Made available in DSpace on 2015-03-05T16:20:40Z (GMT). No. of bitstreams: 0 Previous issue date: 16 / Nenhuma / O presente estudo inserido na linha de pesquisa “Diversidade e manejo de Vida Silvestre” objetivou investigar a ocorrência de artrópodes e a seletividade de lambdacialotrina em populações de inimigos naturais, em áreas de arroz irrigado. Os experimentos foram realizados em Cachoeira do Sul, Eldorado do Sul e Capivari do Sul nos anos agrícolas 2007/08 e 2008/09. Para o levantamento dos artrópodes, em cada localidade foram utilizadas quatro parcelas orizícolas sem tratamentos com inseticidas. As amostragens foram realizadas durante as três fases do cultivo das plantas, utilizando-se rede de varredura. Na análise da seletividade , as áreas orizícolas foram compostas por duas subáreas, sendo que uma delas foi tratada com 150mL/ha-1 de lambdacialotrina, enquanto a outra ficou isenta do produto. As avaliações foram realizadas aproximadamente aos 2, 15, 30 e 45 dias após a aplicação do inseticida, conforme as datas de amostragem nas localidades. Os resultados revelaram que a ocorrência dos artrópodes variou conforme

O objetivo do trabalho foi o de comparar a eficiência de aplicação de agroquímicos na cultura da soja utilizando diferentes pontas de pulverização para aplicações terrestres em alta velocidade. Foram avaliadas as pontas AXI 110 04 na velocidade de 15 km.h-1 (testemunha), APE Cinza, AXI 110 08, TD Hispeed 110 06 e AXI TWIN 120 06, todos na velocidade de deslocamento de 35 km.h-1. O volume de aplicação foi fixado em 120 L.ha-1. A eficiência de aplicação foi avaliada por dois métodos: Análise do percentual de cobertura utilizando marcador fluorescente e luz ultravioleta e análise de depósito através da recuperação e quantificação do corante azul brilhante FD&C N°1 por espectrofotometria. Ambas as analises foram feitas em amostras retiradas de três partes da planta: Superior, média e inferior. As pontas de pulverização mostraram padrões de cobertura e depósito diferenciados, de modo que na parte superior da planta, a cobertura foi favorecida por gotas mais finas e o depósito melhorado pelo uso de gotas médias. Nas demais partes da planta não houve diferença estatística entre os tratamentos tanto para cobertura quanto para depósito. A velocidade de deslocamento não interferiu na eficiência de aplicação para pontas com mesmo padrão de gota, permitindo o aumento da capacidade efetiva do pulverizador sem diminuição na qualidade da aplicação. / The aim of this study was to compare the efficiency of agrochemical application on soybean crop using different types of spray nozzles for ground applications in high travel speed. It was evaluated the nozzles AXI 110 04 with ground speed of 15 km.h-1 (reference), APE Grey, AXI 110 08, TD Hispeed 110 06 and AXI TWIN 120 06, all using travel speed of 35 km.h-1. The volume rate was fixed in 120L.ha-1. The application efficiency was evaluated by two different methods: Analysis of coverage area using fluorescent dye tracer and UV light and analysis of deposits through the recovery and quantification of bright blue tracer FD&C N°1 by Spectrophotometry. Both analysis were done in samples collected from three parts of the plant: Top, medium and bottom. The spray nozzles showed differences in coverage and deposit pattern, so in the top of the plant, the coverage was increased with smaller droplets and the deposit was increased with medium droplets. In the other parts of the plant, there was no statistical difference between the treatments both for coverage and deposit. The travel speed did not influence the application efficiency for droplet with the same droplet pattern, so it is possible to increase the effective capacity of the sprayer without decreasing the application quality.

A aplicação de biocarvão ao solo tem sido divulgada como prática com vantagens agrícolas e ambientais. Devido à sua elevada reatividade, o biocarvão pode interagir com contaminantes orgânicos e inorgânicos do solo, diminuindo o potencial poluidor de elementos tóxicos e pesticidas. Contudo, a eficácia de herbicidas pré-emergentes pode ser anulada devido à presença de biocarvão no solo, o que impõe a necessidade de doses maiores e resulta no aumento do risco de contaminação ambiental. Adicionalmente, pode haver maior persistência de pesticidas no solo devido à retenção e menor disponibilidade das moléculas em solos com biocarvão. As reações que ocorrem entre o biocarvão e os pesticidas dependem das próprias características do solo e da molécula, além do tempo de interação com o solo (aging) e das propriedades intrínsecas ao biocarvão (biomassa de origem, T°C de pirólise e granulometria). O tebuthiuron e a hexazinona são herbicidas com elevado potencial de lixiviação e podem ter seu destino alterado em função da presença de biocarvão no solo. Estas moléculas possuem elevado tempo de meia-vida (t1/2) e biodegradam lentamente no ambiente edáfico. Assim, processos oxidativos avançados (POA) podem acelerar a decomposição dos herbicidas, sendo ainda uma maneira de integrar o biocarvão em processos químicos para a dissipação de poluentes. Objetivou-se avaliar os efeitos da aplicação de biocarvão na dinâmica dos herbicidas tebuthiuron e hexazinona em solos, tendo-se como objetivos específicos: i) verificar o comportamento sortivo desses herbicidas frente à aplicação de biocarvões produzidos a partir de diferentes matérias-primas e T°C de pirólise, incluindo a influência de fatores como o aging dos herbicidas no solo, tamanho das partículas do biocarvão e disponibilidade de carbono orgânico dissolvido (COD) no solo promovida pela adição do biocarvão; ii) avaliar se a interação entre os herbicidas e o biocarvão afeta a eficiência de controle de braquiária (Brachiaria decumbens); iii) analisar a influência do biocarvão na dissipação e lixiviação de tebuthiuron e hexazinona; e iv) identificar o potencial de uso do biocarvão em POA, como suporte para catalisadores metálicos heterogêneos e como fonte de ferro para reações de Fenton, bem como avaliar o desempenho destes materiais na catálise oxidativa de hidrocarbonetos e dos herbicidas. Experimentos de sorção, (verificando a influência de biocarvões de diferentes matérias-primas e T°C de pirólise, aging e granulometria, além da avaliação em solos de texturas contrastantes), bem como de dissipação e lixiviação foram conduzidos, utilizando-se herbicidas radiomarcados. Em paralelo, a liberação de COD pelos biocarvões e pelos solos foi quantificada, enquanto que um experimento de eficiência de controle sobre braquiária em casa de vegetação foi conduzido. Os biocarvões foram, ainda, avaliados quanto ao potencial de uso como suporte para catalisadores metálicos e para reações de Fenton, avaliando-se sua performance para a oxidação dos herbicidas e de hidrocarbonetos. Apesar de não alterar a classe de lixiviação de tebuthiuron e hexazinona em curto prazo, quando considerado o efeito do aging, a presença de biocarvão de palha de cana-de-açúcar 550°C (PC550) no solo, independentemente da granulometria, pode auxiliar no manejo de herbicidas com elevada mobilidade, especialmente em solos de textura arenosa e com baixo teor de carbono. Neste caso, o herbicida tebuthiuron teve sua classificação alterada de \"molécula lixiviável\" (Kd,app < 5,0 L kg-1) para \"molécula não-lixiviável\" (Kd,app > 5,0 L kg-1). No entanto, o biocarvão de dejeto de galinha 350°C (DG350) aumenta o COD do solo, resultando na diminuição da sorção dos herbicidas. A adição dos biocarvões PC550 e DG350 ao solo não modificam a eficiência de controle de braquiária por moléculas altamente solúveis. Doses a partir das doses recomendadas em campo promovem controle eficiente, independentemente da presença ou não de biocarvão no solo. Tebuthiuron e hexazinona são moléculas recalcitrantes no ambiente, sendo muito baixas suas taxas de mineralização e de dissipação, tanto na presença como na ausência dos biocarvões PC550 e DG350. A presença de biocarvão no solo pouco influenciou a dissipação dessas moléculas. Os biocarvões PC550 e DG350 diminuem o potencial de lixiviação da hexazinona no solo de textura areia franca, mas não afetam o movimento vertical do tebuthiuron nas mesmas condições. Apesar do menor potencial para degradação de tebuthiuron e hexazinona em relação à epoxidação de hidrocarbonetos, a inserção do biocarvão para a síntese de catalisadores mostrou-se eficiente e permitiu o emprego deste material em processos de catálise industrial e ambiental, podendo auxiliar para o manejo da remediação de poluentes e contribuindo para expandir o uso do biocarvão. / Biochar amendments to soil has been claimed as a practice with agricultural and environmental advantages. Due to its high reactivity, biochar can interact with organic and inorganic soil contaminants, reducing the pollution potential of toxic elements and pesticides. However, pre-emergent herbicides efficacy can be negatively affected by biochar additions to the soil, which may impose higher doses and increase the environmental contamination risk. In addition, there may be increasing in the pesticide\'s persistence due to retention and lower availability of the molecules induced by biochar amendment to the soil. The interactions between biochar and the pesticides depend on the characteristics of the soil and the herbicide itself, besides the aging and the biochar\'s properties (biomass, pyrolysis T°C and granulometry). Tebuthiuron and hexazinone are herbicides with leaching potential and may have their fate modified due to the presence of biochar in the soil. These molecules have a high half-life time (t1/2) and biodegrade slowly in the environment. Thus, advanced oxidative processes (AOP) can accelerate the decomposition of herbicides and can be a way of incorporate biochar in chemical processes towards pollutants dissipation. We aimed to evaluate the effects of biochar amendments on tebuthiuron and hexazinone dynamics in soils, and the specific objectives were: i) to verify the sorption behavior of these herbicides in response to biochar\'s amendment from different feedstock and pyrolysis T°C, including the influence of factors such as herbicide aging on the soil, biochar particle size and availability of dissolved organic carbon (DOC) in the soil promoted by biochar addition; ii) to evaluate if the interaction between the herbicides and the biochars affects braquiária (Brachiaria decumbens) control efficiency; iii) to analyze the biochars influence on the dissipation and leaching of tebuthiuron and hexazinone; and iv) to identify the potential use of biochar in AOP as heterogeneous metal catalysts support and as a source of iron for Fenton reactions, as well as to evaluate the performance of these materials in oxidative catalysis of hydrocarbons and herbicides. Sorption experiments, (checking the influence of biochars from different feedstocks and pyrolysis T°C, aging and granulometry, as well as accessing the differences among soil textures), and dissipation and leaching experiments were conducted using radiolabeled herbicides. In parallel, the release of DOC by the biochars and soils was quantified, whereas an experiment in a greenhouse for braquiária control was conducted. The biochars were also evaluated for use as metal catalysts supports and for Fenton reactions, evaluating their performance for herbicides and hydrocarbons oxidation. Although it does not change tebuthiuron and hexazinone leaching class in short term, when considering the aging, the sugarcane straw biochar pyrolyzed at 550°C (PC550), regardless of granulometry, may be useful in the management of high mobility herbicides, especially in sandy soils with low carbon content. In this case, tebuthiuron had its classification modified from \"leachable\" (Kd,app < 5.0 L kg-1) for \"non-leachable\" molecule (Kd,app > 5.0 L kg-1). However, the biochar from poultry manure pyrolyzed at 350°C (DG350) increases the DOC content in the soil, resulting in decreased sorption of the herbicides. The additions of PC550 and DG350 to the soil does not modify the control efficiency of braquiária by highly soluble molecules. Doses higher than the recommended ones promote efficient control, regardless of the presence or absence of biochar in the soil. Tebuthiuron and hexazinone are highly recalcitrant molecules in the environment, having low rates of mineralization and dissipation both in the presence or absence of the biochars PC550 and DG350. The biochar application to the soil barely influenced the herbicides dissipation. The biochars PC550 and DG350 decrease the leaching potential of hexazinone in the sandy soil, but do not affect tebuthiuron leaching in the same conditions. Despite the lower potential for tebuthiuron and hexazinone degradation in relation to the epoxidation of hydrocarbons potential, biochar insertion in the synthesis of catalysts has been proved to be efficient, allowing the use of these wastes in industrial and environmental catalysis processes for pollutants remediation purposes and helping to expand the biochar range of uses.

There is currently no published method for the analysis of the herbicide quizalofop-p-tefuryl or its matabolite quizalofop in biological matrices. Quizalofp-p-tefuryl is a relatively new herbicide with apparent low toxicity and is readily degraded. Its metabolite also has herbicide activity. Quizalofop-p-tefuryl is a aryloxyphenoxypropionate and is a post emergence herbicide used for pulses and vegetables. This work reports on a method for the analyses of this pesticide residue and its metabolite in soybean using HPLC on a C-18 column with UV detection at 332 nm. Several methods are tried including some involving the use of solid phase extractors like silica, Florisil and strong cationic exchange cartridges. The main method developed uses an extraction solvent hexane: acetone: acetic acid for extracting the quizalofop-p-tefuryl and quizalofop from the ground soybean. The extracts are then made alkaline with NaOH and this deprotonates the quizalofop separating it from the hexane phase which contains the quizalofop-p-tefuryl. The hexane phase is extracted with ACN and quizalofop-p-tefuryl partitions into this phase. The quizalof-p-tefuryl is repartitioned into a fresh diethyl ether: hexane phase by adding a large quantity of H2O and NaCL to the ACN layer. The organic phase is washed and evaporated to dryness before being made up to volume with ACN for direct analysis by UV detection or by derivatising it to methoxychloroquinoxaline for fluorescence detection. Using the method that directly detects the analytes, for quizalofop-p-tefuryl and quizalofop at spike levels, the method has average recoveries. The precision of recoveries for both compounds is about 9%. The method is fairly robust. Time of analysis per analyte is about 2 hrs. / Master of Science

Ants are highly abundant and ubiquitous in many terrestrial ecosystems. They perform many important ecological functions and have been widely employed as bioindicators for various terrestrial monitoring programmes. In agroecosystems, their role is controversial because ants can act as predators against herbivorous pest but also associate with and protect honeydew-producing hemipteran pests. The ecology, function and interactions of ants with other arthropods in vineyards are poorly known and this thesis therefore examines their distribution and ecology in south-eastern Australian vineyards. / An extensive survey of 50 vineyards distributed in five regions in South Australia and Victoria recorded 147 native ant species and one invasive species, Linepithema humile (Mayr). Species richness, compositional similarities and assemblage structure varied within and across regions. High species turnover and variation in assemblage structure were found across regions and implications of these patterns are discussed. The invasive L. humile was only detected in some vineyards in one region. The potential impact of management practices and off-farm vegetation on augmenting ant diversity and conserving biodiversity are considered. / The impact of non-target agrochemical applications on ants was investigated in 19 vineyards that received varying levels of agrochemical input. Ant assemblage structure and assemblages were not found to be impacted by pesticides. In contrast, ant assemblage structure was influenced by the presence of shelterbelts near the sampling area. Reasons for the resilience of ants to pesticides are given and assessment at the colony level instead of worker abundance is suggested. / An ant-exclusion experiment was designed to test the impact of native ants on both canopy and ground arthropods concurrently. The potential influence of ants on predation and parasitism on eggs of light brown apple moth (LBAM), a grape pest, was also examined. Adult grapevine scale insects and earwigs under bark were also counted after a season of ant-exclusion. While ant exclusion was successful, there was no detectable difference in the abundance of most arthropod orders and feeding groups between ant-excluded and control vines, although ground spiders were more abundant under ant-excluded vines, despite increased ground ant foraging pressure. LBAM egg parasitism and predation were low and probably affected by weather and other arthropods. Ant exclusion did not reduce survival of scale insects, although the distribution and abundance of scale insects were negatively associated with earwigs. Reasons for the lack of negative effects of ants are discussed. / The spatial patterns of ants were investigated with intensive pitfall trappings in two vineyards to examine if non-random patterns occur and whether these might be the result of competitive species interactions as well as non-crop vegetation adjacent to the vineyards. Null model analyses suggested competitive species interactions within ant assemblages that might have been driven by dominant species even though both positive and negative associations between dominants were also found. Consistent spatial aggregations indicated significant spatial overlap in distributions of some species. Such overlap suggests that potential co-existence might be attributed to temporal partitioning or differences in foraging strategies. The presence of vegetation had a marked influence on ant assemblage structure and competitive interactions, and might also facilitate co-existence by increasing resource heterogeneity. The implications of these findings for sampling strategies and ecological processes within vineyards are discussed. / This thesis has provided new information about ants in vineyards. The high ant diversity could be important in maintaining ecosystem services. Among the 33 ant genera recorded, Iridomyrmex, Paratrechina and Rhytidoponera have the greatest potential in contributing to canopy pest suppression although their associations with honeydew-producing hemipterans need to be considered. Stable isotope analysis or/and molecular gut content analysis should reveal their trophic position in vineyards. Evaluation of crop yield that is directly attributed to soil conditioning by ants in agroecosystems should be explored. The importance of landscape composition, complexity and connectivity is highlighted and role of agroecosystems in conserving biodiversity is emphasised. Future research should be directed towards understanding how landscape composition and complexity may enhance ant diversity and alter dynamics and interactions that may be functionally important (biological control, soil conditioning, etc) in a landscape context.

Graduation date: 1998

Prevention of groundwater contamination by agricultural chemicals requires an understanding of the complex processes that control pesticide movement below the soil surface. Through this understanding it is possible to try to predict which areas may be most vulnerable to contamination. The many models that have been developed to characterize pesticide movement vary widely in their conceptual approach and degree of complexity. A soil properties model was developed in this thesis to determine the relative overall pesticide movement potential in Oregon agricultural soils. Its focus is ease of use in both acquisition of input values and running of the model. The model is based on soil properties important in controlling pesticide movement. It is a rating system model that uses scoring of factors and matrices to weigh the soil values. It is organized into two processes: leaching and sorption. The leaching potential is based on soil permeability and drainage class. The sorption potential is based on organic matter content and texture of the soil surface horizon(s). The interaction of these two processes results in the overall pesticide movement potential. / Graduation date: 1991

The organochlorine pesticide endosulfan has been shown to be highly toxic to fish and there is some evidence to support that it may act as an endocrine disrupting chemical. Juvenile rainbow trout (Oncorhynchus mykiss) were caged at 4 sites in Oshawa Creek during the fall and spring of 2008 and 2009 while another group was intra-peritoneal injected in the laboratory with varying concentrations (ppm) of endosulfan. Plasma vitellogenin (VTG) levels, liver ethoxyresorufin-O-deethylase (EROD), citrate synthase (CS), lactate dehydrogenase (LDH), and brain acetylcholine esterase (AChE) (caged fish only) enzymatic activities were measured. Trout injected with endosulfan experienced an increase of the anaerobic (LDH activity) and a decrease of the aerobic (CS activity) metabolic pathways, while male VTG levels increased. Since it was a singular injection, VTG results have to be confirmed. Fall caged trout showed increased EROD activity and inhibited AChE activity while those caged in the spring experienced an unexpected exposure to the lampricide 3-Trifluoro-Methyl-4-Nitro-Phenol (TFM) which disrupted metabolic parameters (inhibited CS and increased LDH activity). Both fall and spring caged trout experienced no induction of VTG activity. Further research is needed since the spring exposure was altered due to the unplanned TFM treatment and thus did not represent a valid temporal replicate.

L'exploitation des terres à des fins agricoles entraîne la présence de nombreux contaminants dans les milieux naturels, ce qui peut nuire à la faune qu'on y retrouve. Nous avons émis l'hypothèse que la présence de contaminants agricoles aurait un impact sur le métabolisme osseux du ouaouaron (Rana catesbeiana), puisque des difformités au niveau des pattes avaient auparavant été observées chez certains individus. Les grenouilles ont été capturées à l'été 2008 en six sites situés aux abords de la rivière Yamaska et choisis selon un gradient d'activité agricole. Elles ont par la suite été disséquées et leurs fémurs et phalanges ont été analysés à l'aide d'une technique d'imagerie numérique, grâce à l'appareil Skyscan 1172. Les phalanges des individus ont été analysées en histologie afin d'estimer leur âge par squelettochronologie. Une analyse sérique des principaux marqueurs du métabolisme osseux a aussi été effectuée. Nos résultats ont démontré que l'activité de la phosphatase alcaline augmentait en fonction du gradient d'exploitation agricole, supposant une atteinte hépatique. Aussi, les ouaouarons provenant du site de plus forte activité agricole présentaient un volume osseux réduit au niveau de la portion trabéculaire de la phalange, ainsi que de la portion corticale du fémur. De plus, les grenouilles capturées à ce site étaient significativement plus jeunes. Nous avons aussi voulu vérifier l'impact de certains pesticides au niveau cellulaire, en utilisant la lignée ostéoblastique murine MC3T3-E1 et la lignée ostéoblastique humaine MG-63. Il s'est avéré que l'atrazine et le métolachlore n'étaient pas cytotoxiques pour les cellules aux concentrations utilisées. Par contre, l'endosulfan, un pesticide organochloré, a été démontré cytotoxique, sa CL50 ayant été mesurée à 42,4µM. Nous avons par la suite tenté de documenter son mécanisme de toxicité par des mesures au cytofluoromètre. Nous avons pu démontrer par un marquage aux sondes PI et Annexine V que l'endosulfan induisait l'apoptose et la nécrose. De plus, le potentiel mitochondrial subit une dépolarisation forte et rapide après traitement à l'endosulfan, ce qui a été mesuré grâce à la sonde JC-1. Bien que l'apoptose soit induite par l'endosulfan et que le potentiel mitochondrial chute, nous n'avons pas été en mesure de mettre en évidence la production de ROS par marquage à la sonde H2DCFDA. Par contre, l'ajout de trois antioxydants différents, soit la vitamine C, la vitamine E et la N-acétyl-cystéine au milieu de culture a significativement réduit la mortalité, ce qui laisse présumer que la production de ROS serait à la base du mécanisme de toxicité de ce pesticide, mais que le marquage au H2DCFDA n' aurait pu le révéler. Le métabolisme osseux est souvent ignoré lors d'études toxicologiques. Ce projet ayant permis de révéler l'impact de contaminants agricoles sur le métabolisme osseux du ouaouaron ainsi que sur des cellules ostéoblastiques indique que cet aspect ne devrait pas être négligé lors de futures études. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : ostéoblaste, apoptose, endosulfan, ouaouaron, pesticides.

Ambient ionization mass spectrometry is a technique used for the analysis of samples under ordinary ambient conditions. It has many advantages, such as fast sample exchange, low operation time and few sample preparation which comparing with thus ion source operating in vacuum. Therefore, several different ambient ionization sources have been developed in the past decade. Direct Electrospray Probe ionization mass spectrometry (DEP-MS) was developed by Shiea, J in 1999, which providing an effective means of analyzing not only large biomolecules, but also small organic and inorganic compounds. It can rapidly generate electrospray from a droplet which was deposited on a probe. The DEP technique provides a number of unique analytical features containing: (a) low sample consumption and sample switching is immediate; (b) the capillary and pump are unnecessary; and (c) the probe is low-cost and easy to construct and clean, and is free to maintenance. The first part of experiment in this research is based on the ideal of DEP. The leaf tissues were cut into a triangular shape, 15 mm long and 8 mm wide at the base, is held by a crocodile clip with the apex facing the inlet of the mass spectrometer and at a distance of 2 cm or more from it. Electrospray solutions are added onto the tissue to mix with the leaf sap, and a high voltage (4.5-5.5 kV) is applied to the leaf tissue through the crocodile clip, and generate ions for MS analysis. This method has been demonstrated to be applicable for the analysis of a wide variety of plant sample, such as the leaves tissue in different color, different growth, diseased and pesticide residue. The second part of experiment is improved from the first research. Electrospray was produced via a metal probe which binding two fine stainless steel needle (0.27 mm diameter) together. This probe plays the role of sampling and ionization. An amount of liquid sample was loaded onto the probe when the tip of probe touched the plant tissue, then electropray solution are introduced by syringe pump into the probe and applied high voltage on the probe to produce electrospray ionization. Therefore, direct rapid analysis was achieved using this probe interfaced and this method can direct profile of phytochemicals in a section of plant tissue in different regions, including root, stem, leaf, outer and inner part of fruit. In addition, using this probe, solid samples are directed sampling equally. The solid materials can be observed on the tip of probe by scanning electron microscope (SEM). It can obtain reasonable strong ion signals rapidly for agrochemicals deposited on the surface of vegetables or fruits peel.