Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM)
Ano de defesa: | 2012 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , |
Tipo de documento: | Dissertação |
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/1/10497 |
Resumo: | In this study, was developed and validated a multi-residue method for the determination of 40 pesticides in green coffee beans. To obtain a very homogeneous sample, the coffee beans were first milled, followed by a slurry preparation of coffee and water (ratio 1:4, w/w). For the extraction procedure modifications of the QuEChERS method were developed. Acetonitrile containing 1% acetic acid and the procedure internal standard (P.I.S.) was used as extraction solvent. After the acetonitrile addition, 3 g of anhydrous magnesium sulfate were added, to promote phase separation between the organic phase (acetonitrile) and the aqueous phase. For the dispersive solid-phase extraction (dSPE) clean-up step, two sorbents were tested in separate and in different amounts and were also tested mixtures of them. Ergo the best results were obtained using 500 mg C18-bonded silica together with 600 mg of magnesium sulfate, for drying. The pesticides were determined by gas chromatography tandem mass spectrometry (GC-MS). Considering the characteristics of the pesticides and the complexity of the coffee matrix the GC-MS had to be operated in negative chemical ionization mode (NCI) and single ion monitoring mode (SIM) which provided high sensitivity and selectivity to pesticide detection. The validation was performed by analyzing spiked samples at three different concentrations (10, 20 and 50 μg kg-1), with 6 replicates (n=6) at each spike concentration. For each one of the 51 pesticides determined by GC-MS (NCI-SIM), the linearity (r) of calibration curves, accuracy (as recovery percent), instrument and method limits of detection and quantification (LOD and LOQ), precision (as RSD percent) and matrix effects (percent) were determined. From the 51 pesticides studied, approximately 76% showed average recoveries between 70-120% and 75% RSD ≤ 20% for the spike concentration of 10 μg kg-1. For the spike concentrations of 20 and 50 μg kg-1, the recoveries (%) and RSD (%) values were even better. The method LOQ was 10, 20 and 50 μg kg-1, for respectively 33, 3 and 6 pesticides, 4 pesticides could only be detected via their degradation products and 5 compounds did not presented recoveries between 70-120% and RSD ≤ 20% thus the method LOQ could not be determined for those pesticides. The matrix effect was present for all the pesticides even with the use of a clean-up step, requiring therefore matrixmatched calibration standards for application in routine analysis. |
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2017-05-112017-05-112012-01-16REICHERT, Bárbara. Development and validation a multi-residue method for pesticides determination in green coffee usin GC-MS (NCI-SIM). 2012. 112 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012.http://repositorio.ufsm.br/handle/1/10497In this study, was developed and validated a multi-residue method for the determination of 40 pesticides in green coffee beans. To obtain a very homogeneous sample, the coffee beans were first milled, followed by a slurry preparation of coffee and water (ratio 1:4, w/w). For the extraction procedure modifications of the QuEChERS method were developed. Acetonitrile containing 1% acetic acid and the procedure internal standard (P.I.S.) was used as extraction solvent. After the acetonitrile addition, 3 g of anhydrous magnesium sulfate were added, to promote phase separation between the organic phase (acetonitrile) and the aqueous phase. For the dispersive solid-phase extraction (dSPE) clean-up step, two sorbents were tested in separate and in different amounts and were also tested mixtures of them. Ergo the best results were obtained using 500 mg C18-bonded silica together with 600 mg of magnesium sulfate, for drying. The pesticides were determined by gas chromatography tandem mass spectrometry (GC-MS). Considering the characteristics of the pesticides and the complexity of the coffee matrix the GC-MS had to be operated in negative chemical ionization mode (NCI) and single ion monitoring mode (SIM) which provided high sensitivity and selectivity to pesticide detection. The validation was performed by analyzing spiked samples at three different concentrations (10, 20 and 50 μg kg-1), with 6 replicates (n=6) at each spike concentration. For each one of the 51 pesticides determined by GC-MS (NCI-SIM), the linearity (r) of calibration curves, accuracy (as recovery percent), instrument and method limits of detection and quantification (LOD and LOQ), precision (as RSD percent) and matrix effects (percent) were determined. From the 51 pesticides studied, approximately 76% showed average recoveries between 70-120% and 75% RSD ≤ 20% for the spike concentration of 10 μg kg-1. For the spike concentrations of 20 and 50 μg kg-1, the recoveries (%) and RSD (%) values were even better. The method LOQ was 10, 20 and 50 μg kg-1, for respectively 33, 3 and 6 pesticides, 4 pesticides could only be detected via their degradation products and 5 compounds did not presented recoveries between 70-120% and RSD ≤ 20% thus the method LOQ could not be determined for those pesticides. The matrix effect was present for all the pesticides even with the use of a clean-up step, requiring therefore matrixmatched calibration standards for application in routine analysis.Neste estudo, foi desenvolvido e validado um método multirresidual para determinação de 40 pesticidas em grãos de café verde. Para se obter uma amostra bem homogênea, os grãos de café verde foram previamente moídos e em seguida preparou-se um slurry de café e água (razão 1:4, m/m). Para o procedimento de extração utilizou-se o método QuEChERS, no qual foram introduzidas algumas modificações. Como solvente extrator, utilizou-se acetonitrila contendo 1% de ácido acético e padrão interno do procedimento (P.I.P.). Após a adição da acetonitrila, para promover o particionamento entre as fases orgânica e aquosa, adicionou-se 3 g de sulfato de magnésio anidro. Para a purificação do extrato de café, foram testados dois adsorventes, separadamente e em diferentes quantidades e também misturas entre os dois adsorventes, em uma etapa de extração em fase sólida dispersiva (dSPE), sendo que os melhores resultados foram obtidos com a utilização de 500 mg de C18 juntamente com 600 mg de sulfato de magnésio, para remoção de água. A determinação dos pesticidas foi feita em um sistema de cromatografia gasosa acoplado a um espectrômetro de massas (GC-MS). Em função das características dos pesticidas e da complexidade da matriz, o GC-MS foi operado no modo de ionização química negativa (NCI) e monitoramento seletivo de íons (SIM), que forneceu grande sensibilidade e seletividade na determinação dos pesticidas. A validação foi realizada pela análise de amostras de café fortificado em três diferentes concentrações (10, 20 e 50 μg kg-1), com 6 replicatas (n=6) para cada concentração. Para cada um dos pesticidas, avaliou-se a linearidade da curva analítica (r), exatidão (recuperação%), limite de detecção e quantificação (LOD e LOQ) do instrumento e do método, precisão (RSD%) e efeito matriz (%). Dos 51 pesticidas estudados, aproximadamente 76% obtiveram recuperações médias entre 70-120% e 75% apresentaram RSD ≤ 20% para amostras fortificadas na concentração de 10 μg kg-1. Para as fortificações de 20 e 50 μg kg-1 os resultados foram ainda melhores. O LOQ do método foi estabelecido em 10, 20 e 50 μg kg-1, respectivamente para 33, 3 e 6 pesticidas, 4 pesticidas somente puderam ser detectados via seus produtos de degradação e 5 compostos não apresentaram recuperações entre 70-120% e RSD≤ 20%, assim o LOQ do método não pode ser estabelecido para esses pesticidas. Mesmo com a utilização de uma etapa de purificação do extrato de café o efeito matriz manteve-se presente para todos os pesticidas, dessa forma, para que o método possa ser implantado em análises de rotina, a confecção das curvas analíticas deve ser feita em matriz (matrix-matched calibration).Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaCafé verdePesticidasGC-MS NCI-SIMMétodo QuEChERSGreen coffeePesticidesQuEChERS methodCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICADesenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM)Development and validation a multi-residue method for pesticides determination in green coffee usin GC-MS (NCI-SIM)info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisCardoso, Carmem Dickowhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4792018P1Pizzutti, Ionara Reginahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797011T5Wagner, Rogerhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4764455Y6Roesler, Rafaelhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797705Y6http://lattes.cnpq.br/5984328766946058Reichert, Bárbara1006000000004005005005005003005e6c09b1-2827-4a21-8cfd-185f61a79161edf3bdc1-289e-4521-96ad-cc175f1daad445db26b1-d4ae-4ebb-bf81-7679f7fe548674b27fe4-c135-437f-b869-245b3b7ae36dff672c60-023b-4251-bb6b-413b20b59d42info:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALREICHERT, BARBARA.pdfapplication/pdf1628057http://repositorio.ufsm.br/bitstream/1/10497/1/REICHERT%2c%20BARBARA.pdf0b1d6c025c6ec38d50cf1d650905620cMD51TEXTREICHERT, BARBARA.pdf.txtREICHERT, BARBARA.pdf.txtExtracted texttext/plain214331http://repositorio.ufsm.br/bitstream/1/10497/2/REICHERT%2c%20BARBARA.pdf.txt958fe8b66ae76c2207fb36f93a66359eMD52THUMBNAILREICHERT, BARBARA.pdf.jpgREICHERT, BARBARA.pdf.jpgIM Thumbnailimage/jpeg5046http://repositorio.ufsm.br/bitstream/1/10497/3/REICHERT%2c%20BARBARA.pdf.jpg03bd97247637c7e2ac6b68a4c32b575aMD531/104972022-07-11 09:28:41.159oai:repositorio.ufsm.br:1/10497Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2022-07-11T12:28:41Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM) |
dc.title.alternative.eng.fl_str_mv |
Development and validation a multi-residue method for pesticides determination in green coffee usin GC-MS (NCI-SIM) |
title |
Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM) |
spellingShingle |
Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM) Reichert, Bárbara Café verde Pesticidas GC-MS NCI-SIM Método QuEChERS Green coffee Pesticides QuEChERS method CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM) |
title_full |
Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM) |
title_fullStr |
Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM) |
title_full_unstemmed |
Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM) |
title_sort |
Desenvolvimento e validação de método multirresidual para determinação de pesticidas em café verde utilizando GC-MS (NCI-SIM) |
author |
Reichert, Bárbara |
author_facet |
Reichert, Bárbara |
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 |
Wagner, Roger |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4764455Y6 |
dc.contributor.referee2.fl_str_mv |
Roesler, Rafael |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797705Y6 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/5984328766946058 |
dc.contributor.author.fl_str_mv |
Reichert, Bárbara |
contributor_str_mv |
Cardoso, Carmem Dickow Pizzutti, Ionara Regina Wagner, Roger Roesler, Rafael |
dc.subject.por.fl_str_mv |
Café verde Pesticidas GC-MS NCI-SIM Método QuEChERS |
topic |
Café verde Pesticidas GC-MS NCI-SIM Método QuEChERS Green coffee Pesticides QuEChERS method CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Green coffee Pesticides QuEChERS method |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In this study, was developed and validated a multi-residue method for the determination of 40 pesticides in green coffee beans. To obtain a very homogeneous sample, the coffee beans were first milled, followed by a slurry preparation of coffee and water (ratio 1:4, w/w). For the extraction procedure modifications of the QuEChERS method were developed. Acetonitrile containing 1% acetic acid and the procedure internal standard (P.I.S.) was used as extraction solvent. After the acetonitrile addition, 3 g of anhydrous magnesium sulfate were added, to promote phase separation between the organic phase (acetonitrile) and the aqueous phase. For the dispersive solid-phase extraction (dSPE) clean-up step, two sorbents were tested in separate and in different amounts and were also tested mixtures of them. Ergo the best results were obtained using 500 mg C18-bonded silica together with 600 mg of magnesium sulfate, for drying. The pesticides were determined by gas chromatography tandem mass spectrometry (GC-MS). Considering the characteristics of the pesticides and the complexity of the coffee matrix the GC-MS had to be operated in negative chemical ionization mode (NCI) and single ion monitoring mode (SIM) which provided high sensitivity and selectivity to pesticide detection. The validation was performed by analyzing spiked samples at three different concentrations (10, 20 and 50 μg kg-1), with 6 replicates (n=6) at each spike concentration. For each one of the 51 pesticides determined by GC-MS (NCI-SIM), the linearity (r) of calibration curves, accuracy (as recovery percent), instrument and method limits of detection and quantification (LOD and LOQ), precision (as RSD percent) and matrix effects (percent) were determined. From the 51 pesticides studied, approximately 76% showed average recoveries between 70-120% and 75% RSD ≤ 20% for the spike concentration of 10 μg kg-1. For the spike concentrations of 20 and 50 μg kg-1, the recoveries (%) and RSD (%) values were even better. The method LOQ was 10, 20 and 50 μg kg-1, for respectively 33, 3 and 6 pesticides, 4 pesticides could only be detected via their degradation products and 5 compounds did not presented recoveries between 70-120% and RSD ≤ 20% thus the method LOQ could not be determined for those pesticides. The matrix effect was present for all the pesticides even with the use of a clean-up step, requiring therefore matrixmatched calibration standards for application in routine analysis. |
publishDate |
2012 |
dc.date.issued.fl_str_mv |
2012-01-16 |
dc.date.accessioned.fl_str_mv |
2017-05-11 |
dc.date.available.fl_str_mv |
2017-05-11 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
REICHERT, Bárbara. Development and validation a multi-residue method for pesticides determination in green coffee usin GC-MS (NCI-SIM). 2012. 112 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10497 |
identifier_str_mv |
REICHERT, Bárbara. Development and validation a multi-residue method for pesticides determination in green coffee usin GC-MS (NCI-SIM). 2012. 112 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012. |
url |
http://repositorio.ufsm.br/handle/1/10497 |
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100600000000 |
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Universidade Federal de Santa Maria |
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Programa de Pós-Graduação em Química |
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Química |
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Universidade Federal de Santa Maria |
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