecticides are approved for direct treatment of wheat. The efficacy of commercial formulations of β-cyfluthrin and chlorpyrifos-methyl plus deltamethrin at labeled rates was evaluated against adults of 16 field strains of the red flour beetle, Tribolium castaneum (Herbst); seven strains of sawtoothed grain beetle, Oryzaephilus surinamensis (L.); and two strains of the lesser grain borer, Rhyzopertha dominica (F.). Concrete arenas in plastic Petri dishes (9 cm diameter) were used to simulate the concrete floor of empty bins. The time for ~100% knockdown and mortality of adults of laboratory strains of the three species was first established by exposing them to insecticide-treated concrete surfaces for 1 to 24 h. Adults of field strains of each species were exposed to specific established insecticide-time combinations. Mortality of all species was lower than knockdown, suggesting recovery after seven days when placed on food. Chlorpyrifos-methyl plus deltamethrin did not control all R. dominica and most O. ]surinamensis field strains. β-cyfluthrin was extremely effective against R. dominica but ineffective against T. castaneum and O. surinamensis field strains, even at four times the high labeled rate. Field strains of R. dominica were highly susceptible to spinosad and chlorpyrifos-methyl plus deltamethrin at labeled rates on hard red winter wheat. Strains of T. castaneum and O. surinamensis were susceptible only to the latter insecticide. Dose-response tests with spinosad on the two least susceptible field strains of each species showed the lethal dose for 99% mortality (LD[subscript]99) for T. castaneum and R. dominica field strains were similar to that of the corresponding laboratory strains. Corresponding values for the two O. surinamensis field strains were significantly greater (~6 times) than the laboratory strain. The effective dose for progeny reduction (ED[subscript]99) of only one R. dominica field strain was significantly greater (~2 times) than that of the laboratory strain. The baseline susceptibility data of field strains of three insect species to spinosad will be useful for monitoring resistance development once this product is commercially released as a grain protectant.

Concurrent outdoor aquatic 1950 L microcosm and 0.04 ha mesocosm experiments with bluegill sunfish evaluated the ecological impact of cyfluthrin. Cyfluthrin effects were not observed on mesocosm bluegill; a slight decrease in growth was observed in the microcosm bluegill. Otolith weight to length relationships between bluegill size-classes from microcosms, local streams, and a fish hatchery revealed no differences. Our results indicated bluegill predation impacts were slight on benthic invertebrates. Extensive predation on emerging insects was observed. Microcosm bluegill impacts on zooplankton populations followed expected predation effects, resulting in larger populations of smaller taxa. Bluegill functioned as "keystone" predators for microcosm taxa and improved taxa richness for benthic colonizing invertebrates and zooplankton.

O tratamento de efluentes industriais tem sido objeto de estudos no sentido da busca de soluções que minimizem impactos ambientais e promovam a conservação do bem natural que é a água. Nesta linha de pensamento, o presente trabalho propôs-se avaliar a viabilidade de recuperação de efluentes industriais contaminados com pesticidas do tipo piretróides em específico: a deltametrina e beta-ciflutrina. A justificativa na escolha deste tipo de componente está fundamentada na alta demanda alimentícia por parte da população mundial e o consequente acréscimo no uso dos agrotóxicos a fim de garantir a eficiência e o elevado volume de produção de alimentos. O objetivo deste trabalho foi estudar a remoção da deltametrina e da beta-ciflutrina de efluentes sintéticos aquosos por meio dos processos de osmose inversa e nanofiltração, com a utilização de membranas de poliamida. O presente estudo se justifica pelo atendimento aos padrões ambientais de concentração de piretróides no meio ambiente e reafirma o uso do sistema com membranas no tratamento de efluentes e remoção destes contaminantes. Para caracterização das membranas, foi realizado o teste de permeabilidade hidráulica, constatando diferentes linearidades de fluxo entre os dois processos, com a variação de pressão de trabalho. O desempenho dos processos foi verificado pela variação de parâmetros de meio reacional, variando a concentração dos piretróides em solução, analisando os princípios ativos isolados e também em mistura de ambos piretróides. Primeiramente se estudou a remoção da deltametrina e da beta-ciflutrina isoladamente em solução, nas concentrações de 5, 25, 50 e 100 mg L-1, sob a pressão de 5 bar. Posteriormente, avaliou-se o desempenho das membranas na remoção dos piretróides em mistura nas soluções sintéticas, com ambos os princípios ativos na concentração de 50 mg L-1, na pressão de 5 bar. Foi estudada a remoção da deltametrina e da beta-ciflutrina nos dois processos: osmose inversa e nanofiltração. Os resultados foram tratados estatisticamente por análise de variância (ANOVA) e pela análise por comparação de amostras independentes a fim de verificar a significância dos valores obtidos e a influência da variação dos parâmetros analisados. Para a faixa de concentração estudada (5, 25, 50 e 100 mg L-1) os valores encontrados de concentração de permeado foram todos consideravelmente baixos. O maior valor encontrado foi de 0,026 mg L-1 no ensaio de nanofiltração com concentração inicial de 5 mg L-1 de beta-ciflutrina em água. Os resultados apresentaram excelentes rejeições em todos os testes, seja com princípio ativo isolado ou em mistura, com rejeições maiores que 99,5% para ambos os piretróides nas concentrações testadas, sob a pressão de 5 bar. O processo de nanofiltração apresentou maiores e melhores fluxos de permeado do que a osmose inversa. Contudo, no que diz respeito à eficácia da separação, ambos processos indicaram ótimo desempenho na remoção dos piretróides, viabilizando assim, a escolha destes métodos para tratamento de efluentes contaminados com este pesticida / Treatment of industrial effluents has been the subject of numerous studies aimed at finding solutions that minimize environmental impacts and promote the recovery and / or reuse of the natural benefit which is the water. With this in mind, this study aims to evaluate the feasibility of recovery of industrial effluents contaminated with pyrethroid pesticide - in particular: the beta-cyfluthrin and deltamethrin. The justification for choosing this type of component is based on the high demand for food for the world population and consequent increase in the use of pesticides to ensure efficiency and high volume food production. The aim of this work was to study the removal of deltamethrin and beta-cyfluthrin from synthetic effluents through process of reverse osmosis and nanofiltration, with the use of polyamide membranes. This study is justified by attendance to environmental standards for pyrethroids concentration in the environment and it reaffirms the use of membranes system in wastewater treatment and in the removal of contaminants. For membranes characterization an hydraulic permeability test was performed, noting different flow linearities between the two processes, under variation of pressure. The process performance was verified by variation of parameters of reaction environment, by varying the concentration of pyrethroids in solution, examining the active ingredients alone and in mixture of both pyrethroids. First of all, we have studied the removal of deltamethrin and beta-cyfluthrin alone in solution, on concentrations of 5, 25, 50 and 100 mg L-1, under the pressure of 5 bar. Subsequently, we assessed the performance of the membranes in the removal of pyrethroid in mixture in the synthetic solutions, with both active ingredients at a concentration of 50 mg L-1, at a pressure of 5 bar. We studied the removal of deltamethrin and beta-cyfluthrin in two processes: reverse osmosis and nanofiltration. The results were statistically analyzed by analysis of variance (ANOVA) and analysis by comparison of independent samples in order to verify the significance of the values obtained and the influence of variation of parameters. For the concentration range studied (5, 25, 50 and 100 mg L-1) the values found in the permeate concentration were all pretty low. The highest value obtained was 0.026 mg L-1 in nanofiltration test with initial concentration of 5 mg L-1 of beta-cyfluthrin in water. The results showed excellent rejections in all tests, either with isolated active ingredient or in coexistence of them, attesting rejections greater than 99,5% for both pyrethroids, under the pressure of 5 bar. The nanofiltration process had higher and better permeate fluxes than the reverse osmosis. However, regarding the effectiveness of separation, both processes showed excellent performance in the removal of pyrethroids, thus enabling the choice of these methods for treatment of wastewater which are contaminated with this kind of pesticide

O tratamento de efluentes industriais tem sido objeto de estudos no sentido da busca de soluções que minimizem impactos ambientais e promovam a conservação do bem natural que é a água. Nesta linha de pensamento, o presente trabalho propôs-se avaliar a viabilidade de recuperação de efluentes industriais contaminados com pesticidas do tipo piretróides em específico: a deltametrina e beta-ciflutrina. A justificativa na escolha deste tipo de componente está fundamentada na alta demanda alimentícia por parte da população mundial e o consequente acréscimo no uso dos agrotóxicos a fim de garantir a eficiência e o elevado volume de produção de alimentos. O objetivo deste trabalho foi estudar a remoção da deltametrina e da beta-ciflutrina de efluentes sintéticos aquosos por meio dos processos de osmose inversa e nanofiltração, com a utilização de membranas de poliamida. O presente estudo se justifica pelo atendimento aos padrões ambientais de concentração de piretróides no meio ambiente e reafirma o uso do sistema com membranas no tratamento de efluentes e remoção destes contaminantes. Para caracterização das membranas, foi realizado o teste de permeabilidade hidráulica, constatando diferentes linearidades de fluxo entre os dois processos, com a variação de pressão de trabalho. O desempenho dos processos foi verificado pela variação de parâmetros de meio reacional, variando a concentração dos piretróides em solução, analisando os princípios ativos isolados e também em mistura de ambos piretróides. Primeiramente se estudou a remoção da deltametrina e da beta-ciflutrina isoladamente em solução, nas concentrações de 5, 25, 50 e 100 mg L-1, sob a pressão de 5 bar. Posteriormente, avaliou-se o desempenho das membranas na remoção dos piretróides em mistura nas soluções sintéticas, com ambos os princípios ativos na concentração de 50 mg L-1, na pressão de 5 bar. Foi estudada a remoção da deltametrina e da beta-ciflutrina nos dois processos: osmose inversa e nanofiltração. Os resultados foram tratados estatisticamente por análise de variância (ANOVA) e pela análise por comparação de amostras independentes a fim de verificar a significância dos valores obtidos e a influência da variação dos parâmetros analisados. Para a faixa de concentração estudada (5, 25, 50 e 100 mg L-1) os valores encontrados de concentração de permeado foram todos consideravelmente baixos. O maior valor encontrado foi de 0,026 mg L-1 no ensaio de nanofiltração com concentração inicial de 5 mg L-1 de beta-ciflutrina em água. Os resultados apresentaram excelentes rejeições em todos os testes, seja com princípio ativo isolado ou em mistura, com rejeições maiores que 99,5% para ambos os piretróides nas concentrações testadas, sob a pressão de 5 bar. O processo de nanofiltração apresentou maiores e melhores fluxos de permeado do que a osmose inversa. Contudo, no que diz respeito à eficácia da separação, ambos processos indicaram ótimo desempenho na remoção dos piretróides, viabilizando assim, a escolha destes métodos para tratamento de efluentes contaminados com este pesticida / Treatment of industrial effluents has been the subject of numerous studies aimed at finding solutions that minimize environmental impacts and promote the recovery and / or reuse of the natural benefit which is the water. With this in mind, this study aims to evaluate the feasibility of recovery of industrial effluents contaminated with pyrethroid pesticide - in particular: the beta-cyfluthrin and deltamethrin. The justification for choosing this type of component is based on the high demand for food for the world population and consequent increase in the use of pesticides to ensure efficiency and high volume food production. The aim of this work was to study the removal of deltamethrin and beta-cyfluthrin from synthetic effluents through process of reverse osmosis and nanofiltration, with the use of polyamide membranes. This study is justified by attendance to environmental standards for pyrethroids concentration in the environment and it reaffirms the use of membranes system in wastewater treatment and in the removal of contaminants. For membranes characterization an hydraulic permeability test was performed, noting different flow linearities between the two processes, under variation of pressure. The process performance was verified by variation of parameters of reaction environment, by varying the concentration of pyrethroids in solution, examining the active ingredients alone and in mixture of both pyrethroids. First of all, we have studied the removal of deltamethrin and beta-cyfluthrin alone in solution, on concentrations of 5, 25, 50 and 100 mg L-1, under the pressure of 5 bar. Subsequently, we assessed the performance of the membranes in the removal of pyrethroid in mixture in the synthetic solutions, with both active ingredients at a concentration of 50 mg L-1, at a pressure of 5 bar. We studied the removal of deltamethrin and beta-cyfluthrin in two processes: reverse osmosis and nanofiltration. The results were statistically analyzed by analysis of variance (ANOVA) and analysis by comparison of independent samples in order to verify the significance of the values obtained and the influence of variation of parameters. For the concentration range studied (5, 25, 50 and 100 mg L-1) the values found in the permeate concentration were all pretty low. The highest value obtained was 0.026 mg L-1 in nanofiltration test with initial concentration of 5 mg L-1 of beta-cyfluthrin in water. The results showed excellent rejections in all tests, either with isolated active ingredient or in coexistence of them, attesting rejections greater than 99,5% for both pyrethroids, under the pressure of 5 bar. The nanofiltration process had higher and better permeate fluxes than the reverse osmosis. However, regarding the effectiveness of separation, both processes showed excellent performance in the removal of pyrethroids, thus enabling the choice of these methods for treatment of wastewater which are contaminated with this kind of pesticide