Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS
Ano de defesa: | 2021 |
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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: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/23034 |
Resumo: | In this work five analytical methods were investigated for rare earth elements determination (REE) in blood by inductively coupled plasma mass spectrometry (ICP-MS): i) Electrothermal vaporization and inductively coupled plasma mass spectrometry (ETV-ICP-MS), ii) conventional wet digestion in open system (CWD-OS), iii) conventional wet digestion in clossed system (CWD-CS), iv) microwaveassisted wet digestion using a single reaction chamber (MAWD-SRC) and v) microwave induced combustion (MIC). For CWD-OS, CWD-CS, MAWD-SRC and MIC, which used ultrassonic nebulization (USN), a systematic investigation of possible interferences for the determination of REE using this sample introduction system was carried out. The effect of Ca, Fe, K, Mg, Na, C (from citric acid, fructose and digested bovine liver) concentration were investigated, as well as the effect of the concentration of HNO3, HCl and aqua regia. In general, signal suppression effects for all REE from 50 mg L-1 of Na and K, 75 mg L-1 of Ca and 100 mg L-1 Mg and Fe were observed in this study. In evaluating the C effect (from citric acid and fructose), an increase in the signal intensity of REE was observed from 250 mg L-1. For the HNO3 and aqua regia concentration, signal suppression of REE was observed from 10 and 20%, respectively. On the other hand, no interferences were observed in the determination of REE in the range of 5 to 30% of HCl. Additionally, a study was carried out from two complete factorial designs (23) investigating the effect of the concomitant concentration of Fe, K and Na and of C, Na and K, respectively, in determination of REE by USN-ICP-MS. It was observed that the sum of Na and K concentrations (50 mg L-1) interfere in the determination of the REE. Furthermore, these suppression effects caused by Na and K compete with the signal intensity increase effects caused by the presence of C (from citric acid). The obtained results by microwaveassisted wet digestion (MAWD) were used as reference values for the developed analytical methods. Each analytical method was optimized as a function of experimental parameters, such as sample mass, temperature, time, concentration of digested solution, among others. The investigated analytical methods were applied to human blood samples (samples A, B and C), bovine and pig blood (sample D and E, respectively). In addition, liver samples of bovine and pig were used (sample F and G, respectively). from the same animals that provided samples D and E. Additionally, a bovine liver sample (sample H) was used for the interference experiments. Regarding to ETV-ICP-MS, regardless of the experimental conditions used, it was observed that this method was not suitable for the determination of REE in blood, possibly due to the difficulty of separating the REE from the metals (Fe, Na and K) that are part of the blood. It is important to highlight that the blood mass used in the CWDOS, CWD-CS, MAWD-SRC and MIC methods is dependent on he concentration of Na and K present in each sample, based on the interferences observed on the systematic study for REE determination by USN-ICP-MS. The CWD-OS method was not considered suitable for blood digestion because regardless of the digestion solution used, it was obtained digests with fat in suspension. On the other hand, the CWD-CS method was suitable for the digestion of 0.4 g of liquid blood using 5 mL of 3 mol L-1 HNO3 + 1 mL of 30%H2O2. In the MAWD-SRC method, it was possible to digest 2 g of blood using 6 mL of 1 mol L-1 HNO3 at 270 ºC for 15 min. The MIC allowed the digestion of 0.45 g of blood using 6 mL of aqua regia as an absorbing solution. In view of the developed sample preparation methods, it is important to emphasize that the choice for each one depends directly on the concentration of the interfering metals in each sample, the analytical frequency and the instrumentation available in each laboratory. |
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2021-11-29T12:30:13Z2021-11-29T12:30:13Z2021-07-31http://repositorio.ufsm.br/handle/1/23034In this work five analytical methods were investigated for rare earth elements determination (REE) in blood by inductively coupled plasma mass spectrometry (ICP-MS): i) Electrothermal vaporization and inductively coupled plasma mass spectrometry (ETV-ICP-MS), ii) conventional wet digestion in open system (CWD-OS), iii) conventional wet digestion in clossed system (CWD-CS), iv) microwaveassisted wet digestion using a single reaction chamber (MAWD-SRC) and v) microwave induced combustion (MIC). For CWD-OS, CWD-CS, MAWD-SRC and MIC, which used ultrassonic nebulization (USN), a systematic investigation of possible interferences for the determination of REE using this sample introduction system was carried out. The effect of Ca, Fe, K, Mg, Na, C (from citric acid, fructose and digested bovine liver) concentration were investigated, as well as the effect of the concentration of HNO3, HCl and aqua regia. In general, signal suppression effects for all REE from 50 mg L-1 of Na and K, 75 mg L-1 of Ca and 100 mg L-1 Mg and Fe were observed in this study. In evaluating the C effect (from citric acid and fructose), an increase in the signal intensity of REE was observed from 250 mg L-1. For the HNO3 and aqua regia concentration, signal suppression of REE was observed from 10 and 20%, respectively. On the other hand, no interferences were observed in the determination of REE in the range of 5 to 30% of HCl. Additionally, a study was carried out from two complete factorial designs (23) investigating the effect of the concomitant concentration of Fe, K and Na and of C, Na and K, respectively, in determination of REE by USN-ICP-MS. It was observed that the sum of Na and K concentrations (50 mg L-1) interfere in the determination of the REE. Furthermore, these suppression effects caused by Na and K compete with the signal intensity increase effects caused by the presence of C (from citric acid). The obtained results by microwaveassisted wet digestion (MAWD) were used as reference values for the developed analytical methods. Each analytical method was optimized as a function of experimental parameters, such as sample mass, temperature, time, concentration of digested solution, among others. The investigated analytical methods were applied to human blood samples (samples A, B and C), bovine and pig blood (sample D and E, respectively). In addition, liver samples of bovine and pig were used (sample F and G, respectively). from the same animals that provided samples D and E. Additionally, a bovine liver sample (sample H) was used for the interference experiments. Regarding to ETV-ICP-MS, regardless of the experimental conditions used, it was observed that this method was not suitable for the determination of REE in blood, possibly due to the difficulty of separating the REE from the metals (Fe, Na and K) that are part of the blood. It is important to highlight that the blood mass used in the CWDOS, CWD-CS, MAWD-SRC and MIC methods is dependent on he concentration of Na and K present in each sample, based on the interferences observed on the systematic study for REE determination by USN-ICP-MS. The CWD-OS method was not considered suitable for blood digestion because regardless of the digestion solution used, it was obtained digests with fat in suspension. On the other hand, the CWD-CS method was suitable for the digestion of 0.4 g of liquid blood using 5 mL of 3 mol L-1 HNO3 + 1 mL of 30%H2O2. In the MAWD-SRC method, it was possible to digest 2 g of blood using 6 mL of 1 mol L-1 HNO3 at 270 ºC for 15 min. The MIC allowed the digestion of 0.45 g of blood using 6 mL of aqua regia as an absorbing solution. In view of the developed sample preparation methods, it is important to emphasize that the choice for each one depends directly on the concentration of the interfering metals in each sample, the analytical frequency and the instrumentation available in each laboratory.Neste trabalho foram investigados cinco métodos analíticos para a determinação de elementos terras raras (REE) em sangue por espectrometria de massas com plasma indutivamente acoplado (ICPMS): i) vaporização eletrotérmica e espectrometria de massa com plasma indutivamente acoplado (ETV-ICP-MS), ii) digestão por via úmida com aquecimento convencional em sistema aberto (CWDOS), iii) digestão por via úmida com aquecimento convencional em sistema fechado (CWD-CS), iv) digestão por via úmida assistida por radiação micro-ondas em câmara única de reação (MAWD-SRC) e v) combustão iniciada por micro-ondas (MIC). Para os métodos da CWD-OS, CWD-CS, MAWDSRC e MIC, os quais utilizaram a nebulização ultrassônica (USN), foi feita uma investigação sistemática de possíveis interferências para a determinação dos REE usando esse sistema de introdução de amostra. Foi investigado o efeito da concentração de Ca, Fe, K, Mg, Na, C (a partir do ácido cítrico, frutose e de digeridos de fígado bovino), bem como o efeito da concentração de HNO3, HCl e água régia. De maneira geral, efeitos de supressão de sinal para todos os REE a partir de 50 mg L-1 de Na e K, 75 mg L-1 de Ca e 100 mg L-1 de Mg e Fe foram observados nesse estudo. Na avaliação do efeito do C (proveniente do ácido cítrico e da frutose), observou-se aumento na intensidade do sinal dos REE a partir de 250 mg L-1. Para a concentração de HNO3 e água régia, observou-se supressão de sinal dos REE a partir de 10 e 20%, respectivamente. Por outro lado, não foram observadas interferências na determinação dos REE na faixa de 5 a 30% de HCl. Adicionalmente, foi feito um estudo a partir de dois delineamentos fatoriais completos (23) investigando o efeito da concentração concomitante de Fe, K e Na e de C, Na e K, respectivamente, na determinação dos REE por USN ICP-MS. Foi observado que o somatório das concentrações de Na e K (50 mg L-1) causam interferências na terminação dos REE. Ainda, estes efeitos de supressão causados pelo Na e K, competem com os efeitos de aumento da intensidade de sinal causados pela presença de C ( a partir do ácido cítrico). Os resultados obtidos por digestão por via úmida assistida por radiação micro-ondas (MAWD) foram utilizados como valores de referência para os métodos analíticos desenvolvidos. Cada método analítico foi otimizado em função de parâmetros experimentais, como massa de amostra, temperatura, tempo, concentração de solução digestora, entre outros. Os métodos analíticos investigados foram aplicados para amostras de sangue humano (amostras A, B e C), sangue bovino e suíno (amostra D e E, respectivamente). Ainda, foi utilizada amostras de fígado bovino e suíno (amostra F e G, respectivamente), provenientes dos mesmos animais que forneceram as amostras D e E. Adicionalmente, uma amostra de fígado bovino (amostra H) foi utilizada para os experimentos de interferências. Com relação a ETV-ICP-MS, independente das condições experimentais utilizadas, observou-se que este método não foi adequado para a determinação de REE em sangue, possivelmente devido a dificuldade de separar os REE dos metais (Fe, Na e K) consituintiuintes do sangue. É importante destacar que a massa de sangue utilizada nos métodos da CWD-OS, CWD-CS, MAWD-SRC e MIC é dependente da concentração de Na e K presentes em cada amostra, visto às interferências observadas no estudo sistemático para a determinação de REE por USN-ICP-MS. O método da CWD-OS, não foi considerado adequado para a digestão de sangue, pois independente da solução de digestão utilizada, obteve-se digeridos com gordura em suspensão. Por outro lado, o método da CWD-CS foi adequado para a digestão de 0,4 g de sangue líquido usando 5 mL de HNO3 3 mol L-1 + 1 mL de H2O2 30%. No método da MAWD-SRC, foi possível a digestão de 2 g de sangue utilizando 6 mL de HNO3 1 mol L-1, a 270 ºC durante 15 min. A MIC permitiu a digestão de 0,45 g de sangue utilizando 6 mL de água régia como solução absorvedora. Em vista dos métodos de preparo de amotras desenvolvidos, é importante salientar que a escolha por cada um deles depende diretamente da concentração dos interferentes presente nas amostras, a frequência analítica e a instrumentação disponível em cada laboratório.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/openAccessSangueElementos terras rarasAmostragem diretaPreparo de amostrasICPM-SCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICADesenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MSDevelopment of analytical methos and interferences study for Rare Earth elements determination in blood by ICP-MSinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisFlores, Érico Marlon de Moraeshttp://lattes.cnpq.br/7167629055579212Müller, Edson IrineuBolzan, Rodrigo CordeiroRodrigues, Luiz FredericoMortari, Sergio Robertohttp://lattes.cnpq.br/9944510855730895Druzian, Gabriel Toneto100600000000600600600600600600600a9c2788c-7913-4d7b-92e1-3429800ac0281d30f0fa-6c82-42eb-989d-41828825bd5e48134181-e983-450f-9543-d2f1522e87a90b6036d2-a4c4-4565-bfc3-5fef0aae6060eb5f6555-ee67-449a-ab4f-ae56ae8070f3ebb296a1-1569-43d1-8946-7cc7e3bec814reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMLICENSElicense.txtlicense.txttext/plain; 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dc.title.por.fl_str_mv |
Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS |
dc.title.alternative.eng.fl_str_mv |
Development of analytical methos and interferences study for Rare Earth elements determination in blood by ICP-MS |
title |
Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS |
spellingShingle |
Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS Druzian, Gabriel Toneto Sangue Elementos terras raras Amostragem direta Preparo de amostras ICPM-S CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS |
title_full |
Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS |
title_fullStr |
Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS |
title_full_unstemmed |
Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS |
title_sort |
Desenvolvimento de métodos analíticos e estudo de interferências para a determinação de elementos Terras Raras em sangue por ICP-MS |
author |
Druzian, Gabriel Toneto |
author_facet |
Druzian, Gabriel Toneto |
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.referee1.fl_str_mv |
Müller, Edson Irineu |
dc.contributor.referee2.fl_str_mv |
Bolzan, Rodrigo Cordeiro |
dc.contributor.referee3.fl_str_mv |
Rodrigues, Luiz Frederico |
dc.contributor.referee4.fl_str_mv |
Mortari, Sergio Roberto |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/9944510855730895 |
dc.contributor.author.fl_str_mv |
Druzian, Gabriel Toneto |
contributor_str_mv |
Flores, Érico Marlon de Moraes Müller, Edson Irineu Bolzan, Rodrigo Cordeiro Rodrigues, Luiz Frederico Mortari, Sergio Roberto |
dc.subject.por.fl_str_mv |
Sangue Elementos terras raras Amostragem direta Preparo de amostras ICPM-S |
topic |
Sangue Elementos terras raras Amostragem direta Preparo de amostras ICPM-S CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In this work five analytical methods were investigated for rare earth elements determination (REE) in blood by inductively coupled plasma mass spectrometry (ICP-MS): i) Electrothermal vaporization and inductively coupled plasma mass spectrometry (ETV-ICP-MS), ii) conventional wet digestion in open system (CWD-OS), iii) conventional wet digestion in clossed system (CWD-CS), iv) microwaveassisted wet digestion using a single reaction chamber (MAWD-SRC) and v) microwave induced combustion (MIC). For CWD-OS, CWD-CS, MAWD-SRC and MIC, which used ultrassonic nebulization (USN), a systematic investigation of possible interferences for the determination of REE using this sample introduction system was carried out. The effect of Ca, Fe, K, Mg, Na, C (from citric acid, fructose and digested bovine liver) concentration were investigated, as well as the effect of the concentration of HNO3, HCl and aqua regia. In general, signal suppression effects for all REE from 50 mg L-1 of Na and K, 75 mg L-1 of Ca and 100 mg L-1 Mg and Fe were observed in this study. In evaluating the C effect (from citric acid and fructose), an increase in the signal intensity of REE was observed from 250 mg L-1. For the HNO3 and aqua regia concentration, signal suppression of REE was observed from 10 and 20%, respectively. On the other hand, no interferences were observed in the determination of REE in the range of 5 to 30% of HCl. Additionally, a study was carried out from two complete factorial designs (23) investigating the effect of the concomitant concentration of Fe, K and Na and of C, Na and K, respectively, in determination of REE by USN-ICP-MS. It was observed that the sum of Na and K concentrations (50 mg L-1) interfere in the determination of the REE. Furthermore, these suppression effects caused by Na and K compete with the signal intensity increase effects caused by the presence of C (from citric acid). The obtained results by microwaveassisted wet digestion (MAWD) were used as reference values for the developed analytical methods. Each analytical method was optimized as a function of experimental parameters, such as sample mass, temperature, time, concentration of digested solution, among others. The investigated analytical methods were applied to human blood samples (samples A, B and C), bovine and pig blood (sample D and E, respectively). In addition, liver samples of bovine and pig were used (sample F and G, respectively). from the same animals that provided samples D and E. Additionally, a bovine liver sample (sample H) was used for the interference experiments. Regarding to ETV-ICP-MS, regardless of the experimental conditions used, it was observed that this method was not suitable for the determination of REE in blood, possibly due to the difficulty of separating the REE from the metals (Fe, Na and K) that are part of the blood. It is important to highlight that the blood mass used in the CWDOS, CWD-CS, MAWD-SRC and MIC methods is dependent on he concentration of Na and K present in each sample, based on the interferences observed on the systematic study for REE determination by USN-ICP-MS. The CWD-OS method was not considered suitable for blood digestion because regardless of the digestion solution used, it was obtained digests with fat in suspension. On the other hand, the CWD-CS method was suitable for the digestion of 0.4 g of liquid blood using 5 mL of 3 mol L-1 HNO3 + 1 mL of 30%H2O2. In the MAWD-SRC method, it was possible to digest 2 g of blood using 6 mL of 1 mol L-1 HNO3 at 270 ºC for 15 min. The MIC allowed the digestion of 0.45 g of blood using 6 mL of aqua regia as an absorbing solution. In view of the developed sample preparation methods, it is important to emphasize that the choice for each one depends directly on the concentration of the interfering metals in each sample, the analytical frequency and the instrumentation available in each laboratory. |
publishDate |
2021 |
dc.date.accessioned.fl_str_mv |
2021-11-29T12:30:13Z |
dc.date.available.fl_str_mv |
2021-11-29T12:30:13Z |
dc.date.issued.fl_str_mv |
2021-07-31 |
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/1/23034 |
url |
http://repositorio.ufsm.br/handle/1/23034 |
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 |
dc.relation.authority.fl_str_mv |
a9c2788c-7913-4d7b-92e1-3429800ac028 1d30f0fa-6c82-42eb-989d-41828825bd5e 48134181-e983-450f-9543-d2f1522e87a9 0b6036d2-a4c4-4565-bfc3-5fef0aae6060 eb5f6555-ee67-449a-ab4f-ae56ae8070f3 ebb296a1-1569-43d1-8946-7cc7e3bec814 |
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 |
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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_ |
1793240163263971328 |