Orientador: Luiz Lonardoni Foloni / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agricola / Made available in DSpace on 2018-08-05T18:46:07Z (GMT). No. of bitstreams: 1 Silva_CelsoLuizda_M.pdf: 2466251 bytes, checksum: ec6d5d80bece33b33227f9238012b5f8 (MD5) Previous issue date: 2004 / Resumo: A utilização de pesticidas na agricultura é uma prática necessária no controle de pragas, doenças ou de plantas daninhas para se atingir altos índices de produtividade e conseguir desta forma atender a demanda crescente de alimentos. Alguns destes pesticidas aplicados podem apresentar propriedades físico-químicas perigosas, seja ao ambiente e aos próprios seres vivos, podendo causar danos ambientais e problemas de saúde ao homem. Muitas vezes isto ocorre devido à falta de estudos sobre o comportamento e destino destes produtos no ambiente e estudos toxicológicos. Uma ferramenta importante para procurar evitar estes tipos de danos são os modelos matemáticos que permitem antecipar para o qual ou quais compartimentos esta molécula tende a caminhar e também, auxiliar no desenvolvimento de pesquisa no campo, diminuindo os gastos e esforços. O objetivo deste projeto foi utilizar um modelo matemático de fugacidade (nível) I na análise de risco do comportamento, como auxílio na avaliação preliminar da distribuição ambiental, dos principais pesticidas registrados junto ao Ministério da Agricultura, usados e aplicados de acordo com as recomendações de seus fabricantes, nos sistemas de produção convencional e plantio direto, nas principais culturas brasileiras: algodão, arroz, café, cana-de-açúcar, citros, milho e soja. A metodologia utilizada foi baseada nas fórmulas matemáticas descritas por Mackay (1991). Como resultados, foram selecionados os 10 produtos que mais se distribuíram nos compartimentos ambientais (ar, água, solo, sedimento, biota, folhas das plantas, caule e raiz) aqui apresentados em ordem decrescente de preferência. Estes pesticidas foram para o compartimento ar: acetochlor> disulfuton> acephate> thiodicarb> quinclorac> thiram> tolifluanid> pendimenthalin> trifluralin> endosulfan; para a água: nicosulfuron> metsulfuron methyl> monocrotofós> bispyribac sodium> metamidofós> thiamethoxam> halosuluron methyl> chlorimuron etílico> imazapic> imidacloprid; para o solo: diquat> paraquat> hexythiazox> parathion metil> benomyl> tiofanato metílico> msma> iprodione> epoxiconazole> propargite; para o sedimento: diquat> paraquat> hexythiazox> parathion metil> benomyl> tiofanato metílico> msma> iprodione> epoxiconazole> propargite; para a biota: propanil> acetochlor> disulfoton> pendimenthalin> bifenthrin> carboxin> endosulfan> clorpirifós> tolyfluanid> thiram; para a folha: aldicarb> fluazifop-p-butil> metconazole> diflubenzuron> tolyfluanid> disulfuton> fludioxonil> difenoconazole> acetochlor> tebuconazole; para a raiz e caule: lambdacyhalothrin> zetacypermethrin> cypermethrin> alfacipermetrina> bifenthrin> acrinathrin> permethrin> lactofen> betacyflutrin> chlorfluazuron. Os pesticidas estudados também foram comparados pelo critério de GUS (índice de vulnerabilidade de águas subterrâneas). Os produtos que apresentaram potencial de lixiviação em ordem alfabética foram: acetochlor, aldicarb, atrazina, bispyribac-sodium, carbendazim, carbofuran, clorimuron, etílico, cyproconazole, difenoconazole, fipronil, flumioxazin, fomezafen, hexazinone, imazapic, imazaquim, imazetapir, metalacloro, metomyl, metribuzin, metsulfuron-methyl, monocrotofós, nicosulfuron, quinclorac, simazine, tebuthiuron, thiamethoxam e triclorfon. As conclusões deste trabalho permitiram verificar que o compartimento ambiental que apresentou maior vulnerabilidade na preferência da distribuição dos pesticidas foi o compartimento água. A avaliação preliminar do risco de contaminação por pesticidas de uma área agrícola pode ser feita a partir das características físico-químicas dos pesticidas utilizando o modelo de fugacidade Mackay nível I (1991). Este modelo pela simplicidade e rapidez nas respostas mostra ser uma excelente ferramenta, como fator de decisão na utilização do pesticida. O critério de GUS também se apresentou como mais um mecanismo para ser utilizado quando não se dispõe de todas as informações, como tomada de decisão na escolha da utilização de um pesticida visando monitorar ou até mesmo impedir a contaminação de águas subterrâneas / Abstract: The utilization of pesticides in agriculture is a necessary practice to control pests, diseases or weeds to reach an excellent index of productivity and get attend the increasing necessity of food. Some of this pesticides applied, show dangerous physical-chemical proprieties to the environmental and health human. Many times it happen because we haven¿t enough studies of the toxicity and behavior or destination of pesticides in the environmental. One of important tool to try avoid this type of damage are the mathematics models, which permit anticipated for which behavior of this molecule tend walk and also help in the development of field research reduce expense and effort. The goal of this project was use a mathematics calculus based on mathematics models of fugacity level 1, which help in the analysis of risk the main environmental behavior of all pesticides, registered in the Ministry of Agriculture, used and applied according to the recommendation of manufactures pesticides industry (WIN FIT; 2000), at the system of conventional production, and no till system of cotton, rice, coffee, sugar-cane, citrus, corn and soybean cultivation. The utilized methodology was mathematics formula describe by Mackay (1991) to figure out of fugacity (¿, Pa), capacity of fugacity (Z, mol m-3 Pa-1) , concentration (C, g mol-1) in the compartment air, water, soil, sediment, biota, leaves, root, stem of plant. It was used the physical-chemical parameters to each pesticides applied to each culture studied (cotton, rice, sugar-cane, coffee, citrus, corn and soybean) with data of each compartment: volume (m³), fraction organic (%) and density (?, g m-3) got from the Mackay (1991). As the results of mathematics calculus it were chose the 10 products which were more distributed in the compartment environmental present such as following the preference, where from the air compartment: acetochlor> disulfuton> acephate> thiodicarb> quinclorac> thiram> tolifluanid> pendimenthalin> trifluralin> endosulfan; from the water compartment: nicosulfuron> metsulfuron-methyl> monocrotofos> bispyribac-sodium> metamidofos> thiamethoxam> halosuluron methyl> chlorimuron etílico> imazapic> imidacloprid; from the soil compartment: diquat> paraquat> hexythiazox> parathion metil> benomyl> tiofanato metílico>msma>iprodione> epoxiconazole> propargite; from the sediment compartment: diquat> paraquat> hexythiazox> parathion metil> benomyl> tiofanato metílico> msma> iprodione> epoxiconazole> propargite; from the biota compartment: propanil> acetochlor> disulfoton> pendimenthalin> bifenthrin> carboxin> endosulfan> clorpirifós> tolyfluanid> thiram; from the leave compartment: aldicarb> fluazifop-p-butil> metconazole> diflubenzuron> tolyfluanid> disulfuton> fludioxonil> difenoconazole> acetochlor> tebuconazole; from the trunk and root compartments: lambdacyhalothrin> zetacypermethrin> cypermethrin> alfacipermetrina> bifentrhin> acrinathrin> permethrin> lactofen> betacyflutrin> chlorfluazuron. The pesticides studied too were also by the GUS (Groundwater Ubiquity Score) where the index is calculated through the half-life value of the compose on the soil and coefficient of adsorption and organic tissue of the soil. The products that showed lixiviation potential by GUS alphabetical order were: acetochlor, aldicarb, atrazina, bispyribac sodium, carbendazim, carbofuran, clorimuron, etilico, cyproconazole, difenoconazole, fipronil, flumioxazin, fomezafen, hexazinone, imazapic, imazaquim, imazetapir, metalacloro, metomyl, metribuzin, metsulfuron-methyl, monocrotofos, nicosulfuron, quinclorac, simazine, tebuthiuron, thiamethoxam and triclorfon. In conclusion, the environmental compartment showed more vulnerability in the preference of pesticide distribution in the compartment water. The preliminary evaluation of risk contamination in agriculture area by pesticides can be made based on physical-chemical pesticide characteristic used in the fugacity model Mackay level 1 (1991). This fugacity model Mackay level 1 (1991) is an excellent tool to be used as a factor of decision in the pesticides use. The GUS criteria showed itself as one more mechanism to be used dire the lack of information, as decision make skill in choice of a pesticide utilization aiming monitoring or even though avoiding groundwater contamination / Mestrado / Agua e Solo / Mestre em Engenharia Agrícola

The Trinity River passes through the Dallas-Fort Worth metroplex receiving point and non-point source contaminant loadings. Lepomis spp. were collected at twelve sampling locations in the Trinity River in August 1987 and September 1988 and analyzed for organochlorine pesticides and heavy metals. Results from the study were compared to existing U.S. FDA action and tolerance levels, LC50s, and historical data. Various longitudinal trends and some concentration patterns were observed. Continual study of pesticide and metal body burdens in fish allow testing for trends, and thereby, lead to a better understanding of the distribution of contaminants in the Trinity River.

The City of Denton Pecan Creek Wastewater Treatment Facility has periodically failed effluent toxicity testing. A Toxicity Identification Evaluation has determined that Diazinon in the effluent is contributing to the observed toxicity. Chlorpyrifos is also implicated as a factor. The City of Denton constructed a half acre experimental wetland to remove Diazinon related toxicity. Results from spiking and microcosm experiments indicate that the wetland can reduce the Diazinon.

M. Tech. (Biotechnology) Vaal University of Technology / One of the major problems encountered in qualitative and quantitative determination of residual pesticides by gas chromatography is the matrix effects. Matrix components have a considerable effect on the way analysis is conducted and the quality of results obtained, introducing problems such as inaccurate quantification, low analyte delectability and reporting of false positive or even false negative results. It was aimed to develop and validate a suitable method for counteracting the matrix effects so as to improve the detection and quantification of selected organochlorine pesticide residues from real water samples. The real water samples used were sampled from three points along the Jukskei River catchment area in Gauteng, South Africa for a period of 7 months from January to July 201 0 so as to create a representative sample. An automated solid phase extraction (SPE) method coupled to Gas ChromatographyMass Spectrometry (GC-MS) method for the analysis of 20 selected organochlorine pesticides was developed and validated for the purposes of studying the matrix effects. The analytical method showed a significant degree of validity when tested against parameters such as linearity, repeatability and sensitivity. Endosulphan beta, 4,4' Dichlorodiphenyldichloroethane, and Heptachlor-epoxide had the broadest linear calibration ranges of 1 ppm- 0.0156 ppm. Benzene hexachloride (BHC) delta and Lindane had the lowest statistical limits of detection of 0.018 ppm. Statistical hypothesis testing indicated that there was significant linearity in all selected organochlorine calibration curves. Four different reversed sorbent phases, including LC18, SC18- E and Strata-X (styrene divinyl benzene) were tested for organochlorine retention efficiency. The LC-18 200 mg cartridge proved to be the most robust and effective sorbent phase as it produced better recoveries varying from 90-130% for most analytes. A breakthrough volume of 100 ml for the LC-18 200 mg cartridge was determined using an optimum matrix load curve. It was then concluded that the method developed was suitable for further research towards the influence of the matrix on selective determination of the selected organochlorine pesticides. Four different calibration methods, namely matrix-free external standard, matrixmatched external standard, matrix-free internal standard and matrix-matched internal standard were applied to test the efficiency of computing recoveries. All calibration curves for the 20 organochlorine pesticides showed significant linearity > 0.99 when plotted on both Chemstation and Excel. The calibration methods were tested on three different matrices composed of a high sample matrix (synthetic matrix), a low sample matrix (real sample matrix) and a no sample matrix (ultrapure water). Statistical hypothesis testing led to the decision that there are significant differences between the mean recoveries of the three water sample matrices and also that the differences in the mean recoveries of the three sample matrices are independent of the both the two calibration techniques (internal standard and external standard) and calibration types (matrix-matched and matrix-free) applied. This led to the overall conclusion that the matrix effects have an overwhelming influence on the selective determination of the selected organochlorine pesticides.