Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS
Ano de defesa: | 2022 |
---|---|
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
|
Departamento: |
Química
|
País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/27776 |
Resumo: | This study investigated the applicability of calcium hydroxyapatite (HA) as a support matrix for laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) multi-element quantitative analysis. HA pellets were prepared and fortified with 5.0 µg g-1 of Ag, Al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sb, Se, Sn, Sr, Ti, Tl, U, V and Zn. The following operating parameters of the LA-ICP-MS system were optimized: energy, laser beam diameter and scanning rate, as well as carrier gas flow rate. Aiming a multi-element quantification, the best analysis conditions were: 80% energy, laser beam diameter of 150 µm, scanning rate of 150 µm s-1 and carrier gas (Ar) flow rate of 1.15 L min-1 , since this arrangement showed feasible results regarding signal/noise ratio for the largest number of elements. Considering that the laser interaction depends on the composition of the sample matrix, internal standards (IS) were evaluated in order to correct possible non-spectral interferences. For this purpose, the following elements were chosen: Ca and P, naturally present in HA, and Au, Ga, Ge, In, Ir, Rh and Sc, fortified to 5.0 µg g-1 . Calibration curves ranged from 0.25 to 10.0 µg g-1 for each analyte, and were linear, with R² superior to 0.99 for 17 elements, for 8 elements used as IS. The quantification limits varied from 25 ng g-1 for 205Tl/193Ir to 4,76 µg g-1 for 60Ni/193Ir. The method was applied to fertilizers, rhyolite and granite, which are inorganic matrices. The obtained results were compared to reference values. Quantitative analyses of As, Ba, Cd, Cu, Mo, Ni, Pb, U and V were achieved in fertilizers; As, Bi, Cu, Li, Mo, Ni, Pb, Sb, Sn, Rb, Tl and U in rhyolite; and Ba, Bi, Co, Li, Pb, Rb, Sn, Tl and U in granite, with concordance ranging from 75 to 120% in relation the reference values. The applicability of the IS depends on the analyte and sample matrix characteristics. |
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2023-02-10T11:50:52Z2023-02-10T11:50:52Z2022-10-31http://repositorio.ufsm.br/handle/1/27776This study investigated the applicability of calcium hydroxyapatite (HA) as a support matrix for laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) multi-element quantitative analysis. HA pellets were prepared and fortified with 5.0 µg g-1 of Ag, Al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sb, Se, Sn, Sr, Ti, Tl, U, V and Zn. The following operating parameters of the LA-ICP-MS system were optimized: energy, laser beam diameter and scanning rate, as well as carrier gas flow rate. Aiming a multi-element quantification, the best analysis conditions were: 80% energy, laser beam diameter of 150 µm, scanning rate of 150 µm s-1 and carrier gas (Ar) flow rate of 1.15 L min-1 , since this arrangement showed feasible results regarding signal/noise ratio for the largest number of elements. Considering that the laser interaction depends on the composition of the sample matrix, internal standards (IS) were evaluated in order to correct possible non-spectral interferences. For this purpose, the following elements were chosen: Ca and P, naturally present in HA, and Au, Ga, Ge, In, Ir, Rh and Sc, fortified to 5.0 µg g-1 . Calibration curves ranged from 0.25 to 10.0 µg g-1 for each analyte, and were linear, with R² superior to 0.99 for 17 elements, for 8 elements used as IS. The quantification limits varied from 25 ng g-1 for 205Tl/193Ir to 4,76 µg g-1 for 60Ni/193Ir. The method was applied to fertilizers, rhyolite and granite, which are inorganic matrices. The obtained results were compared to reference values. Quantitative analyses of As, Ba, Cd, Cu, Mo, Ni, Pb, U and V were achieved in fertilizers; As, Bi, Cu, Li, Mo, Ni, Pb, Sb, Sn, Rb, Tl and U in rhyolite; and Ba, Bi, Co, Li, Pb, Rb, Sn, Tl and U in granite, with concordance ranging from 75 to 120% in relation the reference values. The applicability of the IS depends on the analyte and sample matrix characteristics.Na presente pesquisa foi investigada a aplicabilidade da hidroxiapatita de cálcio (HA) como matriz suporte para a análise multielementar por ablação a laserespectrometria de massa com plasma indutivamente acoplado (LA-ICP-MS). Para esse propósito, foram preparadas pastilhas de HA fortificadas com 5,0 µg g -1 de Ag, Al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sb, Se, Sn, Sr, Ti, Tl, U, V e Zn e avaliados os seguintes parâmetros operacionais do sistema de LA-ICP-MS: a energia, o diâmetro e a velocidade de varredura do feixe de radiação laser, além da vazão do gás carreador. Visando uma determinação multielementar, foram escolhidos 80% de energia, 150 µm de diâmetro do feixe, 150 µm s-1 de velocidade de varredura e 1,15 L min-1 de vazão do gás carreador (argônio), condições que levaram à obtenção de resultados satisfatórios, em relação sinal/ruído, para o maior número de elementos investigados. Considerando-se que a interação do laser difere para cada matriz sólida analisada, foram avaliados padrões internos (PI) para corrigir as possíveis interferências não espectrais da técnica. Os elementos escolhidos para essa finalidade foram Ca e P, presentes naturalmente na HA, e Au, Ga, Ge, In, Ir, Rh e Sc, adicionados à amostra sólida de modo a obter 5,0 µg g-1 desses elementos. As curvas de calibração abrangeram a faixa de concentração de 0,25 a 10,0 µg g-1 dos analitos, sendo obtidas curvas lineares, com R2 superior a 0,99, para 17 elementos mediante a padronização interna. Os limites de quantificação (LOQ) variaram entre 25 ng g-1 (para 205Tl/193Ir) e 4,76 µg g-1 (para 60Ni/193Ir). A aplicação do método foi verificada para fertilizante, riolito e granito, amostras com matrizes predominantemente inorgânica. Os resultados obtidos foram comparados com valores de referência, sendo viável a determinação de As, Ba, Cd, Cu, Mo, Ni, Pb, U e V em fertilizante, As, Bi, Cu, Li, Mo, Ni, Pb, Sb, Sn, Rb, Tl e U em riolito e Ba, Bi, Co, Li, Pb, Rb, Sn, Tl e U em granito, com concordâncias entre 75 e 120% em relação aos valores de referência. O PI mais efetivo para cada analito variou de acordo com a matriz da amostra. Entre os elementos testados como PI, 8 deles mostraram-se viáveis para a finalidade, sendo eles o Au, Ca, Ga, In, Ir, P, Rh e Sc.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqporUniversidade 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/openAccessAblação a laser-espectrometria de massa com plasma indutivamente acopladoHidroxiapatita de cálcioDeterminação multielementarAnálise de sólidosPadrão internoLaser ablation-inductively couple plasma-mass spectrometryCalcium hydroxyapatiteMulti-element quantitative-analysisSolid analysisInternal standardCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAInvestigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MSInvestigation of hydroxyapatite as a support matrix multielemental analysis by LA-ICP-MSinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisDressler, Valderi Luizhttp://lattes.cnpq.br/4054740296547580Müller, Edson IrineuBizzi, Cezar AugustoPozebon, DircePereira Filho, Edenir RodriguesNunes, Matheus Augusto Gonçalveshttp://lattes.cnpq.br/4997000930235386Neves, Vinicius Machado10060000000060060060060029c59cfe-a489-425c-88a5-18fdf7cbf2582ff570ba-580a-40c0-9c73-35e6dfb4b57f335d8f94-921b-46b5-bcb4-4766cf694c91be6876cc-2db6-4d50-8c79-b4b0a2425b0cebaacc9b-884b-4f52-8867-e201fb0187f7d5f1e78d-2814-4d8a-8522-33dddf747dca9961631a-4e88-46a0-b16a-cc6ce07d3dc6reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGQUÍMICA_2022_NEVES_VINICIUS.pdfTES_PPGQUÍMICA_2022_NEVES_VINICIUS.pdfTese de doutoradoapplication/pdf6166709http://repositorio.ufsm.br/bitstream/1/27776/1/TES_PPGQU%c3%8dMICA_2022_NEVES_VINICIUS.pdf43de07c9f2e180423f5b5c2cc5d88f1fMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8805http://repositorio.ufsm.br/bitstream/1/27776/2/license_rdf4460e5956bc1d1639be9ae6146a50347MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81956http://repositorio.ufsm.br/bitstream/1/27776/3/license.txt2f0571ecee68693bd5cd3f17c1e075dfMD531/277762023-02-10 08:50:52.435oai:repositorio.ufsm.br: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 Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2023-02-10T11:50:52Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS |
dc.title.alternative.eng.fl_str_mv |
Investigation of hydroxyapatite as a support matrix multielemental analysis by LA-ICP-MS |
title |
Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS |
spellingShingle |
Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS Neves, Vinicius Machado Ablação a laser-espectrometria de massa com plasma indutivamente acoplado Hidroxiapatita de cálcio Determinação multielementar Análise de sólidos Padrão interno Laser ablation-inductively couple plasma-mass spectrometry Calcium hydroxyapatite Multi-element quantitative-analysis Solid analysis Internal standard CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS |
title_full |
Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS |
title_fullStr |
Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS |
title_full_unstemmed |
Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS |
title_sort |
Investigação da hidroxiapatita como matriz suporte em análise multielementar por LA-ICP-MS |
author |
Neves, Vinicius Machado |
author_facet |
Neves, Vinicius Machado |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Dressler, Valderi Luiz |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/4054740296547580 |
dc.contributor.advisor-co1.fl_str_mv |
Müller, Edson Irineu |
dc.contributor.referee1.fl_str_mv |
Bizzi, Cezar Augusto |
dc.contributor.referee2.fl_str_mv |
Pozebon, Dirce |
dc.contributor.referee3.fl_str_mv |
Pereira Filho, Edenir Rodrigues |
dc.contributor.referee4.fl_str_mv |
Nunes, Matheus Augusto Gonçalves |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/4997000930235386 |
dc.contributor.author.fl_str_mv |
Neves, Vinicius Machado |
contributor_str_mv |
Dressler, Valderi Luiz Müller, Edson Irineu Bizzi, Cezar Augusto Pozebon, Dirce Pereira Filho, Edenir Rodrigues Nunes, Matheus Augusto Gonçalves |
dc.subject.por.fl_str_mv |
Ablação a laser-espectrometria de massa com plasma indutivamente acoplado Hidroxiapatita de cálcio Determinação multielementar Análise de sólidos Padrão interno |
topic |
Ablação a laser-espectrometria de massa com plasma indutivamente acoplado Hidroxiapatita de cálcio Determinação multielementar Análise de sólidos Padrão interno Laser ablation-inductively couple plasma-mass spectrometry Calcium hydroxyapatite Multi-element quantitative-analysis Solid analysis Internal standard CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Laser ablation-inductively couple plasma-mass spectrometry Calcium hydroxyapatite Multi-element quantitative-analysis Solid analysis Internal standard |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This study investigated the applicability of calcium hydroxyapatite (HA) as a support matrix for laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) multi-element quantitative analysis. HA pellets were prepared and fortified with 5.0 µg g-1 of Ag, Al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sb, Se, Sn, Sr, Ti, Tl, U, V and Zn. The following operating parameters of the LA-ICP-MS system were optimized: energy, laser beam diameter and scanning rate, as well as carrier gas flow rate. Aiming a multi-element quantification, the best analysis conditions were: 80% energy, laser beam diameter of 150 µm, scanning rate of 150 µm s-1 and carrier gas (Ar) flow rate of 1.15 L min-1 , since this arrangement showed feasible results regarding signal/noise ratio for the largest number of elements. Considering that the laser interaction depends on the composition of the sample matrix, internal standards (IS) were evaluated in order to correct possible non-spectral interferences. For this purpose, the following elements were chosen: Ca and P, naturally present in HA, and Au, Ga, Ge, In, Ir, Rh and Sc, fortified to 5.0 µg g-1 . Calibration curves ranged from 0.25 to 10.0 µg g-1 for each analyte, and were linear, with R² superior to 0.99 for 17 elements, for 8 elements used as IS. The quantification limits varied from 25 ng g-1 for 205Tl/193Ir to 4,76 µg g-1 for 60Ni/193Ir. The method was applied to fertilizers, rhyolite and granite, which are inorganic matrices. The obtained results were compared to reference values. Quantitative analyses of As, Ba, Cd, Cu, Mo, Ni, Pb, U and V were achieved in fertilizers; As, Bi, Cu, Li, Mo, Ni, Pb, Sb, Sn, Rb, Tl and U in rhyolite; and Ba, Bi, Co, Li, Pb, Rb, Sn, Tl and U in granite, with concordance ranging from 75 to 120% in relation the reference values. The applicability of the IS depends on the analyte and sample matrix characteristics. |
publishDate |
2022 |
dc.date.issued.fl_str_mv |
2022-10-31 |
dc.date.accessioned.fl_str_mv |
2023-02-10T11:50:52Z |
dc.date.available.fl_str_mv |
2023-02-10T11:50:52Z |
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/1/27776 |
url |
http://repositorio.ufsm.br/handle/1/27776 |
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 |
dc.relation.authority.fl_str_mv |
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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 |
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institution |
UFSM |
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Biblioteca Digital de Teses e Dissertações do UFSM |
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