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1
Soares, V. M. "Studies on the residue chemistry of some organophosphorus pesticides." Thesis, London Metropolitan University, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.377904.
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Zamariola, Nathalie [UNESP]. "Resíduos de pesticidas em tecido adiposo associado a órgãos reprodutivos: validação de método analítico e aplicação a animais de experimentação." Universidade Estadual Paulista (UNESP), 2011. http://hdl.handle.net/11449/97813.
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Os pesticidas, quando utilizados de forma adequada, protegem as culturas agrícolas contra danos excessivos causados por pragas e doenças. No entanto, segundo a ANVISA, aproximadamente 29% dos alimentos hortifrutícolas consumidos pela população brasileira apresenta alguma irregularidade quanto aos níveis de resíduos de pesticidas, indicando um uso abusivo e indiscriminado. Tendo em vista a preocupação com a saúde humana, foi proposto um estudo com animais de experimentação (ratos Lewis, Wistar e Sprague-Dawley) para avaliar os efeitos da exposição a misturas de pesticidas em baixas doses, simulando o que ocorre com humanos. Para isso foram escolhidos os pesticidas dicofol, dieldrin, endossulfam e permetrina, que foram encontrados em amostras de alimentos de origem vegetal, coletadas em diversas regiões do país pelo Programa de Análise de Resíduos de Agrotóxicos em Alimentos (PARA) da ANVISA. Dentre os efeitos estudados está a alteração endócrina em fêmeas, que pode afetar o sistema reprodutivo, e como estas moléculas apresentam bioacumulação, o tecido alvo é o adiposo. Considerando-se as baixas concentrações previstas para os analitos, a complexidade da matriz (45% de lipídios) e a pequena massa de amostra disponível (cerca de 2 g por animal), houve a necessidade de desenvolver um método que apresentasse confiabilidade para aplicação a este estudo. O método desenvolvido para extração dos analitos é uma modificação do método QuEChERS. O método consiste basicamente de extração com acetonitrila e posterior extração em fase sólida dispersiva (d-SPE) com PSA e C18. Na avaliação da confiabilidade analítica do método foram incluídos os seguintes parâmetros: seletividade, linearidade, sensibilidade limite de detecção, limite de quantificação, exatidão, precisão e efeito matriz. Todas as amostras...
Os pesticidas, quando utilizados de forma adequada, protegem as culturas agrícolas contra danos excessivos causados por pragas e doenças. No entanto, segundo a ANVISA, aproximadamente 29% dos alimentos hortifrutícolas consumidos pela população brasileira apresenta alguma irregularidade quanto aos níveis de resíduos de pesticidas, indicando um uso abusivo e indiscriminado. Tendo em vista a preocupação com a saúde humana, foi proposto um estudo com animais de experimentação (ratos Lewis, Wistar e Sprague-Dawley) para avaliar os efeitos da exposição a misturas de pesticidas em baixas doses, simulando o que ocorre com humanos. Para isso foram escolhidos os pesticidas dicofol, dieldrin, endossulfam e permetrina, que foram encontrados em amostras de alimentos de origem vegetal, coletadas em diversas regiões do país pelo Programa de Análise de Resíduos de Agrotóxicos em Alimentos (PARA) da ANVISA. Dentre os efeitos estudados está a alteração endócrina em fêmeas, que pode afetar o sistema reprodutivo, e como estas moléculas apresentam bioacumulação, o tecido alvo é o adiposo. Considerando-se as baixas concentrações previstas para os analitos, a complexidade da matriz (45% de lipídios) e a pequena massa de amostra disponível (cerca de 2 g por animal), houve a necessidade de desenvolver um método que apresentasse confiabilidade para aplicação a este estudo. O método desenvolvido para extração dos analitos é uma modificação do método QuEChERS. O método consiste basicamente de extração com acetonitrila e posterior extração em fase sólida dispersiva (d-SPE) com PSA e C18. Na avaliação da confiabilidade analítica do método foram incluídos os seguintes parâmetros: seletividade, linearidade, sensibilidade limite de detecção, limite de quantificação, exatidão, precisão e efeito matriz. Todas as amostras... (Complete abstract click electronic access below)
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Gamboa, Nadia. "DDT, a historical review." Revista de Química, 2014. http://repositorio.pucp.edu.pe/index/handle/123456789/100129.
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El DDT está íntimamente vinculado al siglo XX. Su producción, uso y comercialización están prohibidos por ser un contaminante organoclorado persistente controlado por el Convenio de Estocolmo.DDT is closely linked to the twentieth century. Its production, use and marketing are now banned because it is a persistent organochlorine pollutant controlled by the Stockholm Convention.
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Carbo, Leandro [UNESP]. "Ação mitigadora de faixa de contenção em lavouras de algodão sobre a contaminação de recursos hídricos superficiais por resíduos de pesticidas." Universidade Estadual Paulista (UNESP), 2009. http://hdl.handle.net/11449/105703.
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A contaminação de corpos d'água por pesticidas pode representar uma ameaça significativa para os ecossistemas aquáticos e recursos de água potável. Além das perdas de água e solo, os pesticidas merecem destaque, uma vez que são aplicados na agricultura para atender às necessidades de controlar as populações de pragas e doenças que atacam culturas de interesse agronômico. Quando aplicados, estes compostos podem rapidamente adsorver-se às partículas do solo, e dentre outros fenômenos de transportes, contaminarem os recursos hídricos superficiais por escoamento superficial. Neste sentido, boas práticas de conservação agrícola têm sido recomendadas para reduzir os riscos de contaminação ambiental, dentre elas, tem sido descrito na literatura o uso de faixas de vegetação próximas às margens de rios e córregos de maneira a diminuir a velocidade do escoamento e, conseqüentemente, o transporte de pesticidas para o ambiente aquático. Desta forma, neste trabalho foi avaliada a ação mitigadora de uma faixa de vegetação em lavouras de algodão sobre a contaminação de recursos hídricos superficiais por resíduos de pesticidas. O estudo do efeito da faixa de contenção foi desenvolvido em uma propriedade cotonícola às margens do Córrego Chico Nunes, região de Primavera do Leste, Mato Grosso. Foram delimitadas duas parcelas experimentais numa vertente, sendo uma de 10 metros do capim Brachiaria decumbes, como faixa de contenção. No final de cada parcela, foram instalados coletores de escoamento superficial (água e sedimento), que eram transportados para caixas menores, no qual foi determinada a quantidade de água e solo perdidos, e coletadas três amostras representativas para análise dos resíduos de pesticidas aplicados na lavoura de algodão (metomil, carbofurano, diurom, malationa, metolacloro e endosulfam total)...
The contamination of water bodies by pesticides can pose a significant threat to aquatic ecosystems and drinking water resources. In addition to the loss of water and soil, pesticides are worth mentioning, since they are applied to control the population of pests and diseases in cropping areas. When applied, pesticides can rapidly be adsorbed to soil particles or contaminate surface water by runoff processes. In this way, good agricultural conservation practices have been recommended to reduce the risk of environmental contamination, as for example, the use of vegetative filter strip near to the banks of the rivers and streams in order to reduce the water flow and the transport of pesticides to the aquatic environment. Thus, this study evaluated the mitigation action of a vegetation filter strip in cotton crops on the contamination of surface water resources by pesticides. The buffer zone study was developed in a private property near of Chico Nunes Creek banks, region of Primavera do Leste, Mato Grosso. We delimited two plots (40 m long x 10 m wide) on a slope, one comprising of 10 meters of Brachiaria decumbes as a vegetative filter strip. At the end of each plot, runoff collectors (water and sediment) were installed, that were transported to smaller boxes where the amount of water and soil losses were determined. Three representative samples were collected for the analysis of residues of pesticides used in farming cotton (methomyl, carbofuran, diuron, malathion, metolachlor and total endosulfan). The study of the buffer zone efficiency was performed in two periods, 2005/2006 and 2006/2007 season, to check the behavior between application and detection of pesticides in the plots. Water samples and sediment were collected when natural rainfall events occurred in sufficient quantity to cause runoff. The sampling in 2005/2006 period was made between... (Complete abstract click electronic access below)
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Zamariola, Nathalie. "Resíduos de pesticidas em tecido adiposo associado a órgãos reprodutivos : validação de método analítico e aplicação a animais de experimentação /." Araraquara : [s.n.], 2011. http://hdl.handle.net/11449/97813.
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Orientador: Mary Rosa Rodrigues de MarchiBanca: Silvia Helena Govoni Brondi
Banca: Maria Eliana Lopes Ribeiro de Queiroz
Resumo: Os pesticidas, quando utilizados de forma adequada, protegem as culturas agrícolas contra danos excessivos causados por pragas e doenças. No entanto, segundo a ANVISA, aproximadamente 29% dos alimentos hortifrutícolas consumidos pela população brasileira apresenta alguma irregularidade quanto aos níveis de resíduos de pesticidas, indicando um uso abusivo e indiscriminado. Tendo em vista a preocupação com a saúde humana, foi proposto um estudo com animais de experimentação (ratos Lewis, Wistar e Sprague-Dawley) para avaliar os efeitos da exposição a misturas de pesticidas em baixas doses, simulando o que ocorre com humanos. Para isso foram escolhidos os pesticidas dicofol, dieldrin, endossulfam e permetrina, que foram encontrados em amostras de alimentos de origem vegetal, coletadas em diversas regiões do país pelo Programa de Análise de Resíduos de Agrotóxicos em Alimentos (PARA) da ANVISA. Dentre os efeitos estudados está a alteração endócrina em fêmeas, que pode afetar o sistema reprodutivo, e como estas moléculas apresentam bioacumulação, o tecido alvo é o adiposo. Considerando-se as baixas concentrações previstas para os analitos, a complexidade da matriz (45% de lipídios) e a pequena massa de amostra disponível (cerca de 2 g por animal), houve a necessidade de desenvolver um método que apresentasse confiabilidade para aplicação a este estudo. O método desenvolvido para extração dos analitos é uma modificação do método QuEChERS. O método consiste basicamente de extração com acetonitrila e posterior extração em fase sólida dispersiva (d-SPE) com PSA e C18. Na avaliação da confiabilidade analítica do método foram incluídos os seguintes parâmetros: seletividade, linearidade, sensibilidade limite de detecção, limite de quantificação, exatidão, precisão e efeito matriz. Todas as amostras... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: Os pesticidas, quando utilizados de forma adequada, protegem as culturas agrícolas contra danos excessivos causados por pragas e doenças. No entanto, segundo a ANVISA, aproximadamente 29% dos alimentos hortifrutícolas consumidos pela população brasileira apresenta alguma irregularidade quanto aos níveis de resíduos de pesticidas, indicando um uso abusivo e indiscriminado. Tendo em vista a preocupação com a saúde humana, foi proposto um estudo com animais de experimentação (ratos Lewis, Wistar e Sprague-Dawley) para avaliar os efeitos da exposição a misturas de pesticidas em baixas doses, simulando o que ocorre com humanos. Para isso foram escolhidos os pesticidas dicofol, dieldrin, endossulfam e permetrina, que foram encontrados em amostras de alimentos de origem vegetal, coletadas em diversas regiões do país pelo Programa de Análise de Resíduos de Agrotóxicos em Alimentos (PARA) da ANVISA. Dentre os efeitos estudados está a alteração endócrina em fêmeas, que pode afetar o sistema reprodutivo, e como estas moléculas apresentam bioacumulação, o tecido alvo é o adiposo. Considerando-se as baixas concentrações previstas para os analitos, a complexidade da matriz (45% de lipídios) e a pequena massa de amostra disponível (cerca de 2 g por animal), houve a necessidade de desenvolver um método que apresentasse confiabilidade para aplicação a este estudo. O método desenvolvido para extração dos analitos é uma modificação do método QuEChERS. O método consiste basicamente de extração com acetonitrila e posterior extração em fase sólida dispersiva (d-SPE) com PSA e C18. Na avaliação da confiabilidade analítica do método foram incluídos os seguintes parâmetros: seletividade, linearidade, sensibilidade limite de detecção, limite de quantificação, exatidão, precisão e efeito matriz. Todas as amostras... (Complete abstract click electronic access below)
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Gulamussen, Noor Jehan. "Electrospun sorbents for solid phase extraction (SPE) and colorimetric detection of pesticides." Thesis, Rhodes University, 2014. http://hdl.handle.net/10962/d1013241.
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The thesis presents the evaluation of polysulfone sorbents for solid phase extraction (SPE) and the development of colorimetric probes for pesticides analysis in water. Through electrospraying and electrospinning techniques, different morphologies of sorbents (particles, beaded fibers and bead-free fibers) were fabricated. The sorbents were morphologically characterized by scanning electron microscopy. Adsorption capacities of sorbents were evaluated by conducting recoveries studies for model pesticides; atrazine, chlorpyrifos and DDT using batch and column SPE modes. Better recovery results were achieved by employing the batch mode of fibers, as values ranged from 98 to 105percent. Further sorbent evaluation was conducted using breakthrough experiments and static experiments. The breakthrough studies indicated that 1700 μL was the sample volume that could be percolated with no breakthrough of the analyte that correspond to a concentration of 150 mg/g of sorbent that can be extracted without any loss of analyte. From static studies, quantities of each model compound adsorbed into the fiber at the equilibrium time were evaluated. The adsorbed atrazine was 65, chlorpyrifos 250 and DDT 400 mg/g of sorbent. Kinetic studies suggested retention mechanism following pseudo first and second order model observed by high correlation coefficients (> 0. 96), demonstrating the fiber affinity to retain both polar and non-polar compounds opening a possibility to be used as sorbent for sample preparation of different classes of pesticides in water. For the second part of the study simple strategies for colorimetric sensing based on silver nanoparticles and polivinylpyrrolidone capped nanoparticles were developed, respectively for atrazine and chlorpyrifos detection. The limits of detection of the methods were 3.32 and 0.88 mg/L for atrazine and chlorpyrifos respectively. The applicability of the probe in real samples was demonstrated by the recoveries studies of tap water varying from 94 to 104 percent. The versatility of the probe was demonstrated by affording a simple, rapid and selective detection of atrazine and chlorpyrifos in the presence of other pesticides by direct analysis without employing any sample handling steps. Attempt to incorporate the probes in a solid support was achieved by using nylon 6 as solid support polymer proving to be fast and useful for on-site detection.
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Wilkins, John Patrick Gordon. "The analysis of pesticides & related compounds using mass spectrometry." Thesis, Cardiff University, 2015. http://orca.cf.ac.uk/83140/.
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The determination of pesticides and related materials in food and environmental samples is important and presents an enduring challenge to analytical chemists. For practicality it is important that as many pesticides as possible are compared using a common technique. Mass spectrometry is the method of choice for multi-residue detection techniques, because of its sensitivity and specificity. This thesis comprises a detailed analysis and critical review of the mass spectrometric behaviour of over 600 commonly encountered pesticides and related compounds. The work described in this thesis was undertaken in two tranches, one old and one new. The former experimental work was performed during the author’s employment at the Ministry of Agriculture, Fisheries & Food (Harpenden, Hertfordshire, UK) and at Unilever Research (Colworth House, Sharnbrook, Bedfordshire, UK). The data helped underpin the analytical work of the UK national pesticide residues monitoring surveillance team and the pesticide formulations safety team. Qualitative and quantitative aspects were both important, e.g. for identification and characterisation of active ingredients, contaminants and degradation products in technical pesticide formulations, as well as unambiguous detection and/or confirmation of residue levels in UK fruit and vegetables. The latter experimental work was undertaken recently (2015) at the Cardiff School of Chemistry during the preparation of this thesis. The newly acquired data helped confirm the validity and robustness of the original data, and helped to better understand them. Understanding the complex and sometimes unexpected behaviour of molecules during their extraction/analysis is essential, especially when performing trace analysis at the parts per billion level. Rationalisation of the mass spectrometric fragmentation pathways of these compounds was undertaken in order to better understand the fundamental processes taking place in the mass spectrometer. This improved understanding was essential in order to ensure the quality and validity of the data generated using these techniques. For comparison, some additional data are included, e.g. for chemical warfare agents, using literature data. Mass spectrometry was chosen because of its power as an analytical technique. General approaches and specific precautions which should be taken when using mass spectrometry for pesticide analysis are discussed and explained in this document and literature data were critically reviewed. It is hoped that these data and recommendations will find continued and future use as an adjunct to the plethora of literature data and MS instrument manufacturer databases.
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Kuklenyik, Peter. "Detection and Quantification of Organophosphate Pesticides in Human Serum." Digital Archive @ GSU, 2009. http://digitalarchive.gsu.edu/chemistry_diss/45.
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The United States Environmental Agency permits the use of 39 organophosphate pesticides. Many of these pesticides are acutely toxic and have lasting effect on human health. Organophosphates quickly metabolize in the body, therefore currently human exposure is studied by measuring the metabolic products in urine. In this work a suite of analytical methods was developed to determine the presence of un-metabolized organophosphate pesticides in human serum. First mass spectroscopic detection methods were evaluated. Gas chromatograph coupled tandem mass spectrometer was used to compare the detection limits using chemical and electron impact ionization. Positive chemical ionization was selected, because it provided better detection limits for this set of analytes. Liquid chromatograph coupled tandem mass spectrometry was also evaluated and was found advantageous over the gas chromatographic method for approximately 50% of the compounds. Positive atmospheric pressure chemical ionization was chosen for this group of compounds. Once the analytes were separated by detection methods, analytical separation methods were compared: column and eluent was selected for liquid chromatography, column alone was selected for gas chromatography. Last step of the method development was to produce a suitable sample cleanup process. Solid phase extraction was not suitable because the very wide range of solubility characteristics and hydrolytic stability of the analytes. Lyophilization, liquid-liquid extraction methods were tested and compared. A multi step cleanup method was produced, which starts with liquid-liquid extraction using high pressure ethyl acetate in accelerated solvent extractor, solvent exchange and a lipid removal step. The concentrated extract then injected in a HPLC-MS-MS system then the same extract either directly injected in GC-MS-MS or further purified using headspace solid phase micro extraction before the GC-NS-MS step. The method was used with good results for analyzing samples collected from farm workers using OP pesticides.
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Amato, Sam J. "Enantiomeric Ratios as Tracers of Soil-Air Exchange for Organochlorine Pesticides." Youngstown State University / OhioLINK, 1999. http://rave.ohiolink.edu/etdc/view?acc_num=ysu999015207.
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Grittini, Carina. "Rapid reductive dechlorination of environmentally hazardous aromatic compounds and pesticides." Diss., The University of Arizona, 1997. http://hdl.handle.net/10150/282335.
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Organochlorine compounds, such as polychlorinated biphenyls (PCBs), pentachlorophenol (PCP), p,p'-DDE and Toxaphene, have been widely used in industry and agriculture for more than fifty years. Although they have served their purpose very effectively and at low cost, many of these compounds have been banned in the United States due to their persistence in the environment and their threat to human health. Their natural resistance to degradation has made organochlorine compounds the target of many studies that have been designed to convert them into less toxic compounds. At present there is not a single, simple method than can completely dechlorinate PCBs, PCP, p,p'-DDE and Toxaphene. The work presented here reports the use of a novel bimetallic system, palladized iron (Pd/Fe), to effect the complete dechlorination of these compounds, at ambient temperature and pressure, in a matter of minutes. The dechlorination reaction occurs on the surface of the palladized iron, with removal of all the chlorine atoms from the chlorinated compound and yields the completely dechlorinated molecule and chloride ions as reaction products. The chlorinated compound is reductively dechlorinated while the iron particles are oxidized to Fe²⁺ Water is also reduced in the presence of iron, generating hydrogen, which is collected in the palladium lattice. The palladium is therefore necessary to store hydrogen gas; the "Pd·H₂" acts as a powerful reducing agent and is primarily responsible for the rapid and complete dechlorination of the organochlorine compounds. The Pd/Fe bimetallic system is potentially useful for the large scale remediation of groundwater or soil contaminated with organochlorine compounds. Palladized iron is relatively inexpensive and easy to prepare, and it rapidly and completely dechlorinates organochlorine compounds. For these reasons, the Pd/Fe system should be investigated further for applications in the field.
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Maurel, Vaughan Jean. "Beneficiation of selected pesticides and an antihyperlipidemic agent via cyclodextrin complexation and co-crystallization." Doctoral thesis, University of Cape Town, 2016. http://hdl.handle.net/11427/22911.
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The applications of many bioactive molecules are limited by their undesirable physicochemical properties, such as poor aqueous solubility and low thermal stability. The agrochemicals methyl- 2,5-dichlorobenzoate (fungicide, DCB) and fenthion (insecticide), as well as the medicinal compound acipimox (lipid-lowering agent) were selected for study in this context. The cyclodextrin (CD) complexes γ-CD/DCB, 2,6-dimethylated-β-CD/DCB, β-CD/fenthion, permethylated α-CD/fenthion and permethylated β-CD/fenthion, were synthesised. 1H-NMR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and hot stage microscopy (HSM) were used to assess their stoichiometries and thermal behaviours. The complexes 2,6-dimethylated-β-CD/DCB, permethylated α-CD/fenthion and permethylated β-CD/fenthion have 1:1 host-guest stoichiometries, while those for γ-CD/DCB and β-CD/fenthion are 3:4 and 2:1 respectively. Single crystal X-ray structures were elucidated to investigate the modes of DCB inclusion and crystal packing. All of the solid complexes displayed higher thermal stabilities than those of the untreated pesticides. Furthermore, the volatility of the insecticide fenthion (a liquid at 25 ᵒC) was significantly reduced by its transformation to a solid on CDcomplex formation. The solution-state behaviour of fenthion was qualitatively evaluated using UV-visible spectrophotometry and induced circular dichroism. Phase solubility profiles at 25 ᵒC were of type Bs for solubilisation of DCB by β-CD and (2-hydroxypropyl)-β-CD, and for solubilisation of fenthion by β-CD, the respective 1:1 association constants being 737 ± 108 M⁻¹, 412 ± 53 M⁻¹ and 789 ± 170 M⁻¹. For solubilisation of fenthion by (2-hydroxypropyl)-β-CD and randomlymethylated β-CD, AN- and AP-type behaviours were recorded respectively, with association constants 1863 ± 26 M⁻¹ and 3582 ± 106 M⁻¹ respectively. Eight multi-component crystalline systems (co-crystals and salts) of acipimox were isolated via its reaction with co-formers 4-aminobenzamide, 4-aminopyridine, benzamide, isonicotinamide, tranexamic acid and urea. NMR spectroscopy revealed 1:1 stoichiometries for all products. Their designation as salts or co-crystals was based on unequivocal evidence gleaned from single crystal X-ray structural studies, these assignments being confirmed by infrared spectroscopy. The melting points and decomposition temperatures of the products containing the coformers 4- aminobenzamide, 4-aminopyridine, isonicotinamide and tranexamic acid were significantly higher than those of untreated acipimox. Equilibrium aqueous solubilities of the multicomponent systems ranged from 0.31 to 2.77 times those of untreated acipimox.
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Weldegergis, Berhane Tekle. "Analysis of organochloro-pesticides in Eritrean water and sediment samples." Thesis, Stellenbosch : Stellenbosch University, 2004. http://hdl.handle.net/10019.1/49830.
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Thesis (MSc)--Stellenbosch University, 2004.ENGLISH ABSTRACT: The choice of the sample preparation technique used in combination with a chromatographic technique in environmental analysis strongly influences the performance of the method as a whole. The main aim of this work was to evaluate methods like: micro liquid-liquid extraction (цLLE)and solid phase micro extraction (SPME) in combination with gas chromatography-electron capture detector (GCECD) and a recently developed technique named stir bar sorptive extraction (SBSE) combined with thermal desorption system-programmable temperature vaporizationgas chromatography-mass spectrometer (TDS-PTV-GC-MS) for the analysis of organochloro-pesticides (OCPs) in natural water and to make a comparison between them. The most suitable method was then selected for the analysis of water samples collected from Eritrea. An additional goal was to develop a sensitive method for the analysis ofOCPs in soil and sediment samples. цLLE-GC-ECD and SPME-GC-ECD methods were evaluated for the analysis of OCPs in water. The former allowed achieving a sensitivity of less than 100 ppt and the latter was able to detect down to the 1 ppt level. Both methods were found to be repeatable with %RSD of3% to 19% and 5% to 12% as well as linear with a range of 1:103 and 1:5x103 respectivey. SBSE-TDS-GC-MS was also investigated for the analysis of OCPs in water samples. With this technique a good sensitivity down to 1 ppt was also obtained. The less sensitive nature of the MS compared to ECD was hereby compensated for by the large amount of polydimethylsiloxane (PDMS) phase on the stir bar. The method was repeatable and linear with a range of 1:5000, which is similar to the one obtained for the SPME-GC-ECD method. All three methods were also tested with real contaminated water samples and a comparison of the three techniques in terms of sensitivity, linearity, repeatability, availability and cost effectiveness was done. As a method of choice in terms of the above criteria, SPMEGC- ECD was applied to the water samples collected from Eritrea. The presence of some oePs such as a-BBC (benzenehexachloride), heptachlor, heptachlor epoxide, endosulfan I, p,p'-DDE (dichlorodiphenylchloroethylene), endosulfan II, p,p'-DDD (dichlorodiphenyldichloroethane), endosu!fan sulfate and p,p'-DDT (dichlorodiphenyltrichloroethane) in some of the Eritrean water samples was demonstrated The SPME-GC-ECD technique for the analysis OCPs in soil and sediment samples was investigated. It was shown to be able to detect down to 1 pg/g (lppt) with good linearity and repeatability. The method was also evaluated for authentic soil samples. Due to a lack of time the method could not be applied for the analysis of the soil and sediment samples collected from Eritrea.
AFRIKAANSE OPSOMMING: Die keuse van 'n gepaste monster-voorbereidingsmetode wat gebruik word tesame met 'n chromatografiese skeidingtegniek in omgewings-analise het 'n beduidende effek op die algehele metode. Die doel van hierdie werk was om metodes soos mikrovloeistof- vloeistof ekstraksie (цLLE) en soliede fase mikro ekstraksie (SPME) in kombinasie met gaschromatografie met elektronvangs deteksie (GC-ECD) te ontwikkel vir die analise van organochloor-pestisiede (OCPs) in natuurlike water. Vervolgens is hierdie metodes vergelyk met die onlangs-ontwikkelde roerstaaf sorptiewe ekstraksie tegniek (SBSE) in kombinasie met termiese desorbsie-GCmassaspektrometriese deteksie (TDS-GC-MSD). Die mees geskikte metode is vervolgens gebruik vir die analise van Eritreaanse watermonsters. Daarbenewens was die doelook om 'n sensitiewe metode te ontwikkel vir die analise van OCPs in gronden sedimentmonsters. Beide цLLE en SPME-GC-ECD metodes is gekarakteriseer deur goeie herhaalbaarheid en lineariteit. Die sensitiwiteit van bogenoemde metodes was minder as 100 dele per triljoen (ppt) en 1 ppt, respektiewelik. Ook met SBSE-TDS-GC-MSD kon 'n deteksielimiet van 1 ppt bereik word. In hierdie geval is vir die verlies van sensitiwiteit van die MSD in vergelyking met die ECD, gekompenseer deur die groter hoeveelheid PDMS op die roerstaaf in vergelyking met 'n SPME apparaat. Die herhaalbaarheid en lineariteit van die metode is vergelykbaar met dié van die SPMEGC- ECD metode. Al drie metodes is vergelyk vir die analise van gekontamineerde watermonsters in terme van sensitiwiteit, liniêre bereik, herhaalbaarheid, toeganklikheid en kosteeffektiwiteit. SPME-GC-ECD is vervolgens gekies as metode van voorkeur vir die analise van Eritreaanse watermonsters. Die teenwoordigheid van sekere OCPs soos a-BHC, heptachloor, heptachloorepoksied, endosulfan I, p,p'-DDE, endosulfan II, p,p' -DDD, endosulfan sulfaat en p,p' -DDT in die monsters is gedemonstreer. Die toepasbaarheid van die SPME-GC-ECD metode vir die analise van OCPs in grond-en sedimentmonsters is ook geëvalueer, en dit was moontlik om so min as 1 pg/g waar te neem. Weens tydbeperkings was dit nie moontlik om Eritreaanse grondmonsters met die ontwikkelde metode te analiseer nie.
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Carvalho, Adriana Pimentel de Almeida [UNESP]. "Otimização e validação de método para análise simultânea de dicofol, permetrina, dieldrin, endosulfan e diclorvos em ração animal, fígado e cérebro de ratos." Universidade Estadual Paulista (UNESP), 2010. http://hdl.handle.net/11449/105705.
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carvalho_apa_dr_araiq.pdf: 1244248 bytes, checksum: c31c8ba9a10569c696642941b0232500 (MD5)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Em 2005, a Agência Nacional de Vigilância Sanitária (ANVISA) através do Programa de Análise de Resíduos em Alimentos (PARA) indicou que a população brasileira está exposta aos resíduos de pesticidas. Considerando este contexto, foi proposto um projeto temático, coordenado pelo Prof. Dr. João Lauro Viana de Camargo (Faculdade de Medicina de Botucatu-UNESP), com o apoio da Fapesp. Para investigar o efeito da exposição a baixas doses de misturas de pesticidas quanto à carcinogenicidade e alteração do sistema endócrino em ratos machos de Lewis, foram escolhidos quatro pesticidas dentre os mais encontrados pela ANVISA (2005) em frutas e vegetais consumidos no país: diclorvos, dicofol, permetrina (cis-trans), dieldrin e endosulfan (α- ß). Na avaliação da toxicidade destes pesticidas e sua eventual importância para a saúde humana foram utilizados modelos com ratos machos da linhagem de Lewis expostos a esses agentes por via oral durante 8 semanas alimentados com uma ração basal enriquecida com os pesticidas nas concentrações NOEL e LOEL. Como parte do referido projeto temático, o desenvolvimento deste trabalho contempla a otimização e validação de métodos analíticos para a quantificação dos pesticidas selecionados em amostras de ração e tecidos provenientes dos animais de experimentação (fígado e cérebro). É parte fundamental deste projeto, a garantia da dose que estará sendo ingerida pelo animal, por isso foi desenvolvido e validado um método para análise dos pesticidas na ração animal. 0,5 g da amostra de ração triturada e homogeneizada foi extraída com 5 mL de acetato de etila em banho de ultrassom por 20 minutos seguido de centrifugação. O sobrenadante foi concentrado até à secura sob suave corrente de nitrogênio, redissolvido em 1,0 mL de isooctano e 1µL foi analisado por GC/ECD. Os parâmetros de validação...
In 2005, the National Health Surveillance Agency through the program for the analysis of residues in foods indicated that the Brazilian population was exposed to pesticide residues. Considering this context, a thematic project was proposed, under Prof. Dr. João Lauro Viana de Camargo (Faculdade de Medicina de Botucatu-UNESP), with FAPESP financial support. In order to investigate the carcinogenic and endocrine effect of exposure to low doses of pesticide mixtures in Lewis male mice, were chosen four types of pesticides found in fruits and vegetables by ANVISA survey in 2005. The selected pesticides were: dichlorvos, dicofol, permethrin (cis-trans), dieldrin and endosulfan (α- β). The toxicity evaluation of these pesticides was carried out in Lewis male mice fed for 8 weeks with a basal ration enriched with pesticides at concentrations NOEL and LOEL. The main purpose of this work was to optimize and validate analytical methods for determination pesticides in samples of feed and tissue from the experimental animals (liver and brain). The security of dose in animal feed was also developed and validated; 0.5 g sample of feed was triturated, homogenized and extracted with 5 mL of ethyl acetate in ultrasonic bath for 20 minutes followed by centrifugation. The supernatant was concentrated to dryness in a gentle stream of nitrogen, dissolved in 1.0 mL of isooctane and 1 µL was analyzed by GC / ECD. The validation parameters of the method were: recovery of 70 to 99 %, accuracy of less than 10 % (coefficient of variation) and quantification limits LQ between 0.4 and 0.8 mg/g. The proposed method for analysis of mice liver samples was the extraction of pesticides with ethyl acetate in ultrasonic bath followed by cleanup on florisil cartridges (500 mg). The triturated and homogenized liver sample was initially transferred to a glass tube with lid containing 5 mL of ethyl... (Complete abstract click electronic access below)
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Carbo, Leandro. "Ação mitigadora de faixa de contenção em lavouras de algodão sobre a contaminação de recursos hídricos superficiais por resíduos de pesticidas /." Araraquara : [s.n.], 2009. http://hdl.handle.net/11449/105703.
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Resumo: A contaminação de corpos d'água por pesticidas pode representar uma ameaça significativa para os ecossistemas aquáticos e recursos de água potável. Além das perdas de água e solo, os pesticidas merecem destaque, uma vez que são aplicados na agricultura para atender às necessidades de controlar as populações de pragas e doenças que atacam culturas de interesse agronômico. Quando aplicados, estes compostos podem rapidamente adsorver-se às partículas do solo, e dentre outros fenômenos de transportes, contaminarem os recursos hídricos superficiais por escoamento superficial. Neste sentido, boas práticas de conservação agrícola têm sido recomendadas para reduzir os riscos de contaminação ambiental, dentre elas, tem sido descrito na literatura o uso de faixas de vegetação próximas às margens de rios e córregos de maneira a diminuir a velocidade do escoamento e, conseqüentemente, o transporte de pesticidas para o ambiente aquático. Desta forma, neste trabalho foi avaliada a ação mitigadora de uma faixa de vegetação em lavouras de algodão sobre a contaminação de recursos hídricos superficiais por resíduos de pesticidas. O estudo do efeito da faixa de contenção foi desenvolvido em uma propriedade cotonícola às margens do Córrego Chico Nunes, região de Primavera do Leste, Mato Grosso. Foram delimitadas duas parcelas experimentais numa vertente, sendo uma de 10 metros do capim Brachiaria decumbes, como faixa de contenção. No final de cada parcela, foram instalados coletores de escoamento superficial (água e sedimento), que eram transportados para caixas menores, no qual foi determinada a quantidade de água e solo perdidos, e coletadas três amostras representativas para análise dos resíduos de pesticidas aplicados na lavoura de algodão (metomil, carbofurano, diurom, malationa, metolacloro e endosulfam total)... (Resumo completo, clicar acesso eletrônico abaixo)Abstract: The contamination of water bodies by pesticides can pose a significant threat to aquatic ecosystems and drinking water resources. In addition to the loss of water and soil, pesticides are worth mentioning, since they are applied to control the population of pests and diseases in cropping areas. When applied, pesticides can rapidly be adsorbed to soil particles or contaminate surface water by runoff processes. In this way, good agricultural conservation practices have been recommended to reduce the risk of environmental contamination, as for example, the use of vegetative filter strip near to the banks of the rivers and streams in order to reduce the water flow and the transport of pesticides to the aquatic environment. Thus, this study evaluated the mitigation action of a vegetation filter strip in cotton crops on the contamination of surface water resources by pesticides. The buffer zone study was developed in a private property near of Chico Nunes Creek banks, region of Primavera do Leste, Mato Grosso. We delimited two plots (40 m long x 10 m wide) on a slope, one comprising of 10 meters of Brachiaria decumbes as a vegetative filter strip. At the end of each plot, runoff collectors (water and sediment) were installed, that were transported to smaller boxes where the amount of water and soil losses were determined. Three representative samples were collected for the analysis of residues of pesticides used in farming cotton (methomyl, carbofuran, diuron, malathion, metolachlor and total endosulfan). The study of the buffer zone efficiency was performed in two periods, 2005/2006 and 2006/2007 season, to check the behavior between application and detection of pesticides in the plots. Water samples and sediment were collected when natural rainfall events occurred in sufficient quantity to cause runoff. The sampling in 2005/2006 period was made between... (Complete abstract click electronic access below)
Orientador: Maria Lucia Ribeiro
Coorientador: Eliana Freire Gaspar de Carvalho Dores
Banca: Mary Rosa Rodrigues de Marchi
Banca: Emanuel Carrilho
Banca: Maria Eugênia Queiroz Nassur
Banca: Isabel Cristina Sales Fontes Jardim
Doutor
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Hu, Dingfei. "Environmental fate and chemistry of a veterinary antibiotic-tylosin and monoterpenoid pesticides-thymol and phenethyl propionate." [Ames, Iowa : Iowa State University], 2007.
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Ibrahim, Azza Mahmoud Ahmed. "The development of enzyme-linked immunosorbent assays for the detection of pesticides in milk." Thesis, University of Salford, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.238752.
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Carvalho, Adriana Pimentel de Almeida. "Otimização e validação de método para análise simultânea de dicofol, permetrina, dieldrin, endosulfan e diclorvos em ração animal, fígado e cérebro de ratos /." Araraquara : [s.n.], 2010. http://hdl.handle.net/11449/105705.
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Orientador: Mary Rosa Rodrigues de MarchiBanca: Raquel Fernandes Pupo Nogueira
Banca: Mário Sérgio Galhiane
Banca: Silvia Helena Govoni Brondi
Banca: Valdemar Luiz Tornisielo
Resumo: Em 2005, a Agência Nacional de Vigilância Sanitária (ANVISA) através do Programa de Análise de Resíduos em Alimentos (PARA) indicou que a população brasileira está exposta aos resíduos de pesticidas. Considerando este contexto, foi proposto um projeto temático, coordenado pelo Prof. Dr. João Lauro Viana de Camargo (Faculdade de Medicina de Botucatu-UNESP), com o apoio da Fapesp. Para investigar o efeito da exposição a baixas doses de misturas de pesticidas quanto à carcinogenicidade e alteração do sistema endócrino em ratos machos de Lewis, foram escolhidos quatro pesticidas dentre os mais encontrados pela ANVISA (2005) em frutas e vegetais consumidos no país: diclorvos, dicofol, permetrina (cis-trans), dieldrin e endosulfan (α- ß). Na avaliação da toxicidade destes pesticidas e sua eventual importância para a saúde humana foram utilizados modelos com ratos machos da linhagem de Lewis expostos a esses agentes por via oral durante 8 semanas alimentados com uma ração basal enriquecida com os pesticidas nas concentrações NOEL e LOEL. Como parte do referido projeto temático, o desenvolvimento deste trabalho contempla a otimização e validação de métodos analíticos para a quantificação dos pesticidas selecionados em amostras de ração e tecidos provenientes dos animais de experimentação (fígado e cérebro). É parte fundamental deste projeto, a garantia da dose que estará sendo ingerida pelo animal, por isso foi desenvolvido e validado um método para análise dos pesticidas na ração animal. 0,5 g da amostra de ração triturada e homogeneizada foi extraída com 5 mL de acetato de etila em banho de ultrassom por 20 minutos seguido de centrifugação. O sobrenadante foi concentrado até à secura sob suave corrente de nitrogênio, redissolvido em 1,0 mL de isooctano e 1µL foi analisado por GC/ECD. Os parâmetros de validação... (resumo completo, clicar acesso eletrônico abaixo)
Abstract: In 2005, the National Health Surveillance Agency through the program for the analysis of residues in foods indicated that the Brazilian population was exposed to pesticide residues. Considering this context, a thematic project was proposed, under Prof. Dr. João Lauro Viana de Camargo (Faculdade de Medicina de Botucatu-UNESP), with FAPESP financial support. In order to investigate the carcinogenic and endocrine effect of exposure to low doses of pesticide mixtures in Lewis male mice, were chosen four types of pesticides found in fruits and vegetables by ANVISA survey in 2005. The selected pesticides were: dichlorvos, dicofol, permethrin (cis-trans), dieldrin and endosulfan (α- β). The toxicity evaluation of these pesticides was carried out in Lewis male mice fed for 8 weeks with a basal ration enriched with pesticides at concentrations NOEL and LOEL. The main purpose of this work was to optimize and validate analytical methods for determination pesticides in samples of feed and tissue from the experimental animals (liver and brain). The security of dose in animal feed was also developed and validated; 0.5 g sample of feed was triturated, homogenized and extracted with 5 mL of ethyl acetate in ultrasonic bath for 20 minutes followed by centrifugation. The supernatant was concentrated to dryness in a gentle stream of nitrogen, dissolved in 1.0 mL of isooctane and 1 µL was analyzed by GC / ECD. The validation parameters of the method were: recovery of 70 to 99 %, accuracy of less than 10 % (coefficient of variation) and quantification limits LQ between 0.4 and 0.8 mg/g. The proposed method for analysis of mice liver samples was the extraction of pesticides with ethyl acetate in ultrasonic bath followed by cleanup on florisil cartridges (500 mg). The triturated and homogenized liver sample was initially transferred to a glass tube with lid containing 5 mL of ethyl... (Complete abstract click electronic access below)
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Donohue, Tammy Schumacher. "A Comparison of Common Laboratory Techniques for the Analysis of Thiocarbamate Pesticides." University of Akron / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=akron1342049057.
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Mikalouski, Flavianny Brencis da Silva. "Avaliação dos níveis de pesticidas organoclorados em águas na região de Apucarana-PR usando a microextração em fase líquida com cromatografia gasosa acoplada à espectrometria de massa." Universidade Tecnológica Federal do Paraná, 2015. http://repositorio.utfpr.edu.br/jspui/handle/1/1545.
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Dissertação composta por 3 artigos.CAPES
O meio ambiente está em constante modificação, principalmente devido à influência antrópica. O monitoramento destes ambientes tem como objetivo caracterizar o meio, prever danos futuros e remediar possíveis impactos. No ambiente, as águas superficiais são dinâmicas, com constantes mudanças e crescente demanda, necessitando da garantia de qualidade para seu uso, realizada através de análises físico-químicas, microbiológicas e de compostos traço. Neste estudo, amostras de águas superficiais, de 12 pontos distintos da cidade de Apucarana-Paraná (Brasil), foram coletadas no período de um ano. As amostras foram submetidas às análises físico-químicas e microbiológicas, analisadas com base na quimiometria, a fim de demonstrar a influência do meio urbano e rural, e os fatores mais relevantes para a caracterização do ambiente. Considerando os ambientes de influência rural, foram analisadas a presença de pesticidas organoclorados, com a otimização do método de microextração líquido-líquido dispersiva, e uso instrumental da cromatografia gasosa acoplada a espectrometria de massa. Os dados apontam que os ambientes estão livres de contaminação e dentro dos padrões de aceitação, tanto para os parâmetros físico-químicos quanto microbiológicos. Os ambientes de interesse também apresentaram-se isentos de contaminação por pesticidas organoclorados no período de pesquisa.
The environment is constantly changing, mainly due to human influence. Environmental monitoring has object to environment, predict future damage and remedy potential impacts. Surface water is a dynamic medium, with constant changes and increasing demand, requiring quality assurance for their use, performed by physical-chemical, microbiological and analysis compounds traits. In this study, surface water samples of 12 different points of the city of Apucarana, Paraná (Brazil), were collected within one year. The samples were subjected to physical, chemical and microbiological analyzes, analyzed based on chemometrics in order to demonstrate the influence of urban and rural areas, and the most important factors to characterize the environment. Considering the influence of rural environments were analyzed the presence of organochlorine pesticides in the optimization of the method of liquid-liquid microextraction dispersive, and instrumental use of gas chromatography-mass spectrometry. Data indicates that the environments are free from contamination and within the acceptable standards for both the physical-chemical and microbiological parameters. The environments of interest also presented free of contamination by organochlorine pesticides in the research period.
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Ménager, Matthieu. "Photodégradation de pesticides organophosphorés en solution aqueuse et sur argiles : étude mécanistique." Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2007. http://tel.archives-ouvertes.fr/tel-00718364.
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Le pesticide organophosphoré azinphos-méthyle (AZM) voit son efficacité de photodégradation augmenter avec l'énergie d'excitation, vraisemblablement dû à des différences de réactivité entre états excités. Sa dégradation sous excitation directe conduit à la formation de benzotrione qui se dégrade en l'acide anthranilique. Un autre organophosphoré, le cyanophos, se dégrade sous excitation directe en faisant intervenir les états excités triplet et singulet pour former : le 4-cyanophénol, le cyanophos-oxon et un dérivé de l'acide benzoïque. Le dépot de l'AZM dans l'argile conduit à une meilleur absorption de la lumière solaire. Sa photodégradation sur argiles et oxyde de fer est efficace, avec une vitesse dépendant essentiellement de la nature et de l'épaisseur du solide du taux d'humidité et de fer(III). L'AZM se dégrade par des processus issus d'une excitation directe et d'autres photoinduits par le support. La formation de radicaux hydroxyles a également été mise en évidence
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Franjesevic, Andrew Joseph. "Design, Synthesis, and Evaluation of Therapeutics for the Treatment of Organophosphorus Poisoning by Nerve Agents and Pesticides." The Ohio State University, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=osu1563349257142378.
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Akinsiku, Sileola B. "Detecting Organic Molecules on the Surface of Inorganic Dust Particles Using Aerosol Mass Spectrometry." DigitalCommons@USU, 2009. https://digitalcommons.usu.edu/etd/369.
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Detection of organic molecules present on the surface of dust particles is important in homeland security, agriculture, and several other applications. The research presented reports the ability of the aerosol mass spectrometer (AMS) to detect molecules on the surface of dust particles without detecting the particle core. Experiments were carried out to detect semi-volatile organic compounds adsorbed onto the surface of particulates without interference from the dust particle core. Methyl salicylate, oleic acid, and organophosphorus pesticides such as Malathion were detected on the surface of particles representative of dust-type materials. Zeolite powders were used as aerosol support, representative of a typical silica mineral aerosol present in the atmosphere. Mass spectral fingerprint information was gained by first directly detecting atomized species to record their clean electron impact mass spectrum. This facilitated detection during later experiments of organic molecules coated on an inorganic support. Spectra obtained give mass spectrometric signatures of molecules coated on inorganic particles without detection of the particle core. An important feature of the AMS is the ability to equate an ion rate detected in the mass spectrometer to a mass concentration of a given chemical species in a sample using its ionization efficiency. Based on an average inlet flow rate of 1.2 cm 3sec -1 the ionization efficiencies obtained were 5.89x10-5, 1.15x10-6, and 1.62x10-5 for Malathion, methyl salicylate, and oleic acid, respectively. These experiments and the results obtained show that detection and characterization of organic species adsorbed onto inorganic dust particles are possible at µg m-3 concentrations using the AMS.
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Salvarani, Patricia Ishisaki. "Impact of contaminants in natural populations of marine turtles (Campeche, Mexico)." Doctoral thesis, Universidade de Aveiro, 2017. http://hdl.handle.net/10773/23764.
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Doutoramento em BiologiaAs tartarugas marinhas sofrem um forte impacto populacional devido às atividades antropogênicas, como as causadas pelo aumento da exploração comercial e industrial nas áreas costeiras, alteração do habitat, ingestão de resíduos sólidos, captura acidental nas atividades pesqueiras e a contaminação de poluentes químicos. Das sete espécies de tartarugas marinhas existentes distribuídas por quase todos os oceanos (Caretta caretta, Chelonia mydas, Dermochelys coriacea, Eretmochelys imbricata, Lepidochelys olivacea, Natator depressus e Lepidochelys kempii), exceto o Natator depressus, todos os outros seis são listados como vulneráveis, em perigo ou criticamente ameaçado na lista da IUCN. Os contaminantes ambientais de origem química, como metais pesados, pesticidas, hidrocarbonetos, PCB, organoclorados e dioxinas estão causando um forte impacto na saúde de animais marinhos, incluindo tartarugas marinhas, e a bioacumulação desses poluentes em tecidos e órgãos influenciam o crescimento e desenvolvimento de populações naturais de tartarugas marinhas em todo o mundo, podendo causar mortalidade em vários estágios de seu desenvolvimento. Uma vez que estão em perigo é extremamente importante para a compreensão das respostas às medidas de impacto e conservação à longo prazo nas populações de tartarugas marinhas. Este trabalho é uma visão geral dos estudos sobre a quantificação de contaminantes em ovos e sangue de tartarugas marinhas, buscando relações entre o tamanho da carapaça e a atividade de enzimas antioxidantes usando técnicas não-letais. A concentração de pesticidas organoclorados (OCPs) no plasma das fêmeas adultas e os ovos das tartarugas de pente (Eretmochelys imbricata) e tartaruga verde (Chelonia mydas) que desovam na área costeira de Campeche serão analisados. O objetivo principal desta tese é avaliar o potencial das populações naturais como bioindicadores de contaminação química. Para tal, foram analisados os valores hematológicos, contaminação de OCPs no plasma e ovos de duas espécies de tartarugas marinhas com hábitos alimentares diferentes e uma possível transferência materna na espécie de tartaruga de pente. Por fim, a atividade de biomarcadores enzimáticos foram correlacionadas com a contaminação por OCPs. Os resultados mostraram que foram encontrados OCPs em todos os ovos analisados, mostrando maiores concentrações de ΣHCH e ΣDrines nas duas espécies selecionadas, sendo encontradas diferenças significativas entre as espécies e os anos analisados. Foram encontras diferenças significativas entre as concentrações de OCPs (ΣHCHs, ΣDrines e ΣChlordanes) em relação ao sangue e ovos, indicaram que esses contaminantes químicos estão sendo transferidos maternalmente. Nenhuma enzima antioxidante teve relação significativa com os OCPs mais encontrados no sangue (ΣDDTs, ΣHCHs e ΣDrines).
Sea turtles have been suffering strong population impact due to anthropogenic activities, such as those caused by the increase in commercial and industrial exploitation of coastal areas, habitat alteration, ingestion of solid waste, incidental capture in fishing activities and contamination of chemical pollutants. Of the seven species of marine turtles existing distributed by almost all oceans (Caretta caretta, Chelonia mydas, Dermochelys coriacea, Eretmochelys imbricata, Lepidochelys olivacea, Natator depressus and Lepidochelys kempii), except the Natator depressus, all other six are listed as vulnerable, endangered or critically endangered on the IUCN list. Environmental contaminants of chemical origin such as heavy metals, pesticides, hydrocarbons, PCBs, organochlorine, and dioxins are causing major health impacts of marine animals, including sea turtles, and bioaccumulation of these pollutants in tissues and organs influence the growth and development of natural populations of sea turtles worldwide, may cause mortality in various stages of development. Because they are endangered is extremely important to the understanding of responses to impact and conservation measures in the long term in the populations of sea turtles in developing. This work is an overview of studies on the quantification of contaminants in blood and sea turtle eggs, searching for relationships between, carapace size and the activity of antioxidant enzymes using non-lethal techniques. The concentration of organochlorine pesticides (OCPs) in plasma of adult females and eggs of hawksbill turtles (Eretmochelys imbricata) and green turtle (Chelonia mydas) that nest in the coastal area of Campeche will be analysed. The main objective of this thesis is to evaluate the potential of natural populations as bioindicators of chemical contamination. For this, the hematological values, contamination of OCPs in the plasma and eggs of two species of sea turtles with different feeding habits and a possible maternal transfer in the hawksbill turtles were analysed. Finally, the activity of enzymatic biomarkers was correlated with the contamination by OCPs. The results showed that OCPs were found in all analysed eggs, showing higher concentrations of ΣHCH and ΣDrines in the two species selected, being found significant differences between the species and the studied years. We find significant differences between the concentrations of OCPs (ΣHCHs, ΣDrines and ΣChlordanes) of blood to eggs showed that these chemical contaminants being transferred maternally. No antioxidant enzyme had significant relationship with COPs main found in the blood (ΣDDTs, ΣHCHs and ΣDrines).
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Howard, Angela L. "Strategies for the analytical determination of thermally labile sulfur-containing environmental pollutants." Diss., Virginia Tech, 1992. http://hdl.handle.net/10919/39291.
Full textAbstract:
Increasing public awareness of toxic moieties in our environment has put pressure on regulatory agencies to improve testing methods so that these harmful agents can be identified and quantitated at lower and lower levels. The main objective of this work was to investigate analytical methodologies that would allow the sensitive, selective determination of pollutants to be routinely possible. Polar, thermally labile sulfur-containing pesticides and pollutants were our focus analytes. This objective was achieved in two ways: 1) the development of supercritical fluid extraction procedures suitable for these compounds and 2) the interface of a sulfur-selective detector to chromatographic techniques appropriate for thermally labile compound analysis.
Supercritical fluids, particularly CO₂, have recently been shown to be suitable replacements for traditionally used organic solvents in extraction. However, due to the polarity of the sulfonyl urea herbicides and thiocarbamate insecticides studied, pure CO₂ was found to be an ineffective extractant. Polar SF mixtures (2 and 5 % methanol-modified CO₂) were investigated as alternative supercritical extraction fluids. Of the modified fluids, only 2% methanol-modified fluid could be used due to post-SFE trapping problems encountered with the 5% modified fluid. The quantitative extraction of two of these herbicides from water at the 50 ppb level was achieved using the former SF. This SF was also used to extract three thiocarbamates from apples at the 2 ppm level.
In order to achieve the second objective, a sulfur-selective gas chromatographic detector, the ozone-based sulfur chemiluminescence detector (SCD), was successfully interfaced to both packed column supercritical fluid chromatography (SFC) and microcolumn high performance liquid chromatography (micro-HPLC). The packed column SFC/SCD system was shown to be compatible with both pure CO₂ and methanolmodified CO₂ mobile phases with a detector sensitivity (2 pg S/sec.) comparable to that found with capillary SFC/SCD despite the presence of more CO₂, an effective chemiluminescence quenching agent. The equimolar response of this detector to sulfur was shown to be only somewhat affected by the coelution of other organic species and improper analyte combustion conditions. For micro-column HPLC/SCD, the detector was found to be compatible with methanol/water mobile phases. Mobile phase composition, mobile phase flow rate, air flow rate, and hydrogen flow rate were found to affect the detector's sensitivity. The detector's linear dynamic range, response factor, and detection limits were determined to vary as a function of mobile phase composition. Optimum sensitivity (600 fg S/sec.) was achieved with a mobile phase of 40% methano1l60% water mobile phase compositions investigated. The analysis of polyaromatic sulfur-containing hydrocarbons (PASH's), total sulfur in diesel fuel, and sulfonyl urea herbicides was realized with the SFC/SCD system while thiocarbamate pesticides from an apple matrix were examined with the HPLC/SCD system.Ph. D.
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Rifai, Ahmad. "Etude de la dégradation par photolyse directe de pesticides - Caractérisation structurale et toxicité potentielle des photoproduits." Phd thesis, Ecole Polytechnique X, 2013. http://pastel.archives-ouvertes.fr/pastel-00869289.
Full textAbstract:
Les pesticides appartiennent à la grande famille des polluants organiques. Ils sont destinés à lutter contre les parasites des cultures au sens large.La diffusion des pesticides dans la nature engendre une pollution des différents compartiments de la biosphère (eau, sol et atmosphère) et peut induire des effets toxiques aigus sur les êtres vivants de la biomasse terrestre et aquatique. Il est aujourd'hui démontré que certains pesticides sont des perturbateurs endocriniens et présentent en particulier des effets cancérogènes et mutagènes chez l'être humain. Les pesticides peuvent subir différents processus de transformation dans le cycle biologique naturel (biodégradation, volatilisation, irradiation solaire...) ou suite aux traitements appliqués dans les filières de potabilisation des eaux naturelles et dans les stations de retraitement des eaux usées. La présence de produits de dégradation de pesticides dans notre environnement est d'autant plus alarmante que leurs structures et leurs toxicités potentielles demeurent généralement inconnues. Des molécules qui appartiennent à deux familles de pesticides ont été choisies pour cette étude : les herbicides, représentés par le metholachlore, et les fongicides, représentés par la procymidone, le pyrimethanil et le boscalid. Le premier volet de la thèse a porté sur le développement d'une stratégie analytique permettant de caractériser les structures de composés issus de la dégradation par photolyse de ces pesticides. Le deuxième volet a porté sur l'estimation de la toxicité des produits de dégradation à l'aide d'une base de test in silico. L'identification des produits de dégradation a été réalisée grâce à deux techniques d'analyses complémentaires : la chromatographie en phase gazeuse couplée à un spectromètre de masse "multi étapes" (GC-MSn) et la chromatographie en phase liquide couplée à un spectromètre de masse en tandem (LC-MS/MS). L'estimation de la toxicité des produits de dégradation a été réalisée grâce au programme T.E.S.T. QSAR récemment développés pour tenter de prévoir la toxicité des molécules. La stratégie d'élucidation structurale des produits de dégradation des pesticides étudiés est basée sur l'étude des mécanismes de fragmentation des molécules mères des produits de dégradation. La masse molaire des molécules mères a été précisée par l'identification des masses sur charge (m/z) des ions pseudo moléculaires obtenus à l'aide des différentes modes d'ionisations en spectrométrie de masse : ionisation électronique (EI) et ionisation chimique (CI) en GC-MS et ionisation par électronébulisation (ESI) en LC-MS. La stratégie utilisée pour l'élucidation structurale des produits de dégradation est avérée très efficace, la plupart des structures chimiques des produits formés ayant été élucidées. Une étude cinétique a été réalisée pour visualiser l'apparition et la disparition des produits de dégradation durant la photolyse et pour donner une idée sur le taux de disparition de la molécule mère pour chaque pesticide. Les résultats de photolyse ont montré que le méthalochlore, le procymidone et le boscalid ont été dégradés sous irradiation après un certain temps en libérant des produits de dégradation avec des structures proches ou différentes des molécules mères. Tandis que le pyrimethanil a présenté une grande stabilité pendant 8 heurs d'irradiation (quantité restante après irradiation est de 60%) et a donné des produits de dégradation avec des quantités modérées. Concernant l'estimation de la toxicité, la plupart des produits de dégradation identifiés présentent des toxicités équivalentes ou plus importantes que celles des molécules d'origine. Les méthodes chimiques d'analyses utilisées et l'estimation de toxicités des produits de dégradations identifiés sont avérées complémentaires et indispensables pour mettre en évidence la présence d'autres produits polluants toxiques qui émergent dans l'environnement sans vrai contrôle.
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Östlund, Lena. "Development of a Multiresidue Method for Analysis of Acidic Pesticides in Cereals with Liquid Chromatography-Tandem Mass Spectrometry." Thesis, Mälardalen University, School of Sustainable Development of Society and Technology, 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:mdh:diva-9368.
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A new method for analysis of acidic herbicides, mostly phenoxy acids and their esters, in cereals with liquid chromatography-tandem quadrupole mass spectrometry (LS-MS/MS) has been developed. Samples were hydrolyzed with sodium hydroxide in order to release covalently bound compounds followed by neutralization and finally extraction with acidified ethyl acetate. The extraction efficiency for both ester formulations and acids were studied. Acceptable results (70-120 %) were obtained for 2,4-D, dichlorprop, MCPA and mecoprop for both esters and acids. However, low recoveries were observed for ester formulations of dicamba, fluroxypyr, fluazifop and haloxyfop, possibly due to the complex structure of the compounds in combination with the matrix and/or incomplete hydrolysis step. The limit of quantification (LOQ) for targeted pesticides was 0.01 mg/kg. The method has been tested in the EU Proficiency Test for cereals with good results.
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Farias, Leovergildo Rodrigues. "Investigação de traços de pesticidas em águas superficiais do Rio Branco e no efluente de uma rizicultura irrigada no estado de Roraima." Universidade Federal de Roraima, 2011. http://www.bdtd.ufrr.br/tde_busca/arquivo.php?codArquivo=60.
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Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorO uso de pesticidas na agricultura é considerado uma das principais causas da contaminação de águas superficiais e subterrâneas. Estas contaminações ocorrem principalmente pela ação das águas da chuva e de irrigação que provocam os processos de lixiviação, drenagem e escoamento dos pesticidas presentes nas plantações e no solo, que irão atingir correntes de água ou reservatórios. O Estado de Roraima apresenta o cultivo de arroz irrigado como atividade econômica predominante, aumentando anualmente esta forma de cultivo, aliado a este fato, possivelmente existe um aumento na quantidade de pesticidas utilizados. Resíduos de pesticidas estão presentes em águas superficiais em baixas concentrações. Devido a isso, tem aumentado o interesse de vários pesquisadores na investigação e no desenvolvimento de técnicas de determinação desses compostos em diversas matrizes. Sendo assim, o objetivo deste trabalho foi investigar a ocorrência de traços do pesticida organofosforado paration metílico e dos organoclorados endrin, dieldrin e aldrin em águas superficiais do rio Branco e no efluente de uma rizicultura irrigada no Estado de Roraima, utilizando a técnica da extração em fase sólida e a cromatografia em fase gasosa acoplada à espectrometria de massa.
The use of pesticides in agriculture is considered a major cause of contamination of surface and groundwater. These infections occur mainly by the action of rain water and irrigation causing the leaching processes, drainage and disposal of pesticides on crops and soil, which will reach streams or reservoirs. The State of Roraima presents the cultivation of rice irrigated as predominant economic activity, increasing this cultivation form annually, ally to this fact, possibly an increase exists in the amount of used pesticides. Being like this, the objective of this work was to investigate the occurrence of lines of the pesticide organofosforado paration methyl and of the organoclorados endrin, dieldrin and aldrin in surface waters of the White river and in the efluente of a rizicultura irrigated in the State of Roraima, using the technique of the extraction in solid phase and the cromatografia in gaseous phase coupled to the mass espectrometria.
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Coelho, Christian. "Fluorescence et propriétés photochimiques des matières organiques naturelles." Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2009. http://tel.archives-ouvertes.fr/tel-00724606.
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La matière organique naturelle (MON) est un mélange complexe de molécules provenant de la décomposition des débris végétaux et animaux. Une fraction de ces constituants, regroupés sous le nom générique de substances humiques, absorbent la lumière solaire ce qui lui confère des propriétés photosensibilisatrices. Au cours de cette thèse, nous avons étudié les propriétés photosensibilisatrices de substances humiques de différentes origines. Nous avons également essayé de corréler ces propriétés photodégradantes aux caractéristiques spectrales (absorption, fluorescence). L'objectif général a été la caractérisation des entités chromophores à l'origine des propriétés photosensibilisatrices. Nous avons étudié en parallèle les propriétés spectroscopiques et photochimiques de différents mélanges humiques : acides humiques extraits de sol, fractions d'acides humiques obtenues par ultrafiltration, fractions aqueuses de sol, acides de type humiques extraits de compost, fractions aqueuses de compost. Pour suivre les propriétés photosensibilisatrices, deux types de sondes chimiques ont été utilisées : le 2,4,6-triméthylphénol qui est oxydé par les états excités triplets des substances humiques par transfert d'électrons et l'alcool furfurylique qui subit une photooxygénation par réaction avec l'oxygène singulet. La photodégradation de produits phytosanitaires a également été examinée. Ce travail a permis d'arriver aux conclusions suivantes. Les constituants émissifs au-delà de 500 nm sont concentrés dans des macromolécules de masses moléculaires inférieures à 30 kDa. La bande d'émission très large peut être subdivisée (maximum à 515 nm dans les fractions < 3kDa et maximum à 550 nm dans les fractions >3 kDa). La production d'oxygène singulet se corrèle positivement avec l'intensité d'émission de fluorescence entre 500 et 550 nm. Cette corrélation qui a été observée sur un grand nombre d'échantillons et sur des échantillons très variés prouve que les constituants photosensibilisateurs sont fluorescents à grande longueur d'onde. Ces résultats constituent une avancée et ouvrent la voie à des études de caractérisation plus poussées
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Matos, Tassya Thaiza da Silva. "Avaliação de biocarvões obtidos da acácia negra (Acacia mearnsii de Wildemann) como adsorventes na remoção de pesticidas em água." Pós-Graduação em Química, 2014. https://ri.ufs.br/handle/riufs/6086.
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In accordance with the principles of green chemistry, the use of recycled materials in order to become the raw materials for the same or other process, minimizes or eliminates the generation of waste, reducing the use of materials and energy in process. Usually the alternatives explored are associated to farm products as, for example, the biomass derived of plants together with agricultural waste often lignocellulosic materials. The adsorbants used in this work derived of the tannin extraction from the Acacia mearnsii de Wildemann bark were pyrolyzed, chemically treated and appointed activated biochar (AB) and magnetic biochar (MB). Characterization by FT-IR, TGA, XDR, CHN and SEM allowed to display characteristics such as, for example, the presence of compounds originating from the biomass origin, tannins (TAN) in the BM and exhausted from the bark (CE) for BA. The adsorbents were effective in removing pesticides tiacloprid (TCL) and thiamethoxam (TMX) with values of adsorption capacity q = 0.73 and 0.40 mg g-1 for BM eq = 1.02 and 0.90 mg g-1 for BA, respectively. The removal percentage values were approximately 100% for two pesticides using BA, 72% and 42% using the WB, respectively, for the pesticides TMX and TCL. The kinetic model of pseudo-second order was the one that best fitted the results with values of q (exp) closest to q (calc) and good linearity coefficients ranging from 0.976 to 0.999. The study desorption of pesticides with water was performed in order to evaluate the possibility of the withdrawal of these pesticides for possible reuse of biochars. Attempting to desorption of adsorbed pesticides in biochar no significant results, thus evidencing the strong interaction between them. Thus, the study proposes the reuse of waste from an industrial process, which is the exhausted bark, for environmental purposes, as an alternative in removing pesticides besides assign any application to tannins extracted in the same process.De acordo com o princípio da química verde, a utilização de materiais reciclados a fim de que se tornem matérias-primas para o mesmo processo ou para outro, minimiza ou elimina a geração de resíduos, diminuindo o uso de materiais e energia na produção. As principais alternativas atualmente exploradas estão relacionadas a produtos, como a biomassa de plantas em conjunto com resíduos agrícolas muitas vezes de materiais lignocelulósicos. Os adsorventes utilizados nesse trabalho, derivados da extração de taninos da casca da acácia negra (Acacia mearnsii de Wildemann) foram pirolisados, tratados quimicamente e nomeados de biocarvão ativado (BA) e biocarvão magnético (BM). A caracterização pelas técnicas de FT-IR, TGA, DRX, CHN e MEV permitiram visualizar características como a presença de compostos oriundos da sua biomassa de origem, taninos (TAN) no caso do BM, e a casca esgotada (CE) para o BA. Os adsorventes mostraram-se eficientes na remoção dos pesticidas tiacloprido (TCL) e tiametoxam (TMX) com valores de capacidade de adsorção, q = 0,73 e 0,40 mg g-1 para o BM e q = 1,02 e 0,90 mg g-1 para BA, respectivamente. Os valores de porcentagem de remoção foram aproximadamente 100% para os dois pesticidas usando o BA, 72% e 42% usando o BM, respectivamente, para os pesticidas TCL e TMX. O modelo cinético de pseudo-segunda ordem foi o que mais se ajustou aos resultados encontrados com valores de qe(exp) mais próximos do qe(calc) e bons coeficientes de linearidade variando entre 0,976-0,999. O estudo de dessorção dos pesticidas utilizando água foi realizado no intuito de avaliar a possibilidade da retirada desses pesticidas para possível reutilização dos biocarvões. A tentativa de dessorção dos pesticidas adsorvidos nos biocarvões não apresentou resultados significativos, constatando-se assim a forte interação entre eles. Assim, o estudo propõe a reutilização de um rejeito de um processo industrial, que é a casca esgotada, para fins ambientais, como uma alternativa na remoção de pesticidas além de atribuir outra aplicação aos taninos extraídos no mesmo processo.
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Zappe, Janessa Aline. "AGROTÓXICOS NO CONTEXTO QUÍMICO E SOCIAL." Universidade Federal de Santa Maria, 2011. http://repositorio.ufsm.br/handle/1/6647.
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Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorThrough this work, it was investigated facilitative actions for the teaching and learning process in Chemistry in order to promote the knowledge of basic concepts and of the social implications of the Chemistry and the student's formation as citizen. From this, workshops were developed approaching the thematic pesticides in a school of Candelária-RS. The pesticides are chemical products used in the agriculture to control pests and plant diseases, and consequently, they are the responsible for the increase of the agricultural production. However, they can cause diseases and poisoning if they be used without the necessary cares, as the individual protection equipments. The thematic pesticides were chosen considering that these compositions are related directly to the daily lives of students whose families have their incomes based on the agriculture, some of the characteristics of the researched school. Before the development of the workshops, text books of Chemistry of the High School were analyzed and investigated the students' conceptions regarding the theme. It is observed that in the analyzed text books, the importance of the equipments of individual protection is not approached. Through the questionnaire, it was verified that the participant students of this research have difficulties in relating contents of Chemistry with their daily lives. Considering those results, five thematic workshops were elaborated, that sought to relate topics of the Chemistry with the pesticides, being investigated as these methodological propositions can contribute to the learning of Chemistry and for the student's formation as citizen. Through the questionnaires, textual productions and interviews with the students and of the research diary, it can be noticed that the thematic workshops contributed to the valorization of the learning of Chemistry, because they associate chemical concepts with daily lives of students and it motivates them by the experimentation. What might also have stimulated the learning and the exercise of the citizenship on the part of the students was the educator's posture and the importance of the social theme, pesticides. The students were stimulated to think through the problematization, becoming participant and conscious citizens, through the workshops. As the workshops thematic, several methodological propositions have been investigated. However, the great challenges to be overcome is the gap between the research and the Science teaching.
Através deste trabalho, investigaram-se ações facilitadoras para o processo de ensino e aprendizagem em Química a fim de promover o conhecimento de conceitos básicos e das implicações socias da Química e a formação do estudante como cidadão. A partir disso, foram desenvolvidas oficinas abordando a temática agrotóxicos numa escola de Candelária-RS. Os agrotóxicos são produtos químicos utilizados na agricultura para controlar pragas e doenças de plantas, e conseqüentemente, são os responsáveis pelo aumento da produção agrícola. Entretanto, podem causar doenças e intoxicações se forem utilizados sem os cuidados necessários, como os equipamentos de proteção individual. A temática agrotóxicos foi escolhida considerando que estes compostos estão relacionados diretamente ao dia a dia de estudantes cujas famílias têm a sua fonte de renda baseada na agricultura, umas das características da escola pesquisada. Antes do desenvolvimento das oficinas, foram analisados livros didáticos de Química do Ensino Médio e investigado as concepções dos alunos com relação à temática. Observa-se que nos livros didáticos analisados, não é abordado a importância dos equipamentos de proteção individual. Através do questionário, constatou-se que os alunos participantes desta pesquisa têm dificuldades em relacionar conteúdos de Química com o seu dia a dia. A partir desses resultados, foram elaboradas cinco oficinas temáticas, que visavam relacionar tópicos da Química com os agrotóxicos, investigando-se como estas proposições metodológicas podem contribuir para a aprendizagem de Química e para a formação do estudante como cidadão. Através dos questionários, produções textuais e entrevistas com os alunos e do diário de pesquisa, pode-se perceber que as oficinas temáticas contribuíram para a valorização da aprendizagem de Química, pois associam conceitos químicos ao dia a dia dos alunos e motiva-os através da experimentação. O que pode também ter estimulado o aprendizado e o exercício da cidadania por parte dos alunos foi a postura do educador e a importância do tema social, agrotóxicos. Os alunos foram instigados a pensar através da problematização, oportunizando uma participação cidadã, por meio das oficinas. Assim como as oficinas temáticas, diversas proposições metodológicas têm sido investigadas. Entretanto, um dos grandes desafios a ser superado é o distanciamento entre a pesquisa e o ensino de Ciências.
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Lavieille, Delphine. "Phototransformation d'herbicides tricétoniques et d'insecticides pyréthrinoïdes à la surface des végétaux." Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2008. http://tel.archives-ouvertes.fr/tel-00731153.
Full textAbstract:
Les pesticides appliqués par pulvérisation dans les cultures sont dispersés à la surface des plantes où ils peuvent être transformés sous l'effet de la lumière solaire. Nous avons montré dans ce travail que les herbicides mésotrione et sulcotrione, et les insecticides cypermétrine et deltaméthrine sorbés à la surface des cires cuticulaires, sont photosensibles. Cette propriété est modifiée par l'ajout d'additifs présent dans les formulation commerciales ? Ces derniers peuvent accélèrer ou ralentir la photolyse des principes actifs. Cependant, il ne semble pas y avoir de règle générale permettant de prévoir l'importance de la phototransformation pour chaque matière active. D'autre part, alors qu'en laboratoire la dissipation des pesticides étudiés est uniquement due à la phototranformation ; sur les plantes entières, d'autres phénomènes interviennent. La diffusion dans la cuticule et les pertes dues au lessivage par la pluie ou la rosée peuvent devenir prépondérantes devant la phototransformation.
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Mokgadi, Janes. "Pressurized hot water extraction of nutraceuticals and organic pollutants from medicinal plants." Thesis, Rhodes University, 2011. http://hdl.handle.net/10962/d1004999.
Full textAbstract:
This thesis explores the robustness and the versatility of pressurized hot water extraction (PHWE) for a variety of analytes and matrices. Applications discussed include: selective extraction of alkaloids in goldenseal followed by their degradation studies; in-cell clean-up of pesticides in medicinal plants employing custom made molecularly imprinted polymers (MIPs) sorbents; in-cell pre-concentration followed by desorption of aflatoxins in plants with MIPs; desorption of pesticides from electrospun nanofiber sorbents; and removal of templates from MIPs sorbents. It was demonstrated that selective extractions could be achieved by just changing the temperature of water while adjusting the pressure. For instance, the alkaloids in goldenseal (hydrastine and berberine), were extracted at 140 °C, 50 bars, 1 mL min⁻¹ in 15 min; organochlorine pesticides from medicinal plants were extracted at 260 °C, 80 bars, 1 mL min-1 in 10 min; while aflatoxins AFG2, AFG1, AFB2 and AFB1 were extracted at 180 °C, 60 bars and a flow rate of 0.5 mL min⁻¹ in 10 min. The selectivity of PHWE was further enhanced by combining it with selective MIPs sorbents at higher temperatutes. In-cell clean-up of interfering chlorophyll was successfully removed from the medicinal plants during pesticides analysis while clean-up of aflatoxins AFG2, AFG1, AFB2 and AFB1 was achieved in two extraction cells connected in series. Ultrasound was also combined with PHWE for extraction of hydrastine and berberine at 80 °C and 40 bars in 30 min. PHWE was further evaluated for removal of templates from quercetin, phthalocynine and chlorophyll MIPs. The templates were thoroughly washed off their MIPs within 70 min with PHWE compared to over 8 h for Soxhlet and ultrasound assisted extraction. Pesticides were also desorbed from electrospun nanofibers at 260 °C, 80 bars in 10 min employing only water at 0.5 mL min⁻¹. In the light of green chemistry, the decrease in the usage of organic solvents was 100%, resulting in no organic solvent waste.
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Souza, Erica Rodrigues de. "Avaliação do praguicida aldicarbe e seus produtos de transformação em matriz ambiental -- desenvolvimento e comparação de técnicas analíticas." Universidade de São Paulo, 2009. http://www.teses.usp.br/teses/disponiveis/9/9141/tde-26012017-172922/.
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Os praguicidas carbamatos surgiram na década de 70. Este grupo de substâncias possui atividade anticolinesterásica, com variado grau de toxicidade. São solúveis em água e termicamente instáveis. O praguicida aldicarbe faz parte do grupo dos carbamatos, sendo um metil carbamato de oxima. Contaminações de águas subterrâneas e superficiais pelo aldicarbe já foram demonstradas, devido a alta solubilidade deste composto em água e sua alta capacidade de lixiviação em solo. Este trabalho visa o desenvolvimento de métodos analíticos para separação e quantificação de aldicarbe, aldicarbe sulfóxido e aldicarbe sulfona, por cromatografia líquida de alta eficiência, cromatografia líquida acoplada à espectrometria de massas e eletroforese capilar. O trabalho objetiva ainda avaliar a toxicidade aguda das três substâncias utilizando a bactéria marinha luminescente Vibrio fischeri. Amostras de água ultrapura, superficial e subterrânea foram submetidas a etapas de extração em diferentes cartuchos de fase sólida para avaliação da recuperação dos analitos e a realização da pré concentração dos mesmos. No método proposto por cromatografia líquida acoplada a espectrometria de massas, obteve-se limite de quantificação de 10 µg.L-1, sendo que o alcançado no método proposto por cromatografia líquida com detecção por arranjo de diodos foi de 2 µg.L-1. Já o método desenvolvido por eletroforese capilar com detecção por arranjo de diodos teve um limite de quantificação de 10 mg.L-1. Os resultados de CE50 obtida para o aldicarbe, aldicarbe sulfona e aldicarbe sulfóxido, no teste de toxicidade com a bactéria luminescente Vibrio fischeri foram respectivamente: 56,0 mg.L-1, 47,0 mg.L-1 e 7,8 mg.L-1. O método desenvolvido por cromatografia líquida se mostrou com sensibilidade satisfatória para análise de aldicarbe e seus produtos de transformação em água com níveis de quantificação dos compostos abaixo do limite determinado pela OMS (10 µg.L-1. O método por eletroforese capilar não se mostrou com sensibilidade ideal para detecção dos analitos em níveis de traços. No teste de toxicidade aguda, observou-se que o aldicarbe sulfóxido é cerca de 7 vezes mais tóxico para a bactéria que o próprio aldicarbe, o que já é descrito na literatura para outras espécies.Carbamates pesticides first appeared in the 1970s. This group of substances possesses anticholinesterasic activity, with varied toxicity degree. They are soluble in water and thermally unstable. The aldicarb pesticide belongs to the carbamates group, being an oxime methyl carbamate. Contaminations of underground and superficial waters by aldicarb have been demonstrated, due to the high solubility of this compound in water and its high capacity of lixiviation in soil. This dissertation aims to develop analytical methods for separation and quantification of aldicarb, aldicarb sulfoxide, and aldicarb sulfona, by high efficiency liquid chromatography, liquid chromatography-tandem mass spectrometry and capillary electrophoresis. The dissertation also focuses on evaluating the acute toxicity of the three substances using the luminescent marine bacterium Vibrio fischeri. Samples of ultrapure water, superficial and underground, were submitted to extraction stages in different cartridges of solid phase for evaluating the recovery of analytes and conducting their pre-concentration. In the method proposed by liquid chromatography-tandem mass spectrometry, a quantification limit of 10 µg.L-1 was obtained, in comparison with the 2 µg.L-1 achieved in the method proposed by liquid chromatography with diode-array detection. The method developed by capillary electrophoresis with diode-array detection had a quantification limit of 10 mg L-1. The results of CE50 obtained for the aldicarb, aldicarb sulfone and aldicarb sulfoxide, in the toxicity test with the luminescent bacterium Vibrio fischeri were respectively: 56.0 mg.L-1, 47.0 mg.L-1 e 7.8 mg.L-1 The method developed by liquid chromatography showed satisfactory sensitivity for analysis of aldicarb and its transformation products in water with quantification levels of the compounds below the limit determined by OMS (10 µg.L-1
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Nanna, Saverio <1985>. "Optimization of molecular and crystalline forms of drugs, agrochemicals, pesticides in relation to activity, bioavailability, patentability and to the fabrication of polymorphs, solvates, co-crystals with green chemistry methods." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2015. http://amsdottorato.unibo.it/7050/.
Full textAbstract:
This doctorate was funded by the Regione Emilia Romagna, within a Spinner PhD project coordinated by the University of Parma, and involving the universities of Bologna, Ferrara and Modena.
The aim of the project was:
- Production of polymorphs, solvates, hydrates and co-crystals of active pharmaceutical ingredients (APIs) and agrochemicals with green chemistry methods;
- Optimization of molecular and crystalline forms of APIs and pesticides in relation to activity, bioavailability and patentability.
In the last decades, a growing interest in the solid-state properties of drugs in addition to their solution chemistry has blossomed. The achievement of the desired and/or the more stable polymorph during the production process can be a challenge for the industry. The study of crystalline forms could be a valuable step to produce new polymorphs and/or co-crystals with better physical-chemical properties such as solubility, permeability, thermal stability, habit, bulk density, compressibility, friability, hygroscopicity and dissolution rate in order to have potential industrial applications.
Selected APIs (active pharmaceutical ingredients) were studied and their relationship between crystal structure and properties investigated, both in the solid state and in solution. Polymorph screening and synthesis of solvates and molecular/ionic co-crystals were performed according to green chemistry principles. Part of this project was developed in collaboration with chemical/pharmaceutical companies such as BASF (Germany) and UCB (Belgium). We focused on on the optimization of conditions and parameters of crystallization processes (additives, concentration, temperature), and on the synthesis and characterization of ionic co-crystals.
Moreover, during a four-months research period in the laboratories of Professor Nair Rodriguez-Hormedo (University of Michigan), the stability in aqueous solution at the equilibrium of ionic co-crystals (ICCs) of the API piracetam was investigated, to understand the relationship between their solid-state and solution properties, in view of future design of new crystalline drugs with predefined solid and solution properties.
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Isaac, Giorgis. "Development of Enhanced Analytical Methodology for Lipid Analysis from Sampling to Detection : A Targeted Lipidomics Approach." Doctoral thesis, Uppsala University, Analytical Chemistry, 2005. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-5810.
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This thesis covers a wide range of analytical method development for lipid analysis in complex biological samples; from sample preparation using pressurized fluid extraction (PFE) and separation with reversed phase capillary liquid chromatography (RP-LC) to detection by electrospray ionization mass spectrometry (ESI/MS) and tandem MS.
The requirements for fast, reliable and selective extraction methods with minimal usage of solvents have accelerated the development of new extraction techniques. PFE is one of the new automated, fast and efficient liquid extraction techniques which use elevated temperature and pressure with standard liquid solvents. In this thesis the reliability and efficiency of the PFE technique was investigated for the extraction of total lipid content from cod, herring muscle and human brain tissue as well as for pesticides from fatty foodstuffs. Improved or comparable efficiencies were achieved with reduced time and solvent consumption as compared to traditional methods.
A RP-LC coupled online to ESI/MS for the analysis of phosphatidylcholine (PC) and sphingomyelin (SM) molecular species was developed and used for the analysis of brain lipids from eight groups of mice treated with vehicle and various neuroleptics. The effect of postnatal iron administration in lipid composition and behavior was investigated. Whether or not these effects could be altered by subchronic administration of the neuroleptics (clozapine and haloperidol) were examined. The results support the hypothesis that an association between psychiatric disorders, behavior abnormalities and lipid membrane constitution in the brain exists.
Finally, a tandem MS precursor ion scan was used to analyze the developmental profile of brain sulfatide accumulation in arylsulfatase A (ASA) deficient (ASA -/-) as compared to wild type control (ASA +/+) mice. The ASA -/- mice were developed as a model of the monogenic disease metachromatic leukodystrophy with an established deficiency of the lysosomal enzyme ASA. The results showed that an alteration in the composition of sulfatide molecular species was observed between the ASA -/- and ASA +/+ mice.
This thesis shows that modern analytical methods can provide new insights in the extraction and analysis of lipids from complex biological samples.
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Dias, Mariana Amaral. "Desenvolvimento de método cromatográfico para determinação de pesticidas em fase gasosa utilizando amostradores de baixo volume." Universidade Tecnológica Federal do Paraná, 2018. http://repositorio.utfpr.edu.br/jspui/handle/1/3149.
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Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do ParanáUm método para determinação dos pesticidas trifluralina, atrazina, alaclor e clorpirifós em fase gasosa utilizando espuma de poliuretano (PUF) e resina polimérica de estireno divinilbenzeno (XAD-2) foi desenvolvido. A amostragem foi realizada com a utilização de amostradores de baixo volume na vazão de 4,0 L min-1 por 24 h. Os pesticidas foram extraídos utilizando banho de ultrassom com acetona e determinados por GC-MS/MS. Os picos cromatográficos apresentaram boa resolução e seletividade. O método foi aplicado em amostras de fase gasosa coletadas na cidade de Arapongas/PR entre os meses de fevereiro e novembro de 2017. Foram coletadas amostras na UTFPR/Curitiba, a fim de minimizar os efeitos de matriz. Um, dois e três ciclos de extração foram avaliados e a extração com dois ciclos foi escolhida. Boas recuperações para essa extração foram obtidas para os quatro pesticidas, ambas em PUF (75,1 – 117,8%) e em XAD-2 (71,2 – 109,4%), em dois níveis de concentração. Os limites de detecção utilizando o método de superposição de matriz variaram de 24,1 a 63,1 pg m-3 em PUF e de 70,0 a 101,5 pg m-3 em XAD-2. Foram encontradas concentrações de 1189 pg m-3 para a trifluralina e 1345 pg m-3 para a atrazina. O clorpirifós foi o analito que apresentou maior concentração, sendo essa de 3062 pg m-3 entre os meses de setembro a novembro de 2017. O alaclor foi detectado em alguns meses, porém não pôde ser quantificado devido aos valores abaixo do limite de quantificação. As concentrações de clorpirifós assemelham-se às encontradas em outros estudos em regiões agrícolas. O aumento das concentrações de trifluralina, atrazina e clorpirifós podem estar relacionados à presença de uma área industrial próxima aos pontos de coleta das amostras onde esses compostos são manipulados.
A method for determination of trifluralin, atrazine, alachlor and chlorpyrifos in gas phase using polyurethane foam (PUF) and styrene-divinylbenzene polimeric resin (XAD-2) was developed. The sampling was performed by using low volume samplers at 4.0 L min-1 over 24 h. The pesticides were extracted using ultrassonic bath with acetone and determined by GC-MS/MS. The chromatographic peaks presented good resolution and selectivity. The method was applied in samples of gas phase collected in the city of Arapongas/PR between the months of February and November of 2017. Samples were collected at UTFPR/Curitiba in order to minimize the matrix effects. One, two and three cycles of extraction were evaluated and the extraction with two cycles was chosen. Good recoveries for this extraction were obtained for trifluralin, atrazine, alachlor and chlorpyrifos both in PUF (75.1 – 117.8%) and in XAD-2 (71.2 – 109.4%) in two levels of concentration. Limits of detection using matrix-standard calibrations solutions ranged from 24.1 to 63.1 pg m-3 in PUF and from 70.0 to 101.5 pg m-3 in XAD-2. Maximum concentrations of 1189 pg m-3 were found for the trifluralin and 1345 pg m-3 for the atrazine. Chlorpyrifos was the analyte that presented greater concentration, with a value of 3062 pg m-3 between the months of September and November. Alachlor was detected in a few months but was not quantified due the values below the limit of quantification. The concentrations of chlorpyrifos resemble those found in other studies in agricultural regions. The increase in the concentrations of trifluralin and atrazine may be related to the presence of an industrial area near the collection points of the samples where these compounds are manipulated.
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Kouzayha, Abir. "Développement des méthodes analytiques pour la détection et la quantification de traces des HAP et de pesticides dans l'eau. Application à l'évaluation de la qualité des eaux libanaises." Phd thesis, Université Sciences et Technologies - Bordeaux I, 2011. http://tel.archives-ouvertes.fr/tel-00786974.
Full textAbstract:
La pollution des eaux est particulièrement problématique pour les pays industrialisés et les pays en développement. Des suivis environnementaux se sont alors avérés nécessaires afin de progresser dans la compréhension des origines et des conséquences de la présence de ces polluants. Parmi les polluants organiques les plus dangereux, les Hydrocarbures Aromatiques Polycycliques (HAP) et les pesticides qui peuvent se retrouver à l'état de traces dans les milieux aquatiques. Leur analyse nécessite des méthodes analytiques à la fois spécifiques et sensibles. L'Extraction sur Phase Solide (SPE) suivi d'une analyse par la Chromatographie Gazeuse couplée à la Spectrométrie de Masse (GC-MS) est la méthode la plus couramment employée. Les travaux de thèse s'inscrivent ainsi dans l'optique générale visant à développer des nouvelles méthodes analytiques pour l'extraction et l'analyse de ces deux familles de polluants organiques présents dans l'eau. Afin de pallier les contraintes classiques de la SPE, une nouvelle approche a été développée qui consiste à introduire la technique de centrifugation dans certaines étapes de la procédure SPE. La nouvelle méthode élaborée a permis de réduire considérablement le temps de préparation et d'économiser l'utilisation et le rejet des solvants organiques, en réduisant presque 10 fois les volumes nécessaires à l'obtention des rendements de récupération satisfaisants. Une méthode d'analyse par injection à température programmable (PTV) a été optimisée afin d'améliorer les seuils de détection des HAP. Cette étude a permis également d'avoir les informations sur la qualité des eaux de pluie, eaux souterraines et eaux de surface au Liban quant au niveau de leur contamination pour les HAP et les pesticides.
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Pihlström, Tuija. "Development of Enhanced Analytical Methodology in Pesticide Chemistry." Doctoral thesis, Uppsala University, Analytical Chemistry, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-3406.
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The analysis of pesticide residues in fruit, vegetables, rape seed and water has been improved using developments in sample handling and analytical techniques. The method development is associated with analytical difficulties, since pesticides currently used in agriculture represent a variety of chemical classes having very different physico chemical properties. The method development also encounters difficulties when many various commodity classes with different characteristics are studied. The main task in pesticide residue analysis has been to provide multi residue methods, and traditionally GC has been the main analytical technique.
In order to regulate the use of hazardous pesticides, the EU commission introduces strict maximum residue levels (MRL). The need for improved sample handling and detection techniques are, however, high due to handling of lower detection limits, complex matrices and the need of more efficient sample throughput. Of the new techniques introduced as alternative techniques to the traditional extraction techniques, pressurised fluid extraction (PFE) has shown to be a promising technique in analysis of pesticide residues in fatty foodstuffs.
In water analysis, large sample volumes are needed due to low MRLs. The solid phase extraction (SPE) technique allows a concentration of large sample volumes and simplifies the tedious laboratory work with traditional separation funnels. A new approach was to use non-polar solvents for the sample extraction from the earlier used polymeric column. Both these techniques provide low solvent consumption, short extraction times and ability to automate the manual steps.
An LC-MS/MS multi residue method was finally developed for pesticide residues in fruit and vegetables. The technique is robust and sensitive and allows a simultaneous determination of 57 pesticides and metabolites in one single analysis and without any clean-up steps. The sensitivity was improved to achieve the maximum residue limits needed by EU. Several multi step methods, which involve more costly analysis, has been replaced by this technique.
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Tegenaw, Ayenachew G. Ph D. "Environmental Implications of Cu-Based Nanoparticles and Biocides Products." University of Cincinnati / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1573573946625869.
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Jesus, Jemmyson Romário de. "Avaliação de material alternativo para uso como adsorvente na extração em fase sólida de resíduos de pesticidas em estipe de coqueiro (Cocos nucifera L)." Pós-Graduação em Química, 2014. https://ri.ufs.br/handle/riufs/6095.
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The coconut (Cocos nucifera L) is a rich source of nutrient and as well as other plants is under attack from different types of pests and diseases, causing losses to producers. Pesticide use remains the primary control strategy and combat pests and diseases in agricultural crops. However, the excessive and indiscriminate use of these products can cause serious harm to human health and the environment due to the high toxicity these products. In Brazil, until now no stipulated values of maximum residue limits (MRLs) for pesticides in coconut crops. Similarly, there is little information about the degree of contamination. Therefore analytical methodologies must be developed for the determination of pesticide residues in coconut cultivation, aiming to ensure human health. Thus, this work proposes a methodology to determine residue of bromopropylate, clofentezine, coumaphos, difenoxuron, diniconazole, fenvalerate, flumetralin, flumeturon, teflubenzuron in greens stipe, appling the matrix solid phase dispersion (MSPD) and liquid chromatography with diode array detector (LC-DAD) for analysis. In this study we evaluated the best sorbent/solvent combinations (using silica, Florisil, neutral alumina, C18 and coordination polymers [Zn(BDC)(H2O)2]n, [Zn(BDC)0.99(NH2-BDC)0.01)(H2O)2]n, [Zn(BDC)0.95(NH2-BDC)0.05)(H2O)2]n, [Zn(BDC)0.90(NH2-BDC)0.10)(H2O)2]n/acetonitrile), the best ratio of sample/ adsorbent mass, as volume of the elution solvent used for extraction were evaluated. Among the investigated combinations, the system comprising 0.25 g of stem, 1 g of neutral alumina and 5 mL of acetonitrile was the most efficient in recovery resulting from 70 and 93%, with relative standard between 1.6% and 10%, in the levels of concentration 0.04, 0.08, 0.2, 0.4, 2.0, 3.0; 4.0 ìg g-1. The linearity was above 0.9991 and the limits of detection between 0.01 and 0.05 ìg g-1 and quantification 0.05 and 0.2 ìg g-1. Among the polymeric phases, the [Zn(NH2BDC)0.1(BDC)0.9(H2O)2]n was most eficiente in the extraction of bromopropylate, clofentezine, coumaphos, difenoxuron, diniconazole, fenvalerate, flumetralin, flumeturon and teflubenzuron.O coqueiro (Cocos nucifera L.) e uma rica fonte de nutrientes e, assim como outras plantas e alvo de ataque de diferentes tipos de pragas e doencas, causando prejuizos aos produtores. O uso de pesticidas continua sendo a principal estrategia de controle e combate de pragas e doencas nas plantacoes agricolas. No entanto, o uso excessivo e indiscriminado desses produtos podem ocasionar serios danos a saude humana e ao ambiente, devido a elevada toxicidade desses produtos. No Brasil, ate o momento, nao ha valores estipulados de limites maximos de residuos (LMR) para pesticidas na cocoicultura. Do mesmo modo, ha pouca informacao quanto ao grau de contaminacao. Portanto metodologias analiticas tem de ser desenvolvidas para determinacao de residuos de pesticidas na cultura de coqueiro, com intuito de assegura essencialmente a saude humana. Nesse sentido, esse trabalho propoe uma metodologia que determine residuo de bromopropilato, clofentezina, cumafos, difenoxurom, diniconazol, fenvalerato, flumetralina, flumeturom, teflubenzurom em estipe de coqueiro, fazendo uso da tecnica de DMFS para extracao e CL-DAD para analise. Nesse estudo foram avaliados as melhores combinacoes sorvente/solvente (utilizando silica gel, Florisil, alumina neutra, C18, e polimeros de coordenacao [Zn(BDC)(H2O)2]n, [Zn(BDC)0,99(NH2-BDC)0,01)(H2O)2]n, [Zn(BDC)0,95(NH2-BDC)0,05)(H2O)2]n, [Zn(BDC)0,90(NH2-BDC)0,10)(H2O)2]n/acetonitrila). Avaliou-se a melhor relacao de massa amostra/adsorvente, alem do volume do solvente de eluicao utilizado para extracao. Dentre as combinacoes avaliadas, o sistema constituido de 0,25 g de estipe, 1 g de alumina neutra e 5 mL de acetonitrila foi o mais eficiente resultando em recuperacao entre 70 e 93% com precisao entre 1,6% e 10% nos niveis de concentracao 0,04, 0,08, 0,2, 0,4, 2,0, 3,0; 4,0 Êg g-1. As linearidades foram acima de 0,9991 e os limites de deteccao foram entre 0,01 e 0,05 Êg g-1 e de quantificacao entre 0,05 e 0,2 Êg g-1. Entre as fases polimericas estudadas, o [Zn(NH2BDC)0,1(BDC)0,9(H2O)2]n foi o mais eficiente na recuperacao de bromopropilato, clofentezina, cumafos, difenoxurom, diniconazol, fenvalerato, flumetralina, flumeturom e teflubenzurom.
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Dubus, Igor G. "Calibration of pesticide leaching models." Thesis, Cranfield University, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.269528.
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Gokmen, Pinar. "Evaluation Of Persistent Organic Pollutants (pops) In Balikesir Dam Lake Sediments." Master's thesis, METU, 2011. http://etd.lib.metu.edu.tr/upload/12612916/index.pdf.
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In this study, the Persistent Organic Pollutants (POPs) specifically17 Organochlorine Pesticides (OCPs) and 19 Polycyclic Aromatic Hydrocarbons (PAHs) were evaluated in the sediment samples of Balikesir (Ikizcetepeler) Dam Lake. Sixteen sampling points were chosen for determination of concentrations of OCPs and PAHs After ultrasonic bath extraction of the sediment samples GC-MS was used as analytical tool. Extraction efficiencies changes from 63.8 to 87.4% depending on the type of the POPs. Average OCP concentration was found in the range of 3.33-379 µ
g/kg a, average PAH concentration was found in the range of 3.28-32.9 µ
g/kg. Pollution maps regarding OCP and PAH distributions were drawn and the correlation between these two pollutant types was investigated. The quality control (QC) and quality assurance tests were applied by the analysis of standard reference materials (SRMs), surrogate standards and analysis replicates.
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Rios, Magda Dias Gonçalves. "Degradação de atrazina por processo foto-Fenton monitorado por injeção seqüencial e cromatografia a líquido de alta eficiência." Universidade de São Paulo, 2006. http://www.teses.usp.br/teses/disponiveis/46/46133/tde-24052016-110708/.
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Processos de fotodegradação de compostos orgânicos tóxicos têm sido bastante estudados. Este trabalho trata da aplicação do processo foto-Fenton para a degradação de atrazina em água (composto modelo). O efeito das concentrações dos seguintes compostos foi avaliado: peróxido de hidrogênio (2 a 6 mmol L-1) e ferrioxalato de potássio (0,2 a 1 mmol L-1). Os experimentos foram realizados em um reator com lâmpada UV - 8W (254nm). O processo de fotodegradação foi monitorado por medidas de espectrofotometria de absorção molecular automatizada por injeção seqüencial (SIA) para determinação de peróxido de hidrogênio e por cromatografia a líquido de alta eficiência (CLAE) para determinação de atrazina e metabólitos. Os experimentos demonstram que o processo de foto-Fenton é viável para o tratamento de atrazina em água.Photo-degradation processes of toxic organic compounds have been widely studied. This work describes the application of the photo-Fenton process for degradation of atrazine in water. Atrazine was used as a model compound. The effects of the concentration of the following substances were evaluated: hydrogen peroxide (1 to 6 mmol L-1) and potassium ferrioxalate (0.2 to 1 mmol L-1). The experiments were accomplished in a reactor with an 8W UV lamp at 254 nm. The photo-degradation was monitored by molecular absorption spectrophotometry automated by sequential injection analysis (SIA) for determination of hydrogen peroxide and by high performance liquid chromatography (HPLC) for determínation of atrazine and its metabolites. Experimental results demonstrated that the photo-Fenton process is feasíble for the treatment of atrazine.
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Risangud, Nuttapol. "Synthesis and application of new polymers for agriculture : pesticide formulation." Thesis, University of Warwick, 2017. http://wrap.warwick.ac.uk/96908/.
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The objective of this work was to synthesise potential polymeric materials to use in agricultural applications, particularly as pesticide carriers. Synthesis of solid microcapsules, which contain hydrophobic pesticides, from functional polymers, was the primary goal. In addition, promising materials such as poly(dimethylsiloxane) (PDMS) and acid-labile containing polymers were also explored. The extraordinary reactivity of isocyanates towards nucleophiles offers an interesting synthetic tool as a catalyst-free reaction. Unfortunately, the high reactivity of isocyanate during the polymerisation process is a major concern, thus a facile approach in order to synthesise stable functional polymer was first investigated. Chapter 2 details the synthesis of two types of isocyanate side chain containing copolymers, poly(methyl methacrylate-co-isocyanatoethyl methacrylate) (P(MMAm-co-IEMn)) and poly(benzyl methacrylate-co-isocyanatoethyl methacrylate) P(BnMAm-co-IEMn), via Cu(0)-mediated controlled radical polymerisation. Both copolymers were functionalised with dibutylamine, octylamine, and (R)-(+)-α-methylbenzylamine, which further proved the successful incorporation of the isocyanate groups. Subsequently, P(BnMAm-co-IEMn) was used for the fabrication of liquid core microcapsules via an oil-in-water interfacial polymerisation with diethylenetriamine as a crosslinker. Furthermore, chapter 3 illustrates the synthetic route of solid microcapsules containing hydrophobic pesticides; this illustrates the incorporation of biodegradable materials, modern controlled radical polymerisation techniques and isocyanate chemistry. An α, ω-poly (ɛ-caprolactone) SET-LRP initiator is first prepared by esterification to obtain a degradable halide initiator. Subsequently, biodegradable P(BnMAn-co-IEMn) was polymerised via the conditions from chapter 2. An isocyanate-containing copolymer was used to fabricate a microcapsule which consists of imidacloprid (IMI), followed by water removal via spray dryer. Chapter 4 details an efficient tool to synthesise an amphiphilic copolymer containing PDMS. The versatility of hydrosilylation has been exploited for the preparation of an ABA block copolymer of PDMS and poly(ethylene glycol) methacrylate (PEGMA), which can be potentially used to prepare polymeric micelles. Also, to demonstrate the adaptability of this method, different methacrylates and vinyl terminated methacrylic macromonomers were applied to modified hydride terminated PDMS. Finally, the α, ω-hydroxyl terminated poly(acetal) SET-LRP initiator was synthesised from the condensation and esterification reaction. A favourable Cu(0)-mediated controlled radical polymerisation and degradation under an acidic conditions of acetal initiator was affirmed. Thus, this offers a great opportunity of using this initiator to synthesise isocyanate-containing copolymers, certainly, an acid-labile microcapsule to use as an agrochemical carrier is potentially achievable.
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Chunsanit, Suchada. "Pesticide use and training needs of Thai rice farmers : a case study." Thesis, Imperial College London, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.248668.
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Fillatre, Yoann. "Produits phytosanitaires : Développement d'une méthode d'analyse multi-résidus dans les huiles essentielles par couplage de la chromatographie liquide avec la spectrométrie de masse en mode tandem." Phd thesis, Université d'Angers, 2011. http://tel.archives-ouvertes.fr/tel-00675561.
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De nos jours, environ 3000 huiles essentielles sont produites et utilisées dans le monde avec des champs d'application aussi variés que la cosmétique, la parfumerie l'agro-alimentaire, la pharmacie et l'aromathérapie. Ces huiles sont extraites des hespéridés ou des plantes aromatiques et médicinales. Étant donné que la culture de ces matières premières implique généralement l'application de pesticides, la présence de tels résidus dans les huiles essentielles ne peut pas être écartée. Compte tenu du nombre important de pesticides employés et des nombreux champs d'application des huiles essentielles, il apparaît nécessaire, afin d'assurer la santé du consommateur, de disposer d'une méthode d'analyse multi-résidus capable de doser les pesticides dans les huiles essentielles. L'état de l'art des méthodes d'analyse lié à cette problématique a révélé un manque évident de performance des méthodes actuelles aussi bien en termes de limite de détection que du nombre de pesticides analysés. Ce mémoire propose donc la mise au point d'une méthode d'analyse multi-résidus de pesticides dans les huiles essentielles par couplage de la chromatographie liquide et de la spectrométrie de masse, technologie la plus à même de répondre à la problématique au vue de la bibliographie. Après avoir mis en évidence les performances du nouveau mode d'acquisition Scheduled SRM, disponible sur le spectromètre de masse 4000 QTrap, pour la détection et la quantification de 250 pesticides dans un solvant déterminé, l'importance de considérer la nature de la matrice, aussi bien dans les méthodes de préparation que lors de l'analyse de l'échantillon, a ensuite été démontrée en étudiant deux huiles essentielles représentatives (lavandin et citron). Enfin, la méthode d'analyse multi-résidus LC-MS/MS a été appliquée à la recherche de pesticides dans des échantillons réels d'huiles essentielles. Elle a démontré sa capacité à détecter, quantifier et identifier les pesticides dans ces matrices au travers de l'utilisation d'un mode d'acquisition couplé SRM-EPI faisant appel aux spécificités du spectromètre de masse hybride et notamment de sa trappe d'ion linéaire. Ce travail a de plus révélé l'importance de disposer d'une telle méthode au regard du nombre de pesticides détectés dans les échantillons et de leurs concentrations relativement élevées. Celles-ci peuvent en effet atteindre des teneurs supérieures au milligramme par litre dans les huiles essentielles analysées.
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Sgobbi, Lívia Flório. "Desenvolvimento de um biossensor mimético descartável para pesticidas organofosforados e carbamatos para o controle de qualidade de águas de abastecimento." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/75/75135/tde-26042016-141206/.
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A enzima acetilcolinesterase (AChE) tem sido amplamente aplicada no desenvolvimento de biossensores para detecção de pesticidas. No entanto, a aplicação de tais dispositivos é limitada devido à falta de robustez, que está associada com a baixa estabilidade enzimática, além de seu alto custo. Uma alternativa às enzimas é a utilização de moléculas sintéticas que mimetizem o comportamento enzimático, com menor custo e maior estabilidade; tais moléculas são denominadas moléculas biomiméticas. Neste trabalho são apresentados três potenciais catalisadores: o ácido [4-(1E)etanohidrazonoil]benzóico, o iodeto de pralidoxima (2-PAM) e o polímero polihidroxamicalcanoato (PHA); com grupos funcionais alfa nucleófilos hidrazona, oxima e ácido hidroxâmico, respectivamente. Tais moléculas foram avaliadas baseando-se em dois critérios para classificação de biomiméticos da AChE: 1) catálise da hidrólise do substrato acetiltiocolina (ATCh) e 2) interação com pesticida organofosforado. O método espectrofotométrico de Ellman revelou que o polímero PHA foi a molécula mais eficiente, uma vez que a constante de velocidade de segunda ordem obtida foi de 13867 mol-1 L s-1, 5 vezes superior a da 2-PAM e 232 vezes a da hidrazona. Posteriormente, todas as moléculas foram avaliadas por método espectrofotométrico em relação à interação com o organofosforado paraoxon. Apenas o PHA apresentou interação nas condições estudadas. Cálculos teóricos mostraram como ocorre a aproximação entre o PHA e ATCh, e com o paraoxon. Diante dos resultados obtidos, o PHA foi a molécula biomimética escolhida para aplicação no sensor eletroquímico para detecção de organofosforados. Primeiramente, o PHA foi imobilizado na superfície de um eletrodo impresso descartável a partir da formação de uma blenda com o polímero polietileno glicol metil éter, evitando sua solubilização. A oxidação da tiocolina formada a partir da catálise do ATCh realizada pelo PHA imobilizado foi verificada em 0,46 V vs Ag/AgCl, por voltametria de pulso diferencial. A equação obtida a partir da curva de calibração referente ao intervalo de concentração de paraoxon de 1,0 a 10,0 µmol L-1 foi I(%) = [4,8x106 C (mol L-1) + 0,8169]×100 (R2 = 0,99969), com limite de detecção de 3,63x10-7 mol L-1. Amostras de água de abastecimento foram analisadas, com concentrações adicionadas de paraoxon de 3,0; 6,0 e 8,0 µmol L-1, com recuperação de 115%; 106% e 94,5%, respectivamente. Os resultados apresentados mostraram que foi possível desenvolver um sensor eletroquímico biomimético para detecção de pesticida paraoxon.Acetylcholinesterase enzyme (AChE) has been widely applied in biosensor development for pesticide detection. However, the application of those biosensors is limited due to their lack of robustness associated with low enzymatic stability and AChE high cost. An alternative to enzymes, it is the use of synthetic molecules which mimic enzymatic behavior, besides its low cost and superior stability, those are classified as biomimetic molecules. In this work is presented three potential catalysts: [4-(1E)ethanehydrazonoyl]benzoic acid, pralidoxime iodide (2-PAM), and polyhydroxamicalkalnoate polymer (PHA) with alpha nucleophile functional groups, such as hydrazone, oxime, and hydroxamic acid, respectively. The aforementioned molecules were evaluated based on two criteria for classification as AChE biomimetic: 1) catalysis of acetylthiocholine substrate (ATCh) hydrolysis and 2) interaction with organophosphorus pesticide. Spectrophotometrical Ellman´s method revealed that PHA polymer was the most efficient one, since its second order rate constant was 13867 mol-1 L s-1, which was 5 times superior than 2-PAM one and 232 times higher than hydrazone. Then, each molecule was analyzed through spectrophotometric method to verify the interaction with paraoxon organophosphorus pesticide. Only the PHA exhibited such interaction in the studied conditions. Theoretical calculations showed how the approach between PHA and ATCh, and also with paraoxon occurred. Regarding the obtained results, PHA was the chosen biomimetic molecule to be applied in the electrochemical sensor for organophosphorus detection. First of all, PHA was immobilized on the surface of disposable screen printed electrode through blend formation with polyethylene glycol methyl ether (mpEG), avoiding PHA dissolution. The oxidation of thiocholine generated towards ATCh catalysis performed by immobilized PHA was verified at 0.46 V vs Ag/AgCl by differential pulse voltammetry. The linear equation obtained through calibration curve for paraoxon concentration range of 1.0 to 10.0 µmol L-1 was I(%) = [4.8x106 C (mol L-1) + 0.8169]×100 (R2 = 0.99969), with limit of detection of 3.63x10-7 mol L-1. Water supply samples were analyzed considering the added paraoxon concentrations of 3.0; 6.0 e 8.0 µmol L-1, recovering 115%; 106% and 94.5%, respectively. The presented results showed that a biomimetic electrochemical sensor was successfully developed for detection of paraoxon organophosphorus pesticide.
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Mézin, Laurent C. "Effects of humic acids and salinity on pesticide bioavailability and toxicity as estimated by SPME and toxicity tests." W&M ScholarWorks, 2001. https://scholarworks.wm.edu/etd/1539616775.
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The interactive effects of humic acids (HAs) and salinity on the bioavailability and toxicity of the pesticides chlorpyrifos and 4,4'-dichlorodiphenyltrichloroethane (DDT) were investigated. The effects of various HAs on the toxicity of chlorpyrifos were initially assessed with the chronic MicrotoxRTM test. Environmentally relevant concentrations of Aldrich, Peat, Leonardite and Suwannee River HAs had no significant effect on the toxicity of either chlorpyrifos or copper (Cu), the test's positive control. as reductions in contaminant toxicity had previously been reported for some contaminants by HAs, it appeared that salinity might be a mitigating factor. Thus salinity effects were further investigated with Aldrich HA only, in freshwater and at lower salinities. HA-pesticide associations were assessed through the pesticides' relative uptake by solid-phase microextraction (SPME) in the presence of Aldrich HA. Such binding has been hypothesized to reduce contaminant bioavailability. Increasing salinity (0--20 ppt) had no effect on the uptake of DDT by SPME, but generally enhanced that of chlorpyrifos. Aldrich HA alone greatly decreased the relative uptake of both pesticides at environmentally relevant DOM concentrations (∼0--20 mg C/l), and the effect was more pronounced for DDT. Increases in salinity reduced the effects of HA on uptake by SPME, and seemed to have an "effect threshold" between 1 and 5 ppt. to examine the biological consequences of possible HA-salinity interactions, the acute toxicities of chlorpyrifos and DDT were assessed using both freshwater (Ceriodaphnia dubia) and saltwater (Americamysis bahia) crustaceans. The DDT 24 hour LC50 for C. dubia was 1050 ng/l. No definitive value was obtained for A. bahia. CPF was more acutely toxic, with LC50s of 326 ng/l for A. bahia and 78.8 ng/l for C. dubia. Results of the acute toxicity experiments were in good agreement with the SPME data; i.e. while pesticide toxicities were reduced by HAs in freshwater, no reductions were seen in saline water (20 ppt). The toxicity reduction in freshwater was proportional to the HA concentration. The difference in toxicity mitigation is believed to be a function of salinity effects on HA-pesticide binding, likely due to conformational changes in the HA molecules, rather than organismal effects.
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Oztas, Nur Banu. "Pesticide Pollution In Surface And Ground Water Of An Agricultural Area, Kumluca, Turkey." Phd thesis, METU, 2007. http://etd.lib.metu.edu.tr/upload/3/12609445/index.pdf.
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Concentrations of 17 organochlorine and 14 organophosphorus pesticides were measured in 27 ground and 11 surface water samples collected from a heavily agricultural area, Kumluca, in spring and fall seasons of 2005. The samples were preconcentrated by Solid Phase Extraction. GC-ECD and GC-NPD systems were used for quantitative determination of organochlorine and organophosphorus pesticides respectively.
The quality check/quality assurance tests were performed by the analysis of field and laboratory blanks, standard reference materials, spiked control and sample matrices, surrogate standards, sampling and analysis replicates. It is observed that, sample matrix lowers average percent recoveries from 89% to 76%.
The uncertainties of measurements were calculated to determine major factors affecting the analysis results. It was observed that uncertainty arising from extraction procedure was generally the highest.
The most commonly observed pesticide was endosulfan (70%) and chlorpyriphos (53%) for organophosphorus and organochlorine pesticides. The highest average concentration was observed for heptachlor (26 ng/L) and fenamiphos (184 ng/L).
Generally pesticides were detected more often in surface waters, where the concentrations were also higher. The concentrations of organophosphorus pesticides in spring, and organochlorine pesticides in fall season were higher.
The high occurrences and detection of degradation products of chlorinated pesticides clearly indicate their intense use before 1980s. It is shown that, in Kumluca environment, degradation of these pesticides mostly occurs in surface waters.
It is observed that agricultural activities affect water quality in the region. The total concentration limit (500ng/L) was exceeded for 27% of surface and 14% of ground water samples, at least once in both seasons. The legal limit for a single pesticide (100ng/L) was exceeded by 32 % of surface, 24 % of ground water samples.
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Toledo, Netto Pedro. "Exposição à mistura de pesticidas em baixas doses : validação de método e aplicação a tecido adiposo de animais de experimentação (ratos Lewis) /." Araraquara : [s.n.], 2009. http://hdl.handle.net/11449/97812.
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Resumo: A presença de pesticidas em matrizes ambientais e biológicas vem sendo investigada há décadas e estudos sobre a atuação de baixas concentrações destes contaminantes, como possíveis alteradores endócrinos e agentes carcinogênicos, ainda são incipientes. Portanto, o desenvolvimento de métodos analíticos para determinação destes compostos em matrizes biológicas torna-se necessário para se ter uma estimativa da quantidade que pode ser bioacumulada e relacioná-la ao desenvolvimento de alterações em diversos tecidos do organismo. O objetivo deste trabalho foi desenvolver e validar um método eficiente e rápido para determinação de resíduos dos pesticidas dicofol, dieldrin, endosulfan e permetrina em matriz de tecido adiposo de ratos. Estes pesticidas foram selecionados por apresentarem controvérsias quanto aos efeitos nocivos que podem causar ao homem, como por exemplo desregulação do sistema endócrino e, coincidentemente, por terem sido encontrados pela Agência Nacional de Vigilância Sanitária (ANVISA) em matrizes vegetais consumidas pela população brasilerira nos últimos anos. A principal dificuldade do trabalho foi estabelecer um procedimento experimental que permitisse a remoção de lipídios. Nesse sentido diversas condições experimentais foram avaliadas para eliminação destas macromoléculas, entre elas: extração em fase sólida, dispersão da matriz em fase sólida, envolvendo combinações de diversos adsorventes e extração por congelamento da amostra. Finalmente o método otimizado incluiu a extração das amostras de tecido adiposo com hexano em banho de ultrasom, seguida da extração em fase sólida (alumina) utilizando uma alíquota (1 mL) do extrato, sendo a eluição processada com hexano:diclorometano e, finalmente a concentração do eluato a secura, sua redissolução em isooctano e análise por GC/ECD. O método foi validado com sucesso... (Resumo completo, clicar acesso eletrônico abaixo)Abstract: The presence of pesticides in environmental and biological materials have been known for decades, but studies regarding their low concentration on potential carcinogenic and endocrine disruption effects are only beggining. Therefore, the development of quantitative analytical methods for pesticides in complex biological samples is important not only to estimate pesticide accumulation but also to evaluate possible tissue damages. The aim of this work was to develop and validade a simple, fast and senstive method for the pesticides dicofol, dieldrin, endosulfan and permethrin in rat adipose tissue. These specific molecules have been selected because they are the most frequently found in fruit and vegetables consumed in Brazil, according a survey performed by the National Health Surveillance Agency (Anvisa) and because they have been recently found to affect the endocrine system. The stablishment of an efficient procedure to eliminate lipids was a very difficult step. Therefore, several combinations of sorbents and eluents were tested copled to solid phase extraction, matrix solid phase dispersion and sample freezing extraction. Finally the optimized method includes the extraction from rat adipose tissue samples with hexane in ultrasonic bath. The resulting extract is submitted to solid phase extraction using alumina and eluted with hexane:dichloromethane. Extracted solvent was dried and redissolved in isooctane and analysed by GC/ECD. The method was sucessfully validated by following parameters: linearity range (analytical curve in sample extract): 5 to 1200 ng g-1; recovery at three different levels of sample fortification (50, 100 and 500 ng g-1 for dieldrin and endosulfan, 500, 1000 and 5000 ng g-1 for dicofol and permethrin); accuracy (recovery:75 - 119%); precision (coefficient of variation: 3 - 19%); selectivity... (Complete abstract click electronic access below)
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