Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo
Ano de defesa: | 2020 |
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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/1/29739 |
Resumo: | The main difficulty in relation to the methodology development in crude oil separated water is related to the high concentration of salts (up to 150 g L-1 of Cl-) of this type of sample, which can cause interferences in the chromatographic separation stage. In this work, ion chromatography with conductivity and mass spectrometer (MS) detectors was proposed for determination of anions and organic acids in crude oil separated water. Initially, the separation in the ion exchange column it was optimized, with optimal separation using a KOH mobile phase gradient (1 to 60 mmol L-1), column temperature of 35 ºC and 50 min chromatographic run. The organic acids C1 to C8 and the anions F- , Cl- , Br- , NO3 - , CO3 2-, SO4 2- and PO4 3- were separated with good resolution limits of quantification (LOQs) ranging from 10 to 500 µg L-1, for anions and organic acids, respectively. Due to overlapping signals for high chloride content, it was not possible to quantify anions and organic acids simultaneously by ion chromatography in samples with more than 100 mg L-1 of Cl- . Most samples need to be diluted, increasing the LOQs in the same order. As an alternative, the organic acids separation it was evaluated using ion-exclusion chromatography and conductivity detection, using heptafluorobutyric acid 1 mmol L1 as mobile phase in the isocratic mode, 35 ºC and chemical suppression with external regeneration of tetrabutylammonium hydroxide 0,5 mmol L-1. It was possible to separate and quantify the organic acids C1, C2, C3, C4 e C5 with limits of quantification of 2.5, 5, 8, 5 and 5 mg L-1, respectively. However, as with the ion-exchange column, the samples needed to be diluted to Cl- concentrations below 5000 mg L -1 to minimize signal overlap. C1 and C2 are presented in most samples with concentrations ranging from bellow of 2.5 to 1680 mg L-1 and bellow of 5 to 15310 mg L-1, respectively. For the acids C3, C4 and C5, due to the need for sample dilution and consequent increase in LOQs proportionally to the dilution factor used it was bellow of LOQ with exception of C3 in only one sample, with 352 mg L-1. Twodimensional ion chromatography with ion-exclusion pre-column was used to eliminate the Cl- from the matrix in the first dimension and to separate organic acids in the second dimension (with ion-exclusion column) and minimize the need for sample dilution. It was necessary 3,8 min in the first dimension to eliminate the most of Cl- of the sample matrix and enable quantification of C3, C4 and C5 organic acids of the water samples separated from emulsions of crude oil injected directly into the chromatographic system, without the need sample dilution, with LOQs up to 30 times lower (samples with 150 g L-1 of Cl- ). The quantification of C1 and C2 organic acids it was not possible in this method because most of them are eliminated with the sample matrix in the first dimension. The organic acids C5 to C10 were quantify using ion-pairing chromatography and MS detection, with acetonitrile, methanol and water acid mobile phase, 35 min of run and 25 ºC. The separation of C1 to C5 it was not quantify because they was eliminated in the Cl- matrix removal step using C18 SPE cartridges (washing with water and eluting with 75% acetonitrile + 25% methanol). The eluted samples were injected directly into the chromatographic system and the LOQs were 0.5 mg L-1 for C5, C6 and C7 and 1.0 mg L-1 for C8, C9 and C10. The values found for organic acids C5, C6 and C7 ranged from 0.557 to 22.1 mg L-1, from 0.686 to 5.06 mg L-1 and 0.685 to 1.4 mg L-1, respectively. For C8, C9 and C10, the values were lower than LOQ (1 mg L-1). It should be noted that, for all methods used, recovery tests were performed using a reference solution and the recoveries were about 80 to 110%. In addition, the accuracy was evaluated using certified reference material (CRM 46975) and the results were in agreement with the reference values (85 to 110%). |
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2023-07-21T15:14:11Z2023-07-21T15:14:11Z2020-03-31http://repositorio.ufsm.br/handle/1/29739The main difficulty in relation to the methodology development in crude oil separated water is related to the high concentration of salts (up to 150 g L-1 of Cl-) of this type of sample, which can cause interferences in the chromatographic separation stage. In this work, ion chromatography with conductivity and mass spectrometer (MS) detectors was proposed for determination of anions and organic acids in crude oil separated water. Initially, the separation in the ion exchange column it was optimized, with optimal separation using a KOH mobile phase gradient (1 to 60 mmol L-1), column temperature of 35 ºC and 50 min chromatographic run. The organic acids C1 to C8 and the anions F- , Cl- , Br- , NO3 - , CO3 2-, SO4 2- and PO4 3- were separated with good resolution limits of quantification (LOQs) ranging from 10 to 500 µg L-1, for anions and organic acids, respectively. Due to overlapping signals for high chloride content, it was not possible to quantify anions and organic acids simultaneously by ion chromatography in samples with more than 100 mg L-1 of Cl- . Most samples need to be diluted, increasing the LOQs in the same order. As an alternative, the organic acids separation it was evaluated using ion-exclusion chromatography and conductivity detection, using heptafluorobutyric acid 1 mmol L1 as mobile phase in the isocratic mode, 35 ºC and chemical suppression with external regeneration of tetrabutylammonium hydroxide 0,5 mmol L-1. It was possible to separate and quantify the organic acids C1, C2, C3, C4 e C5 with limits of quantification of 2.5, 5, 8, 5 and 5 mg L-1, respectively. However, as with the ion-exchange column, the samples needed to be diluted to Cl- concentrations below 5000 mg L -1 to minimize signal overlap. C1 and C2 are presented in most samples with concentrations ranging from bellow of 2.5 to 1680 mg L-1 and bellow of 5 to 15310 mg L-1, respectively. For the acids C3, C4 and C5, due to the need for sample dilution and consequent increase in LOQs proportionally to the dilution factor used it was bellow of LOQ with exception of C3 in only one sample, with 352 mg L-1. Twodimensional ion chromatography with ion-exclusion pre-column was used to eliminate the Cl- from the matrix in the first dimension and to separate organic acids in the second dimension (with ion-exclusion column) and minimize the need for sample dilution. It was necessary 3,8 min in the first dimension to eliminate the most of Cl- of the sample matrix and enable quantification of C3, C4 and C5 organic acids of the water samples separated from emulsions of crude oil injected directly into the chromatographic system, without the need sample dilution, with LOQs up to 30 times lower (samples with 150 g L-1 of Cl- ). The quantification of C1 and C2 organic acids it was not possible in this method because most of them are eliminated with the sample matrix in the first dimension. The organic acids C5 to C10 were quantify using ion-pairing chromatography and MS detection, with acetonitrile, methanol and water acid mobile phase, 35 min of run and 25 ºC. The separation of C1 to C5 it was not quantify because they was eliminated in the Cl- matrix removal step using C18 SPE cartridges (washing with water and eluting with 75% acetonitrile + 25% methanol). The eluted samples were injected directly into the chromatographic system and the LOQs were 0.5 mg L-1 for C5, C6 and C7 and 1.0 mg L-1 for C8, C9 and C10. The values found for organic acids C5, C6 and C7 ranged from 0.557 to 22.1 mg L-1, from 0.686 to 5.06 mg L-1 and 0.685 to 1.4 mg L-1, respectively. For C8, C9 and C10, the values were lower than LOQ (1 mg L-1). It should be noted that, for all methods used, recovery tests were performed using a reference solution and the recoveries were about 80 to 110%. In addition, the accuracy was evaluated using certified reference material (CRM 46975) and the results were in agreement with the reference values (85 to 110%).Devido à sua origem, as águas separadas de emulsões de petróleo do pré-sal possuem alta concentração salina (até 150 g L-1 de Cl-), o que dificulta o desenvolvimento de metodologias analíticas, principalmente por meio da cromatografia líquida. Neste trabalho foi proposto o uso da cromatografia líquida, usando detectores de condutividade e de espectrometria de massas (MS), para a separação e posterior quantificação de ácidos orgânicos de cadeia curta e linear e ânions, em águas separadas de emulsões de petróleo. Inicialmente foi feita a otimização da separação em coluna de troca iônica, e as melhores condições de separação encontradas foram utilizando gradiente de fase móvel de KOH (1 a 60 mmol L-1), 35 ºC e 50 min de corrida cromatográfica. Foi possível obter boa resolução na separação dos ácidos orgânicos C1 a C8 e os ânions F- , Cl- , Br- , NO3 - , CO3 2-, SO4 2- e PO4 3-, com limites de quantificação (LOQs) variando de 10 a 50 e 100 a 500 µg L-1, para ânions e ácidos orgânicos, respectivamente. Porém, devido a sobreposição de sinais pela alta concentração de Cl- , não foi possível quantificar ânions e ácidos orgânicos, simultaneamente, utilizando cromatografia de troca iônica, em amostras com concentração de Cl- superior a 100 mg L-1 devido a necessidade de diluição da amostra e consequente aumento dos LOQs de maneira proporcional ao fator de diluição utilizado. Como alternativa, a separação dos ácidos orgânicos C1 a C10 foi avaliada em coluna de exclusão iônica, com fase móvel no modo isocrático de ácido heptafluorbutírico 1 mmol L-1, 35 ºC e supressão química com regeneração externa de hidróxido de tetrabutilamônio 0,5 mmol L-1. Foi possível separar e quantificar os ácidos orgânicos C1, C2, C3, C4 e C5, com LOQs de 2,5, 5, 8, 5 e 5 mg L-1, respectivamente. Porém, foi necessária a diluição das amostras com concentração de Cl- superiores a 5000 mg L-1 a fim de evitar interferências por sobreposição de sinal. Os ácidos fórmico e acético foram quantificados com concentrações variando de 2,5 a 1680 mg L-1 e de 5 a 15310 mg L-1, respectivamente. Para os ácidos C3, C4 e C5, devido ao alto fator de diluição e consequente aumento do LOQ, os valores encontrados para todas as amostras, foram menores que os LOQs, com exceção do ácido propiônico em uma amostra (352 mg L-1). Para eliminar a necessidade de diluição das amostras, foi utilizada a cromatografia bidimensional, utilizando uma pré-coluna e coluna de exclusão iônica, na primeira e segunda dimensão, respectivamente, objetivando a separação do Cl- da matriz na primeira dimensão. Foram necessários 3,8 min na primeira dimensão para a eliminação da maior parte da matriz e possibilitar a quantificação dos ácidos orgânicos C3, C4 e C5 nas amostras de águas separadas de emulsões injetadas diretamente no sistema cromatográfico, sem necessidade de diluição, com LOQs até 30 vezes menores (amostras com 150 g L-1 de Cl-). Os ácidos orgânicos C1 e C2 são eliminados, em sua maior parte, junto com a matriz na primeira dimensão, não sendo quantificados neste método. A determinação dos ácidos orgânicos C5 a C10 foi feita após a separação, em coluna de pareamento iônico e determinação por MS, utilizando fase móvel acidificada de acetonitrila, metanol e água, 35 min de corrida cromatográfica e 25 ºC. Os ácidos C1 a C5 não foram quantificados neste método pois foram eliminados na etapa de remoção do Cl- da matriz que foi feita utilizando cartuchos para extração em fase sólida (SPE) de C18 (lavagem com água e eluição com 75% de acetonitrila + 25% de metanol). As amostras eluídas foram injetadas diretamente no sistema cromatográfico e os LOQs foram de 0,5 mg L-1 para C5, C6 e C7 e de 1,0 mg L-1 para C8, C9 e C10. Os valores encontrados para os ácidos orgânicos C5, C6 e C7 variaram de 0,557 a 22,1 mg L-1, de 0,686 a 5,06 mg L-1 e 0,685 a 1,4 mg L-1 , respectivamente. Para C8, C9 e C10, os valores ficaram abaixo do LOQ (1 mg L-1). Cabe salientar que, para todos os métodos utilizados, foram feitos ensaios de recuperação utilizando solução de referência e as recuperações estiveram na faixa de 80 a 110%. Além disso, a exatidão foi avaliada usando material de referência certificado (CRM 46975) e os resultados foram concordantes com os valores de referência (85 a 110%).Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESporUniversidade 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/openAccessÁcidos orgânicosCromatografia líquidaLC-MSÁguas separadas de emulsões de petróleoRemoção de Cl-Organic acidsIon chromatographyIC-MSCrude oil separated waterCl- removalCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICACromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleoMass spectrometry ion chromatography for the determination of organic acids and anions in crude oil separated waterinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisFlores, Érico Marlon de Moraeshttp://lattes.cnpq.br/7167629055579212Mello, Paola de AzevedoFlores, Érico Marlon de MoraesCosta, Adilson Ben daMüller, Edson IrineuMesko, Márcia FosterPicoloto, Rochele Sogarihttp://lattes.cnpq.br/7167629055579212Doneda, Morgana100600000000600600600600600600600600600a9c2788c-7913-4d7b-92e1-3429800ac028900319df-c13b-4f5c-9c66-1acf16dc6b0a29b2a4d2-2523-43eb-b167-7e0185fedaccbce48fa2-be48-48b8-8c70-998ba4302656a453756f-c5f8-44d3-b2a5-b722712058a15340e61b-ef9c-45e3-9754-7c9649711f61f4f59694-8614-4813-b490-f750c0e68be157e4eea3-dc6c-4451-89ff-67989e4ae304reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGQUÍMICA_2020_DONEDA_MORGANA.pdfTES_PPGQUÍMICA_2020_DONEDA_MORGANA.pdfTese de doutoradoapplication/pdf3918199http://repositorio.ufsm.br/bitstream/1/29739/1/TES_PPGQU%c3%8dMICA_2020_DONEDA_MORGANA.pdf77891b6e7a42c7883625d9ff58bb1ef1MD51LICENSElicense.txtlicense.txttext/plain; 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dc.title.por.fl_str_mv |
Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo |
dc.title.alternative.eng.fl_str_mv |
Mass spectrometry ion chromatography for the determination of organic acids and anions in crude oil separated water |
title |
Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo |
spellingShingle |
Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo Doneda, Morgana Ácidos orgânicos Cromatografia líquida LC-MS Águas separadas de emulsões de petróleo Remoção de Cl- Organic acids Ion chromatography IC-MS Crude oil separated water Cl- removal CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo |
title_full |
Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo |
title_fullStr |
Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo |
title_full_unstemmed |
Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo |
title_sort |
Cromatografia líquida com espectrometria de massas para a determinação de ácidos orgânicos e ânions em água separada de emulsões de petróleo |
author |
Doneda, Morgana |
author_facet |
Doneda, Morgana |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Flores, Érico Marlon de Moraes |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/7167629055579212 |
dc.contributor.advisor-co1.fl_str_mv |
Mello, Paola de Azevedo |
dc.contributor.referee1.fl_str_mv |
Flores, Érico Marlon de Moraes |
dc.contributor.referee2.fl_str_mv |
Costa, Adilson Ben da |
dc.contributor.referee3.fl_str_mv |
Müller, Edson Irineu |
dc.contributor.referee4.fl_str_mv |
Mesko, Márcia Foster |
dc.contributor.referee5.fl_str_mv |
Picoloto, Rochele Sogari |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/7167629055579212 |
dc.contributor.author.fl_str_mv |
Doneda, Morgana |
contributor_str_mv |
Flores, Érico Marlon de Moraes Mello, Paola de Azevedo Flores, Érico Marlon de Moraes Costa, Adilson Ben da Müller, Edson Irineu Mesko, Márcia Foster Picoloto, Rochele Sogari |
dc.subject.por.fl_str_mv |
Ácidos orgânicos Cromatografia líquida LC-MS Águas separadas de emulsões de petróleo Remoção de Cl- |
topic |
Ácidos orgânicos Cromatografia líquida LC-MS Águas separadas de emulsões de petróleo Remoção de Cl- Organic acids Ion chromatography IC-MS Crude oil separated water Cl- removal CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Organic acids Ion chromatography IC-MS Crude oil separated water Cl- removal |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The main difficulty in relation to the methodology development in crude oil separated water is related to the high concentration of salts (up to 150 g L-1 of Cl-) of this type of sample, which can cause interferences in the chromatographic separation stage. In this work, ion chromatography with conductivity and mass spectrometer (MS) detectors was proposed for determination of anions and organic acids in crude oil separated water. Initially, the separation in the ion exchange column it was optimized, with optimal separation using a KOH mobile phase gradient (1 to 60 mmol L-1), column temperature of 35 ºC and 50 min chromatographic run. The organic acids C1 to C8 and the anions F- , Cl- , Br- , NO3 - , CO3 2-, SO4 2- and PO4 3- were separated with good resolution limits of quantification (LOQs) ranging from 10 to 500 µg L-1, for anions and organic acids, respectively. Due to overlapping signals for high chloride content, it was not possible to quantify anions and organic acids simultaneously by ion chromatography in samples with more than 100 mg L-1 of Cl- . Most samples need to be diluted, increasing the LOQs in the same order. As an alternative, the organic acids separation it was evaluated using ion-exclusion chromatography and conductivity detection, using heptafluorobutyric acid 1 mmol L1 as mobile phase in the isocratic mode, 35 ºC and chemical suppression with external regeneration of tetrabutylammonium hydroxide 0,5 mmol L-1. It was possible to separate and quantify the organic acids C1, C2, C3, C4 e C5 with limits of quantification of 2.5, 5, 8, 5 and 5 mg L-1, respectively. However, as with the ion-exchange column, the samples needed to be diluted to Cl- concentrations below 5000 mg L -1 to minimize signal overlap. C1 and C2 are presented in most samples with concentrations ranging from bellow of 2.5 to 1680 mg L-1 and bellow of 5 to 15310 mg L-1, respectively. For the acids C3, C4 and C5, due to the need for sample dilution and consequent increase in LOQs proportionally to the dilution factor used it was bellow of LOQ with exception of C3 in only one sample, with 352 mg L-1. Twodimensional ion chromatography with ion-exclusion pre-column was used to eliminate the Cl- from the matrix in the first dimension and to separate organic acids in the second dimension (with ion-exclusion column) and minimize the need for sample dilution. It was necessary 3,8 min in the first dimension to eliminate the most of Cl- of the sample matrix and enable quantification of C3, C4 and C5 organic acids of the water samples separated from emulsions of crude oil injected directly into the chromatographic system, without the need sample dilution, with LOQs up to 30 times lower (samples with 150 g L-1 of Cl- ). The quantification of C1 and C2 organic acids it was not possible in this method because most of them are eliminated with the sample matrix in the first dimension. The organic acids C5 to C10 were quantify using ion-pairing chromatography and MS detection, with acetonitrile, methanol and water acid mobile phase, 35 min of run and 25 ºC. The separation of C1 to C5 it was not quantify because they was eliminated in the Cl- matrix removal step using C18 SPE cartridges (washing with water and eluting with 75% acetonitrile + 25% methanol). The eluted samples were injected directly into the chromatographic system and the LOQs were 0.5 mg L-1 for C5, C6 and C7 and 1.0 mg L-1 for C8, C9 and C10. The values found for organic acids C5, C6 and C7 ranged from 0.557 to 22.1 mg L-1, from 0.686 to 5.06 mg L-1 and 0.685 to 1.4 mg L-1, respectively. For C8, C9 and C10, the values were lower than LOQ (1 mg L-1). It should be noted that, for all methods used, recovery tests were performed using a reference solution and the recoveries were about 80 to 110%. In addition, the accuracy was evaluated using certified reference material (CRM 46975) and the results were in agreement with the reference values (85 to 110%). |
publishDate |
2020 |
dc.date.issued.fl_str_mv |
2020-03-31 |
dc.date.accessioned.fl_str_mv |
2023-07-21T15:14:11Z |
dc.date.available.fl_str_mv |
2023-07-21T15:14:11Z |
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/1/29739 |
url |
http://repositorio.ufsm.br/handle/1/29739 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 600 600 600 600 600 600 600 600 |
dc.relation.authority.fl_str_mv |
a9c2788c-7913-4d7b-92e1-3429800ac028 900319df-c13b-4f5c-9c66-1acf16dc6b0a 29b2a4d2-2523-43eb-b167-7e0185fedacc bce48fa2-be48-48b8-8c70-998ba4302656 a453756f-c5f8-44d3-b2a5-b722712058a1 5340e61b-ef9c-45e3-9754-7c9649711f61 f4f59694-8614-4813-b490-f750c0e68be1 57e4eea3-dc6c-4451-89ff-67989e4ae304 |
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/1/29739/1/TES_PPGQU%c3%8dMICA_2020_DONEDA_MORGANA.pdf http://repositorio.ufsm.br/bitstream/1/29739/3/license.txt http://repositorio.ufsm.br/bitstream/1/29739/2/license_rdf |
bitstream.checksum.fl_str_mv |
77891b6e7a42c7883625d9ff58bb1ef1 2f0571ecee68693bd5cd3f17c1e075df 4460e5956bc1d1639be9ae6146a50347 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 |
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_ |
1793240108832391168 |