Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas
Ano de defesa: | 2018 |
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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
Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
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Departamento: |
Química
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País: |
Brasil
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Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/15713 |
Resumo: | Besides the possibility to perform determination of a large number of pesticides in only a single chromatographyc analysis using multiresidual methods, sometimes, due to diversity in pesticides chemical composition and particular characteristics, it is still required develop single-residue method, such as for dithiocarbamates (DTC). Therefore, in this study, firstly, was optimized and validated a single method to determine DTC (mancozeb) in biobeds using GC-MS to evaluate biobeds efficiency on DTC degradation. Validation study was performed and assessed the analytical curve linearity (r2), detection and quantification limits (LOD and LOQ), accuracy (recovery%), precision (RSD%) and matrix effect. Recovery experiments were carried out with a standard spiking solution of the DTC pesticide thiram. Blank biomixture samples were spiked at the three levels corresponding to the CS2 concentrations of 1, 3 and 5 mg kg-1, with seven replicates each (n = 7). The method presented recoveries within the range of 89-96% and RSD ≤ 11%. The analytical curves were linear in the concentration range of 0.05 to 10 μg CS2 mL-1 (r2 > 0.9946). LOD and LOQ were 0.2 and 1.0 mg CS2 kg-1, respectively, and the calculated matrix effects were not significant (≤ 20%). The validated method was applied to 80 samples (biomixture), from sixteen different biobeds. Ten percent of samples presented CS2 concentration below the LOD (0.2 mg CS2 kg-1) and 70% of them showed results below the LOQ (1.0 mg CS2 kg-1), which demonstrates the biobeds capability to degrade DTC. The second step was to devepol and validated a method (modification of the New Dutch mini-Luke method) for multiresidue determination of captan and its degradation product (tetrahydrophytalimide), chlorothalonil, chlorpyrifos-ethyl, fenithrothion, methidathion, phosmet and tebuconazole in biobed, using GC-MS/MS. The dichloromethane use and the evaporation step were eliminated. This improvement avoids chlorinated solvents use and allows final extract direct injection into the GC-MS/MS system. After method optimization, validation study was performed based on SANTE Guidance Document. Linearity of analytical curves (r2), residuals, limits of detection (LOD) and quantification (LOQ) and matrix effects (%), were assessed by the analysis of standards solutions prepared in organic solvent and in blank biobed extract at eight concentrations, with seven replicate injections of each standard solution. Accuracy (as recoveries %) precision (as repeatability of recoveries experiments-RSD% and as intermediate precision) were also determinate. Two labeled internal standards were used for quality control. PCB-153 was used as procedure internal standard (P.I.S.), and HCB-C13 was used as instrument internal standard (I.I.S.). Recovery study was performed by the analysis of blank biobed samples spiked at 50, 100 and 200 μg kg-1 (n=7). All pesticides presented average recoveries within the range of 74 and 117%, except captan which was indirectly detected via tetrahydrophytalimide, its degradation product, and also had acceptable recoveries. The RSD values calculated from the 7 replicated recovery samples at 3 concentration levels were below 20% (2 to 14%). The residuals was lower than 20% for all pesticides. The method was linear within the range of 1 to 300 ng mL-1 for 2 pesticides and of 5 to 300 ng mL-1 for 4 pesticides and for tetrahydrophytalimide (the degradation product of captan). The r2 of the analytical curves calculated from matrix-matched standards were > 0.99 for all pesticides except for chlorpyrifos-ethyl, that had an r2 0.98. All studied pesticides presented the LODs of 10 or 20 μg kg-1 and LOQs of 50 μg kg-1. The calculated matrix effects were higher than 25% for all pesticides, excepted for chlorpiripfós-ethyl, that was -20%. |
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2019-02-22T12:38:45Z2019-02-22T12:38:45Z2018-06-08http://repositorio.ufsm.br/handle/1/15713Besides the possibility to perform determination of a large number of pesticides in only a single chromatographyc analysis using multiresidual methods, sometimes, due to diversity in pesticides chemical composition and particular characteristics, it is still required develop single-residue method, such as for dithiocarbamates (DTC). Therefore, in this study, firstly, was optimized and validated a single method to determine DTC (mancozeb) in biobeds using GC-MS to evaluate biobeds efficiency on DTC degradation. Validation study was performed and assessed the analytical curve linearity (r2), detection and quantification limits (LOD and LOQ), accuracy (recovery%), precision (RSD%) and matrix effect. Recovery experiments were carried out with a standard spiking solution of the DTC pesticide thiram. Blank biomixture samples were spiked at the three levels corresponding to the CS2 concentrations of 1, 3 and 5 mg kg-1, with seven replicates each (n = 7). The method presented recoveries within the range of 89-96% and RSD ≤ 11%. The analytical curves were linear in the concentration range of 0.05 to 10 μg CS2 mL-1 (r2 > 0.9946). LOD and LOQ were 0.2 and 1.0 mg CS2 kg-1, respectively, and the calculated matrix effects were not significant (≤ 20%). The validated method was applied to 80 samples (biomixture), from sixteen different biobeds. Ten percent of samples presented CS2 concentration below the LOD (0.2 mg CS2 kg-1) and 70% of them showed results below the LOQ (1.0 mg CS2 kg-1), which demonstrates the biobeds capability to degrade DTC. The second step was to devepol and validated a method (modification of the New Dutch mini-Luke method) for multiresidue determination of captan and its degradation product (tetrahydrophytalimide), chlorothalonil, chlorpyrifos-ethyl, fenithrothion, methidathion, phosmet and tebuconazole in biobed, using GC-MS/MS. The dichloromethane use and the evaporation step were eliminated. This improvement avoids chlorinated solvents use and allows final extract direct injection into the GC-MS/MS system. After method optimization, validation study was performed based on SANTE Guidance Document. Linearity of analytical curves (r2), residuals, limits of detection (LOD) and quantification (LOQ) and matrix effects (%), were assessed by the analysis of standards solutions prepared in organic solvent and in blank biobed extract at eight concentrations, with seven replicate injections of each standard solution. Accuracy (as recoveries %) precision (as repeatability of recoveries experiments-RSD% and as intermediate precision) were also determinate. Two labeled internal standards were used for quality control. PCB-153 was used as procedure internal standard (P.I.S.), and HCB-C13 was used as instrument internal standard (I.I.S.). Recovery study was performed by the analysis of blank biobed samples spiked at 50, 100 and 200 μg kg-1 (n=7). All pesticides presented average recoveries within the range of 74 and 117%, except captan which was indirectly detected via tetrahydrophytalimide, its degradation product, and also had acceptable recoveries. The RSD values calculated from the 7 replicated recovery samples at 3 concentration levels were below 20% (2 to 14%). The residuals was lower than 20% for all pesticides. The method was linear within the range of 1 to 300 ng mL-1 for 2 pesticides and of 5 to 300 ng mL-1 for 4 pesticides and for tetrahydrophytalimide (the degradation product of captan). The r2 of the analytical curves calculated from matrix-matched standards were > 0.99 for all pesticides except for chlorpyrifos-ethyl, that had an r2 0.98. All studied pesticides presented the LODs of 10 or 20 μg kg-1 and LOQs of 50 μg kg-1. The calculated matrix effects were higher than 25% for all pesticides, excepted for chlorpiripfós-ethyl, that was -20%.Embora o emprego dos métodos multirresiduais possibilite a determinação de um grande número de agrotóxicos em uma única análise cromatográfica, para agrotóxicos da classe dos ditiocarbamatos (DTC), ainda é necessário o desenvolvimento de métodos individuais. Dessa forma, na primeira parte deste trabalho, otimizou-se e validou-se um método individual para determinação de DTC (mancozebe) em camas biológicas utilizando GC-MS. Foram avaliados os parâmetros de linearidade da curva analítica (r2), limites de detecção e de quantificação, exatidão, precisão e efeito matriz. Os estudos de recuperação foram realizados empregando o agrotóxico tiram como solução padrão de fortificação. As amostras “branco” de biomistura foram fortificadas em três concentrações, 1; 3 e 5 mg CS2 kg-1, em sete replicatas (n = 7). O método apresentou recuperações na faixa de 89-96% e RSD ≤ 11%, com linearidade na faixa de concentração de 0,05 a 10 μg CS2 mL-1 (r2> 0,9946). LODm e LOQm foram 0,2 e 1,0 mg CS2 kg-1, respectivamente, e o efeito matriz calculado não foi significativo (≤ 20%). O método validado foi aplicado para análise de 80 amostras (biomistura), de dezesseis reatores diferentes (coletadas em cinco tempos de amostragem) durante quatorze meses. Dez por cento das amostras apresentaram concentração de CS2 abaixo do LODm (0,2 mg CS2 kg-1) e 70% apresentaram resultados abaixo do LOQ (1,0 mg CS2 kg-1), o que confirma a eficiência das camas biológicas para degradar DTC. Na segunda etapa deste trabalho otimizou-se e validou-se um método multirresidual para a determinação de captana e seu produto de degradação (tetrahidroftalimida), clorotalonil, clorpirifós, fenitrotiona, metidationa, fosmete e tebuconazol em camas biológicas, utilizando GC-MS/MS. A otimização do método “ND” mini-Luke foi efetuada em nosso grupo de pesquisa realizando-se a troca de solventes para eliminar o uso de diclorometano e também evitar o passo de evaporação, permitindo a injeção direta do extrato final no GC-MS/MS, o que reduz tempo de análise e o uso de reagentes. Após otimização do método, a validação do mesmo para determinação multirresidual de agrotóxicos em camas biológicas foi realizada com base nas diretrizes do Documento Guia SANTE/11813/2017 avaliando-se a linearidade (r2), os limites de detecção e de quantificação (LOD e LOQ), o efeito matriz, a exatidão e a precisão. Dois padrões internos foram empregados para controle de qualidade, o PCB-153 foi usado como padrão interno do procedimento e o HCB-C13 como padrão interno do instrumento. No estudo de fortificação e recuperação, as amostras “branco” de biomistura foram fortificadas à 50, 100 e 200 μg kg-1 (n = 7) e todos os agrotóxicos, exceto captana a qual foi determinada indiretamente através do seu produto de degradação tetrahidroftalimida, apresentaram recuperações entre 74 e 117%, com valores de RSD% entre 2 e 14%. Os resíduos foram inferiores a 20% para todos os agrotóxicos avaliados. O método foi linear de 1 a 300 ng mL-1 para 3 agrotóxicos e 5 a 300 ng mL-1 para outros 4 agrotóxicos, com coeficientes de determinação maiores do que 0,99 para quase todos os agrotóxicos, exceto para clorpirifós (r2> 0,98). Todos os agrotóxicos apresentaram LODm de 10 ou 20 μg kg-1 e LOQm de 50 μg kg-1. Os valores calculados de efeito matriz ficaram acima de 25% para todos os agrotóxicos estudados, exceto para clorpirifós que foi de -20%.porUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessCamas biológicasAgrotóxicosCromatografia gasosaEspectrometria de massasDitiocarbamatosBiobedsMultiresidueChromatographyPesticidesDithiocarbamatesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAMétodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massasMultiresidue and single residue method to determine pesticides in biobeds by gas chromatograpy tandem mass spectrometryinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisPizzutti, Ionara Reginahttp://lattes.cnpq.br/3883506164936996Silva, Rosselei Caiél dahttp://lattes.cnpq.br/2187197138622302Gebler, Lucianohttp://lattes.cnpq.br/3800729962480769Jerez, Maria Cristina DiezCesconi, Maria Veronica Cesiohttp://lattes.cnpq.br/7154857962290517Vareli, Catiucia Souza100600000000600500500961b4a4a-1465-4d87-b4e8-6428b5a3ad38e3258556-56d0-4c3f-8561-4053a933d47ea44174cb-8124-43d7-858f-82a8799621738e5b76c8-7237-49b4-9a3b-1ad829f79dd56bd6f048-e91a-455c-a216-bc6cc0ceb1dae4bbaeee-3ded-43e8-a9d1-c28e6cbf73cdreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGQUIMICA_2018_VARELI_CATIUCIA.pdfTES_PPGQUIMICA_2018_VARELI_CATIUCIA.pdfTese de Doutoradoapplication/pdf2627257http://repositorio.ufsm.br/bitstream/1/15713/1/TES_PPGQUIMICA_2018_VARELI_CATIUCIA.pdf20c058378d964bcb87460de783e225aaMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas |
dc.title.alternative.eng.fl_str_mv |
Multiresidue and single residue method to determine pesticides in biobeds by gas chromatograpy tandem mass spectrometry |
title |
Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas |
spellingShingle |
Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas Vareli, Catiucia Souza Camas biológicas Agrotóxicos Cromatografia gasosa Espectrometria de massas Ditiocarbamatos Biobeds Multiresidue Chromatography Pesticides Dithiocarbamates CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas |
title_full |
Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas |
title_fullStr |
Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas |
title_full_unstemmed |
Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas |
title_sort |
Métodos individual e multirresidual para determinação de agrotóxicos em camas biológicas por cromatografia gasosa acoplada à espectrometria de massas |
author |
Vareli, Catiucia Souza |
author_facet |
Vareli, Catiucia Souza |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Pizzutti, Ionara Regina |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/3883506164936996 |
dc.contributor.referee1.fl_str_mv |
Silva, Rosselei Caiél da |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/2187197138622302 |
dc.contributor.referee2.fl_str_mv |
Gebler, Luciano |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/3800729962480769 |
dc.contributor.referee3.fl_str_mv |
Jerez, Maria Cristina Diez |
dc.contributor.referee4.fl_str_mv |
Cesconi, Maria Veronica Cesio |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/7154857962290517 |
dc.contributor.author.fl_str_mv |
Vareli, Catiucia Souza |
contributor_str_mv |
Pizzutti, Ionara Regina Silva, Rosselei Caiél da Gebler, Luciano Jerez, Maria Cristina Diez Cesconi, Maria Veronica Cesio |
dc.subject.por.fl_str_mv |
Camas biológicas Agrotóxicos Cromatografia gasosa Espectrometria de massas Ditiocarbamatos |
topic |
Camas biológicas Agrotóxicos Cromatografia gasosa Espectrometria de massas Ditiocarbamatos Biobeds Multiresidue Chromatography Pesticides Dithiocarbamates CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Biobeds Multiresidue Chromatography Pesticides Dithiocarbamates |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Besides the possibility to perform determination of a large number of pesticides in only a single chromatographyc analysis using multiresidual methods, sometimes, due to diversity in pesticides chemical composition and particular characteristics, it is still required develop single-residue method, such as for dithiocarbamates (DTC). Therefore, in this study, firstly, was optimized and validated a single method to determine DTC (mancozeb) in biobeds using GC-MS to evaluate biobeds efficiency on DTC degradation. Validation study was performed and assessed the analytical curve linearity (r2), detection and quantification limits (LOD and LOQ), accuracy (recovery%), precision (RSD%) and matrix effect. Recovery experiments were carried out with a standard spiking solution of the DTC pesticide thiram. Blank biomixture samples were spiked at the three levels corresponding to the CS2 concentrations of 1, 3 and 5 mg kg-1, with seven replicates each (n = 7). The method presented recoveries within the range of 89-96% and RSD ≤ 11%. The analytical curves were linear in the concentration range of 0.05 to 10 μg CS2 mL-1 (r2 > 0.9946). LOD and LOQ were 0.2 and 1.0 mg CS2 kg-1, respectively, and the calculated matrix effects were not significant (≤ 20%). The validated method was applied to 80 samples (biomixture), from sixteen different biobeds. Ten percent of samples presented CS2 concentration below the LOD (0.2 mg CS2 kg-1) and 70% of them showed results below the LOQ (1.0 mg CS2 kg-1), which demonstrates the biobeds capability to degrade DTC. The second step was to devepol and validated a method (modification of the New Dutch mini-Luke method) for multiresidue determination of captan and its degradation product (tetrahydrophytalimide), chlorothalonil, chlorpyrifos-ethyl, fenithrothion, methidathion, phosmet and tebuconazole in biobed, using GC-MS/MS. The dichloromethane use and the evaporation step were eliminated. This improvement avoids chlorinated solvents use and allows final extract direct injection into the GC-MS/MS system. After method optimization, validation study was performed based on SANTE Guidance Document. Linearity of analytical curves (r2), residuals, limits of detection (LOD) and quantification (LOQ) and matrix effects (%), were assessed by the analysis of standards solutions prepared in organic solvent and in blank biobed extract at eight concentrations, with seven replicate injections of each standard solution. Accuracy (as recoveries %) precision (as repeatability of recoveries experiments-RSD% and as intermediate precision) were also determinate. Two labeled internal standards were used for quality control. PCB-153 was used as procedure internal standard (P.I.S.), and HCB-C13 was used as instrument internal standard (I.I.S.). Recovery study was performed by the analysis of blank biobed samples spiked at 50, 100 and 200 μg kg-1 (n=7). All pesticides presented average recoveries within the range of 74 and 117%, except captan which was indirectly detected via tetrahydrophytalimide, its degradation product, and also had acceptable recoveries. The RSD values calculated from the 7 replicated recovery samples at 3 concentration levels were below 20% (2 to 14%). The residuals was lower than 20% for all pesticides. The method was linear within the range of 1 to 300 ng mL-1 for 2 pesticides and of 5 to 300 ng mL-1 for 4 pesticides and for tetrahydrophytalimide (the degradation product of captan). The r2 of the analytical curves calculated from matrix-matched standards were > 0.99 for all pesticides except for chlorpyrifos-ethyl, that had an r2 0.98. All studied pesticides presented the LODs of 10 or 20 μg kg-1 and LOQs of 50 μg kg-1. The calculated matrix effects were higher than 25% for all pesticides, excepted for chlorpiripfós-ethyl, that was -20%. |
publishDate |
2018 |
dc.date.issued.fl_str_mv |
2018-06-08 |
dc.date.accessioned.fl_str_mv |
2019-02-22T12:38:45Z |
dc.date.available.fl_str_mv |
2019-02-22T12:38:45Z |
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.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/15713 |
url |
http://repositorio.ufsm.br/handle/1/15713 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 500 500 |
dc.relation.authority.fl_str_mv |
961b4a4a-1465-4d87-b4e8-6428b5a3ad38 e3258556-56d0-4c3f-8561-4053a933d47e a44174cb-8124-43d7-858f-82a879962173 8e5b76c8-7237-49b4-9a3b-1ad829f79dd5 6bd6f048-e91a-455c-a216-bc6cc0ceb1da e4bbaeee-3ded-43e8-a9d1-c28e6cbf73cd |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações do UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Biblioteca Digital de Teses e Dissertações do UFSM |
collection |
Biblioteca Digital de Teses e Dissertações do UFSM |
bitstream.url.fl_str_mv |
http://repositorio.ufsm.br/bitstream/1/15713/1/TES_PPGQUIMICA_2018_VARELI_CATIUCIA.pdf http://repositorio.ufsm.br/bitstream/1/15713/2/license_rdf http://repositorio.ufsm.br/bitstream/1/15713/3/license.txt http://repositorio.ufsm.br/bitstream/1/15713/4/TES_PPGQUIMICA_2018_VARELI_CATIUCIA.pdf.txt http://repositorio.ufsm.br/bitstream/1/15713/5/TES_PPGQUIMICA_2018_VARELI_CATIUCIA.pdf.jpg |
bitstream.checksum.fl_str_mv |
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bitstream.checksumAlgorithm.fl_str_mv |
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repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1793240121352388608 |