Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS
Ano de defesa: | 2011 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4212 |
Resumo: | Due to the complexity of grains like soybean, corn and rice, and the very low pesticide concentration expected for these samples, it is really necessary to develop efficient and reliable analytical methods to identify and quantify their residues. The possibility to perform the determination of a large number of pesticides in just a single chromatographic analysis is the major advantage of the multi-residue methods. However, there are important compounds that are not possible to be analyzed together, like the dithiocarbamates (DTC). For that, is so important to develop and validate single methods. Due to low acute toxicity, combined with strong action, low-cost production and low environmental persistence, the dithiocarbamates are still using worldwide. The first part of this study reports a sensitive analytical single method suitable for the quantitative analysis of DTCs in soybeans, rice and corn, using GC-PFPD and GCITD- MS. For the method validation studies, the following parameters were assessed: detection limit (LOD), quantification limit (LOQ), precision (repeatability and intermediate precision) and accuracy, via recovery experiments at 0.05, 0.1 and 0.5 mg CS2 kg-1 spiking levels. For soybeans is necessary a clean-up step due the high fat content in that crop, because of it, same sorbents (Aluminum oxide, Florisil®, Silica, PSA, C18 and C18OH) were tested and the best results were obtained applying silica gel. For the extraction procedure, an amount of sample was weighed and water added. The spike solution (thiram) was added to the sample, 25 mL of isoctane and 150 mL of tin (II) chloride solution in hydrochloric acid were added. The bottles were closed immediately and heated for 1 h in a water bath at 80 °C, under shaking. After cooling, 2 mL aliquot of the upper organic layer of each bottle was pipetted into a tube containing 50 mg of silica gel, for the clean-up step. The analytical curves were linear from 0.02 to 1.0 mg CS2 L-1 with determination coefficients (r2) higher than 0.99 for both detection systems and to all crops. Method LOD and LOQ values were 20 and 50 μg CS2 kg-1, respectively, for soybeans and corn. For rice LOQ was just 40 μg CS2 kg-1. Very good precision was obtained with RSD between 1.8 and 7.9% and recoveries from 67 to 103%, for all matrices. The results obtained in the validation step allow us to conclude that both chromatographic detection systems are appropriate to determine residues of DTCs in grains. The second step was to develop and validate a method for the analysis of 75 pesticides in corn grain and breakfast cereals using LC-MS/MS, ESI positive mode. The extraction procedure was the modified QuEChERS method, however, excluding the dispersive SPE clean-up step. To that end, milled and homogenized corn grain and breakfast cereals with water were spiked with 75 pesticides, at 3 spiking levels (10, 20 and 50 μg kg-1, n=6), plus the procedure internal standard (quinalfos). A volume of 10 mL of acetonitrile with 1% acetic acid was added and the tubes were vigorously shaken for 1 minute. The tubes were uncapped, anhydrous magnesium sulfate were added, the shaking procedure was repeated and the extract was centrifuged at 4000 rpm, for 4 min. The upper layer of the extracts was transferred to chromatographic vial, containing 0.5 mL of the instrumental internal standard (propoxur) in methanol. The linear range wasevaluated and validated between 0.1 and 50 μg L-1 of the analytical curves (7 concentrations, n=6). Also LOD, LOQ, matrix effect, as well as precision (as RSD%) and accuracy (as recovery), for 75 pesticides, were studied The LOD were calculated based on practically realized repeatability RSD. To determine the precision, accuracy and LOQ, blank samples were spiked at 10, 20 and 50 μg kg-1. The results showed recoveries between 70 and 120% and RSDs <20% for the majority of the pesticides studied, even at the lowest level. As expected, the matrix effect did not have influence on the results, and the values of LOD and r2 were considered as satisfactory for the purpose of this study. |
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2017-05-252017-05-252011-08-29SILVA, Rosselei Caiél da. Single and multi-residue methods for pesticide analysis in grains and derivates by GC-PFPD, GC-ITD-MS and LC-MS/MS. 2011. 160 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2011.http://repositorio.ufsm.br/handle/1/4212Due to the complexity of grains like soybean, corn and rice, and the very low pesticide concentration expected for these samples, it is really necessary to develop efficient and reliable analytical methods to identify and quantify their residues. The possibility to perform the determination of a large number of pesticides in just a single chromatographic analysis is the major advantage of the multi-residue methods. However, there are important compounds that are not possible to be analyzed together, like the dithiocarbamates (DTC). For that, is so important to develop and validate single methods. Due to low acute toxicity, combined with strong action, low-cost production and low environmental persistence, the dithiocarbamates are still using worldwide. The first part of this study reports a sensitive analytical single method suitable for the quantitative analysis of DTCs in soybeans, rice and corn, using GC-PFPD and GCITD- MS. For the method validation studies, the following parameters were assessed: detection limit (LOD), quantification limit (LOQ), precision (repeatability and intermediate precision) and accuracy, via recovery experiments at 0.05, 0.1 and 0.5 mg CS2 kg-1 spiking levels. For soybeans is necessary a clean-up step due the high fat content in that crop, because of it, same sorbents (Aluminum oxide, Florisil®, Silica, PSA, C18 and C18OH) were tested and the best results were obtained applying silica gel. For the extraction procedure, an amount of sample was weighed and water added. The spike solution (thiram) was added to the sample, 25 mL of isoctane and 150 mL of tin (II) chloride solution in hydrochloric acid were added. The bottles were closed immediately and heated for 1 h in a water bath at 80 °C, under shaking. After cooling, 2 mL aliquot of the upper organic layer of each bottle was pipetted into a tube containing 50 mg of silica gel, for the clean-up step. The analytical curves were linear from 0.02 to 1.0 mg CS2 L-1 with determination coefficients (r2) higher than 0.99 for both detection systems and to all crops. Method LOD and LOQ values were 20 and 50 μg CS2 kg-1, respectively, for soybeans and corn. For rice LOQ was just 40 μg CS2 kg-1. Very good precision was obtained with RSD between 1.8 and 7.9% and recoveries from 67 to 103%, for all matrices. The results obtained in the validation step allow us to conclude that both chromatographic detection systems are appropriate to determine residues of DTCs in grains. The second step was to develop and validate a method for the analysis of 75 pesticides in corn grain and breakfast cereals using LC-MS/MS, ESI positive mode. The extraction procedure was the modified QuEChERS method, however, excluding the dispersive SPE clean-up step. To that end, milled and homogenized corn grain and breakfast cereals with water were spiked with 75 pesticides, at 3 spiking levels (10, 20 and 50 μg kg-1, n=6), plus the procedure internal standard (quinalfos). A volume of 10 mL of acetonitrile with 1% acetic acid was added and the tubes were vigorously shaken for 1 minute. The tubes were uncapped, anhydrous magnesium sulfate were added, the shaking procedure was repeated and the extract was centrifuged at 4000 rpm, for 4 min. The upper layer of the extracts was transferred to chromatographic vial, containing 0.5 mL of the instrumental internal standard (propoxur) in methanol. The linear range wasevaluated and validated between 0.1 and 50 μg L-1 of the analytical curves (7 concentrations, n=6). Also LOD, LOQ, matrix effect, as well as precision (as RSD%) and accuracy (as recovery), for 75 pesticides, were studied The LOD were calculated based on practically realized repeatability RSD. To determine the precision, accuracy and LOQ, blank samples were spiked at 10, 20 and 50 μg kg-1. The results showed recoveries between 70 and 120% and RSDs <20% for the majority of the pesticides studied, even at the lowest level. As expected, the matrix effect did not have influence on the results, and the values of LOD and r2 were considered as satisfactory for the purpose of this study.Devido a complexidade de matrizes de grãos como soja, milho e arroz, e das baixas concentrações dos pesticidas presentes, há uma grande necessidade de desenvolvimento de métodos analíticos eficientes e confiáveis para a identificação e quantificação desses resíduos. A maior vantagem de um método multirresidual é a possibilidade de se determinar um grande número de pesticidas na mesma análise cromatográfica. Entretanto, alguns compostos, devido suas características específicas, não podem ser determinados em conjunto com outros analitos. Assim, é importante que também se desenvolva e valide métodos individuais de análise, comoo método para determinação de ditiocarbamatos (DTC). Os DTC apresentam baixa toxicidade aguda, combinado com forte ação fúngica, baixo custo e baixa persistência ambiental, por isto, estes continuam sendo largamente utilizados na agricultura. Na primeira parte deste estudo, foi desenvolvido um método individual de análise para determinar DTC em soja, arroz e milho, empregando GC-PFPD e GC-ITD-MS. Para o estudo de validação do método, os seguintes parâmetros foram avaliados: limite de detecção (LOD), limite de quantificação (LOQ), precisão e exatidão, através do estudo de fortificação e recuperação, nas seguintes concentrações: 0,05; 0,1 e 0,5 mg CS2 kg-1. Para a determinação de ditiocarbamatos, adicionou-se um volume de água à amostra (arroz, milho e soja). Fortificou-se com solução de tiram, adicionou-se 25 mL de isoctano e 150 mL de solução de SnCl2 em HCl. Os frascos foram fechados e levados ao banho de agitação, a 80 °C, por 1 hora. Após o resfriamento, 2 mL da fase orgânica foram transferidos para outro frasco contendo 50 mg de sílica gel, para a etapa de purificação. As curvas analíticas foram lineares na faixa de 0,02 a 1,0 mg CS2 L-1, com coeficiente de determinação (r2) maior do que 0,99, para todas as culturas, nos dois sistemas de detecção. O LOD e LOQ do método apresentaram os mesmos valores para soja e milho, sendo, respectivamente, 20 e 50 μg CS2 kg-1. Já o LOQ para arroz foi de 62 μg CS2 kg-1, devido a menor quantidade de amostra utilizada. Observa-se, desta forma, que os valores de LOQ encontrados são inferiores ao limites máximos de resíduos permitidos (LMR) pela legislação nacional, que são de 0,3 mg CS2 kg-1 para soja e milho, e de 3 mg CS2 kg-1 para o arroz, indicando que os métodos podem ser utilizados para este tipo de determinação. A precisão mostrou-se muita boa, com valores de RSD entre 1,8 e 8,7%, e recuperações de 63 a 103%. Assim, os resultados obtidos pela validação do método permitem concluir que ambos os sistemas cromatográficos são adequados para determinar DTC em grãos. A segunda etapa do estudo foi validar o método multirresidual para determinação de 75 pesticidas em milho (grão) e cereais matinais, empregando LCMS/ MS, no modo ESI positivo. O procedimento de extração foi baseado no método QuEChERS, com algumas modificações. Grãos de milho e cereais matinais foram moídos e homogeneizados, e um volume de água de, respectivamente, 7,5 e 8 mL foi adicionado. Após, executou-se a fortificação com uma solução contendo os 75 pesticidas do estudo, nos níveis de concentração de 10, 20 e 50 μg kg-1. Um volume de 10 mL de solução de ácido acético 1% em acetonitrila contendo o padrão interno quinalfós foi adicionado, e os tubos agitados por 1 minuto. Os tubos foram abertos e MgSO4 anidro adicionado seguido de agitação e centrifugação a 4000 rpm, por 4 minutos. Um volume de 0,5 mL da fase superior foi transferido para vial contendo 0,5 mL do padrão interno propoxur em metanol. Os resultados obtidos para esta validação foram satisfatórios. Recuperações entre 70 e 120%, com RSD <20% foram obtidos para a maioria dos pesticidas estudados, nas duas matrizes, conforme recomendando pela SANCO (2009). Conforme esperado em LC-MS/MS, o efeito matriz não influenciou os resultados.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaPesticidasDitiocarbamatosGrãosCromatografia gasosaCromatografia líquidaEspectrometria de massasPesticidesDithiocarbamatesGrainGas chromatographyTandem liquid chromatographyCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAMétodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MSSingle and multi-residue methods for pesticide analysis in grains and derivates by GC-PFPD, GC-ITD-MS and LC-MS/MSinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisCardoso, Carmem Dickowhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4792018P1Pizzutti, Ionara Reginahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797011T5Schneider, Rosana de Cassia de Souzahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4790001A1Rossi, Rochele Cassantahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4764348T9Césio, Maria Verónicahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4702731E3Silva, Rosselei Caiél da1006000000004003003003003003003005e6c09b1-2827-4a21-8cfd-185f61a7916148829437-e618-4b83-afcd-e4d79ede85eb45db26b1-d4ae-4ebb-bf81-7679f7fe5486a7243a36-17d0-4480-aaf4-1e61e9bc4ef429544f6f-d71e-4a71-8806-4f825073950f009f80b2-cb8e-4a27-bc21-9195c0d243c4info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALSILVA, ROSSELEI CAIEL DA.pdfapplication/pdf3126960http://repositorio.ufsm.br/bitstream/1/4212/1/SILVA%2c%20ROSSELEI%20CAIEL%20DA.pdf418e8277971171300d7bba9f280fdfb2MD51TEXTSILVA, ROSSELEI CAIEL DA.pdf.txtSILVA, ROSSELEI CAIEL DA.pdf.txtExtracted texttext/plain252325http://repositorio.ufsm.br/bitstream/1/4212/2/SILVA%2c%20ROSSELEI%20CAIEL%20DA.pdf.txt8dd4f0f51389826a41c38713c99f1ae7MD52THUMBNAILSILVA, ROSSELEI CAIEL DA.pdf.jpgSILVA, ROSSELEI CAIEL DA.pdf.jpgIM Thumbnailimage/jpeg5183http://repositorio.ufsm.br/bitstream/1/4212/3/SILVA%2c%20ROSSELEI%20CAIEL%20DA.pdf.jpge315a7031ce9ae4ed14618d81d8e6dddMD531/42122017-07-25 11:05:12.273oai:repositorio.ufsm.br:1/4212Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T14:05:12Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS |
dc.title.alternative.eng.fl_str_mv |
Single and multi-residue methods for pesticide analysis in grains and derivates by GC-PFPD, GC-ITD-MS and LC-MS/MS |
title |
Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS |
spellingShingle |
Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS Silva, Rosselei Caiél da Pesticidas Ditiocarbamatos Grãos Cromatografia gasosa Cromatografia líquida Espectrometria de massas Pesticides Dithiocarbamates Grain Gas chromatography Tandem liquid chromatography CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS |
title_full |
Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS |
title_fullStr |
Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS |
title_full_unstemmed |
Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS |
title_sort |
Métodos individual e multirresidual para determinação de pesticidas em grãos e derivados por GC-PFPD, GC-ITD-MS e LC-MS/MS |
author |
Silva, Rosselei Caiél da |
author_facet |
Silva, Rosselei Caiél da |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Cardoso, Carmem Dickow |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4792018P1 |
dc.contributor.advisor-co1.fl_str_mv |
Pizzutti, Ionara Regina |
dc.contributor.advisor-co1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797011T5 |
dc.contributor.referee1.fl_str_mv |
Schneider, Rosana de Cassia de Souza |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4790001A1 |
dc.contributor.referee2.fl_str_mv |
Rossi, Rochele Cassanta |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4764348T9 |
dc.contributor.referee3.fl_str_mv |
Césio, Maria Verónica |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4702731E3 |
dc.contributor.author.fl_str_mv |
Silva, Rosselei Caiél da |
contributor_str_mv |
Cardoso, Carmem Dickow Pizzutti, Ionara Regina Schneider, Rosana de Cassia de Souza Rossi, Rochele Cassanta Césio, Maria Verónica |
dc.subject.por.fl_str_mv |
Pesticidas Ditiocarbamatos Grãos Cromatografia gasosa Cromatografia líquida Espectrometria de massas |
topic |
Pesticidas Ditiocarbamatos Grãos Cromatografia gasosa Cromatografia líquida Espectrometria de massas Pesticides Dithiocarbamates Grain Gas chromatography Tandem liquid chromatography CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Pesticides Dithiocarbamates Grain Gas chromatography Tandem liquid chromatography |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Due to the complexity of grains like soybean, corn and rice, and the very low pesticide concentration expected for these samples, it is really necessary to develop efficient and reliable analytical methods to identify and quantify their residues. The possibility to perform the determination of a large number of pesticides in just a single chromatographic analysis is the major advantage of the multi-residue methods. However, there are important compounds that are not possible to be analyzed together, like the dithiocarbamates (DTC). For that, is so important to develop and validate single methods. Due to low acute toxicity, combined with strong action, low-cost production and low environmental persistence, the dithiocarbamates are still using worldwide. The first part of this study reports a sensitive analytical single method suitable for the quantitative analysis of DTCs in soybeans, rice and corn, using GC-PFPD and GCITD- MS. For the method validation studies, the following parameters were assessed: detection limit (LOD), quantification limit (LOQ), precision (repeatability and intermediate precision) and accuracy, via recovery experiments at 0.05, 0.1 and 0.5 mg CS2 kg-1 spiking levels. For soybeans is necessary a clean-up step due the high fat content in that crop, because of it, same sorbents (Aluminum oxide, Florisil®, Silica, PSA, C18 and C18OH) were tested and the best results were obtained applying silica gel. For the extraction procedure, an amount of sample was weighed and water added. The spike solution (thiram) was added to the sample, 25 mL of isoctane and 150 mL of tin (II) chloride solution in hydrochloric acid were added. The bottles were closed immediately and heated for 1 h in a water bath at 80 °C, under shaking. After cooling, 2 mL aliquot of the upper organic layer of each bottle was pipetted into a tube containing 50 mg of silica gel, for the clean-up step. The analytical curves were linear from 0.02 to 1.0 mg CS2 L-1 with determination coefficients (r2) higher than 0.99 for both detection systems and to all crops. Method LOD and LOQ values were 20 and 50 μg CS2 kg-1, respectively, for soybeans and corn. For rice LOQ was just 40 μg CS2 kg-1. Very good precision was obtained with RSD between 1.8 and 7.9% and recoveries from 67 to 103%, for all matrices. The results obtained in the validation step allow us to conclude that both chromatographic detection systems are appropriate to determine residues of DTCs in grains. The second step was to develop and validate a method for the analysis of 75 pesticides in corn grain and breakfast cereals using LC-MS/MS, ESI positive mode. The extraction procedure was the modified QuEChERS method, however, excluding the dispersive SPE clean-up step. To that end, milled and homogenized corn grain and breakfast cereals with water were spiked with 75 pesticides, at 3 spiking levels (10, 20 and 50 μg kg-1, n=6), plus the procedure internal standard (quinalfos). A volume of 10 mL of acetonitrile with 1% acetic acid was added and the tubes were vigorously shaken for 1 minute. The tubes were uncapped, anhydrous magnesium sulfate were added, the shaking procedure was repeated and the extract was centrifuged at 4000 rpm, for 4 min. The upper layer of the extracts was transferred to chromatographic vial, containing 0.5 mL of the instrumental internal standard (propoxur) in methanol. The linear range wasevaluated and validated between 0.1 and 50 μg L-1 of the analytical curves (7 concentrations, n=6). Also LOD, LOQ, matrix effect, as well as precision (as RSD%) and accuracy (as recovery), for 75 pesticides, were studied The LOD were calculated based on practically realized repeatability RSD. To determine the precision, accuracy and LOQ, blank samples were spiked at 10, 20 and 50 μg kg-1. The results showed recoveries between 70 and 120% and RSDs <20% for the majority of the pesticides studied, even at the lowest level. As expected, the matrix effect did not have influence on the results, and the values of LOD and r2 were considered as satisfactory for the purpose of this study. |
publishDate |
2011 |
dc.date.issued.fl_str_mv |
2011-08-29 |
dc.date.accessioned.fl_str_mv |
2017-05-25 |
dc.date.available.fl_str_mv |
2017-05-25 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
SILVA, Rosselei Caiél da. Single and multi-residue methods for pesticide analysis in grains and derivates by GC-PFPD, GC-ITD-MS and LC-MS/MS. 2011. 160 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2011. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4212 |
identifier_str_mv |
SILVA, Rosselei Caiél da. Single and multi-residue methods for pesticide analysis in grains and derivates by GC-PFPD, GC-ITD-MS and LC-MS/MS. 2011. 160 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2011. |
url |
http://repositorio.ufsm.br/handle/1/4212 |
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MD5 MD5 MD5 |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
|
_version_ |
1794524333156073472 |