Desenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável
Ano de defesa: | 2007 |
---|---|
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: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/10430 |
Resumo: | The water resources contamination has caused great environmental impact worldwide. In Brazil, the Ministry of Health through the Law 518 defines potability parameters, between them, the maximum limits for a list of pesticides. In this work it was developed and validated a method for a pesticide determination in drinking water using gas chromatography coupled with mass spectrometry in selective ion monitoring mode (GC-MS-SIM). In the chromatographic separation a HP-5MS (30 m x 0.25 mm id x 0.25 μm) column was used, with a total analysis time below 30 min. In agreement of the concentration level demanded in the determination of some pesticides, in the ng L-1 order, a concentration factor of 400 times was necessary, carried through a solid phase extraction (SPE). After an initial evaluation with different sorbents and solvents, the cartridge Strata X® of 30 mg/3 mL and dichloromethane for the elution were selected. During the method development, optimizations were carried out through factorial models for evaluation of variable effects to the sensitivity and the extraction step. The method validation involved all the usual parameters of internal validation including detection and quantification limits, precision (instrumental precision, repeatability and intermediate precision), accuracy (recovery), linearity, selectivity, robustness, uncertainty of measurement, practical reporting limit and range of application. The gotten results had presented limits of instrumental quantification between 1 and 37 μg L-1 and method reporting limits between 0.003 and 0.093 μg L-1, attending the legislation limits. Only three compounds had presented recoveries below 50% (hexachlorobenzene, aldrin and permethrin). The others presented average recoveries between 51 and 116%. Although the differentiated chemical nature of the analyzed pesticides becomes difficult a good recovery for all the evaluated compounds, the intermediate precisions had guaranteed excellent results being well below of the Horwitz curve. Correlation factors between surrogate standards and pesticides allow the correction of recovery values in the samples, supplying more accurate results. In the robustness study, the method demonstrated to be consistent to external changes having to be taken a special attention to be solvent evaporation step before redissolution. Through the uncertainty estimate was possible to verify that the main sources are the repeatability, the evaporations and the sample turbidity. The analyses in real samples had satisfied the criteria of instrumental qualification and system suitability. The method selectivity has been considered in agreement and evaluated through the relative recovery of quantification and qualification ions. The method has been considered fitness for purpose and in compliance with the quality demanded by the ISO IEC 17025. |
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2017-05-162017-05-162007-09-05SABIN, Guilherme Post. Development and validation of method using SPE AND GC-MS for the multiresidue determination of pesticides in drinking water. 2007. 166 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2007.http://repositorio.ufsm.br/handle/1/10430The water resources contamination has caused great environmental impact worldwide. In Brazil, the Ministry of Health through the Law 518 defines potability parameters, between them, the maximum limits for a list of pesticides. In this work it was developed and validated a method for a pesticide determination in drinking water using gas chromatography coupled with mass spectrometry in selective ion monitoring mode (GC-MS-SIM). In the chromatographic separation a HP-5MS (30 m x 0.25 mm id x 0.25 μm) column was used, with a total analysis time below 30 min. In agreement of the concentration level demanded in the determination of some pesticides, in the ng L-1 order, a concentration factor of 400 times was necessary, carried through a solid phase extraction (SPE). After an initial evaluation with different sorbents and solvents, the cartridge Strata X® of 30 mg/3 mL and dichloromethane for the elution were selected. During the method development, optimizations were carried out through factorial models for evaluation of variable effects to the sensitivity and the extraction step. The method validation involved all the usual parameters of internal validation including detection and quantification limits, precision (instrumental precision, repeatability and intermediate precision), accuracy (recovery), linearity, selectivity, robustness, uncertainty of measurement, practical reporting limit and range of application. The gotten results had presented limits of instrumental quantification between 1 and 37 μg L-1 and method reporting limits between 0.003 and 0.093 μg L-1, attending the legislation limits. Only three compounds had presented recoveries below 50% (hexachlorobenzene, aldrin and permethrin). The others presented average recoveries between 51 and 116%. Although the differentiated chemical nature of the analyzed pesticides becomes difficult a good recovery for all the evaluated compounds, the intermediate precisions had guaranteed excellent results being well below of the Horwitz curve. Correlation factors between surrogate standards and pesticides allow the correction of recovery values in the samples, supplying more accurate results. In the robustness study, the method demonstrated to be consistent to external changes having to be taken a special attention to be solvent evaporation step before redissolution. Through the uncertainty estimate was possible to verify that the main sources are the repeatability, the evaporations and the sample turbidity. The analyses in real samples had satisfied the criteria of instrumental qualification and system suitability. The method selectivity has been considered in agreement and evaluated through the relative recovery of quantification and qualification ions. The method has been considered fitness for purpose and in compliance with the quality demanded by the ISO IEC 17025.A contaminação dos recursos hídricos tem causado grande impacto para o meio ambiente. No Brasil, o Ministério da Saúde através da Portaria 518 define parâmetros de potabilidade, entre eles, os limites máximos permitidos para uma série de pesticidas. Neste trabalho foi desenvolvido e validado um método para a determinação de pesticidas em água potável, utilizando cromatografia gasosa acoplada à espectrometria de massas com monitoramento seletivo de íons (GC-MSSIM). Na separação cromatográfica foi utilizada coluna capilar HP-5MS (30 m x 0,25 mm x 0,25 μm), com tempo total de análise inferior a 30 min. Devido ao nível de concentração exigido na determinação de alguns pesticidas, na ordem de ng L-1, foi necessário atingir um fator de concentração de 400 vezes, obtido através de extração em fase sólida (SPE). Após uma avaliação inicial com diferentes sorventes e solventes foi selecionado o cartucho Strata X® de 30 mg/3 mL e diclorometano para eluição. Durante o desenvolvimento do método foram realizadas otimizações utilizando modelos fatoriais para avaliação de efeitos de variáveis pertinentes à sensibilidade e à etapa de extração. A validação do método envolveu todos os parâmetros usuais de validação interna, incluindo limites de detecção e quantificação, precisão (precisão instrumental, repetitividade e precisão intermediária), exatidão (recuperação), linearidade, seletividade, robustez, incerteza de medição, limite prático de reportagem e faixa de trabalho. Os resultados obtidos apresentaram limites de quantificação instrumental entre 1 e 37 μg L-1 e limites de reportagem do método entre 0,003 e 0,093 μg L-1, atendendo aos limites da legislação. Apenas três compostos apresentaram recuperações inferiores a 50% (hexaclorobenzeno, aldrin e permetrina). Os demais apresentaram recuperações médias entre 51 e 116%. Embora a natureza química diferenciada dos pesticidas analisados dificulte uma boa recuperação para a totalidade dos compostos avaliados, as precisões intermediárias garantiram excelentes resultados estando bem abaixo da curva de Horwitz. Fatores de correlação entre padrões de substituição e pesticidas permitem a correção de valores de recuperação em amostras, fornecendo resultados mais exatos. No estudo de robustez, o método demonstrou ser consistente à mudanças externas devendo ser tomada uma atenção especial para a etapa de evaporação do solvente antes da redissolução. Através da estimativa de incerteza foi possível verificar que as principais fontes são as repetitividades, as evaporações e a turbidez da amostra. As análises em amostras reais satisfizeram os critérios de qualificação instrumental e avaliação de adequação do sistema. A seletividade do método foi considerada adequada e avaliada através da recuperação relativa de íons de quantificação e qualificação. O método foi considerado adequado para o uso pretendido e em conformidade com a qualidade exigida para norma ISO IEC 17025.application/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaValidação de metodologiaGC-MSAnálise multirresidualAnálise de traçosQuímica ambientalCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICADesenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potávelDevelopment and validation of method using SPE AND GC-MS for the multiresidue determination of pesticides in drinking waterinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisZanella, Renatohttp://lattes.cnpq.br/2541865299438479Zini, Cláudia Alcarazhttp://lattes.cnpq.br/6032268532760866Adaime, Martha Bohrerhttp://lattes.cnpq.br/4385786922516848http://lattes.cnpq.br/9584193081809850Sabin, Guilherme Post1006000000004005003003005000aa2baab-94e8-4d3d-bbb2-85495ba77db5144214be-efc3-4c2f-9a65-2f4c42d6dacfbfd3edaf-0259-47a5-bf30-f4ef92e0ea5fa0f5a1bf-e731-4df0-9010-ddadda7ae90ainfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALGUILHERMEPOSTSABIN.pdfapplication/pdf5628913http://repositorio.ufsm.br/bitstream/1/10430/1/GUILHERMEPOSTSABIN.pdf2cb7b34f7f9bf91220f2e6cbed593eb8MD51TEXTGUILHERMEPOSTSABIN.pdf.txtGUILHERMEPOSTSABIN.pdf.txtExtracted texttext/plain294293http://repositorio.ufsm.br/bitstream/1/10430/2/GUILHERMEPOSTSABIN.pdf.txt5cbe91fb3e76dc42944306624d96e779MD52THUMBNAILGUILHERMEPOSTSABIN.pdf.jpgGUILHERMEPOSTSABIN.pdf.jpgIM Thumbnailimage/jpeg4972http://repositorio.ufsm.br/bitstream/1/10430/3/GUILHERMEPOSTSABIN.pdf.jpg73b55c01d1b55dd61c37eae1065fc243MD531/104302023-02-10 08:39:09.614oai:repositorio.ufsm.br:1/10430Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2023-02-10T11:39:09Biblioteca 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 utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável |
dc.title.alternative.eng.fl_str_mv |
Development and validation of method using SPE AND GC-MS for the multiresidue determination of pesticides in drinking water |
title |
Desenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável |
spellingShingle |
Desenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável Sabin, Guilherme Post Validação de metodologia GC-MS Análise multirresidual Análise de traços Química ambiental CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Desenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável |
title_full |
Desenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável |
title_fullStr |
Desenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável |
title_full_unstemmed |
Desenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável |
title_sort |
Desenvolvimento e validação de método utilizando SPE E GC-MS para a determinação multirresíduo de pesticidas em água potável |
author |
Sabin, Guilherme Post |
author_facet |
Sabin, Guilherme Post |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Zanella, Renato |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2541865299438479 |
dc.contributor.referee1.fl_str_mv |
Zini, Cláudia Alcaraz |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/6032268532760866 |
dc.contributor.referee2.fl_str_mv |
Adaime, Martha Bohrer |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/4385786922516848 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/9584193081809850 |
dc.contributor.author.fl_str_mv |
Sabin, Guilherme Post |
contributor_str_mv |
Zanella, Renato Zini, Cláudia Alcaraz Adaime, Martha Bohrer |
dc.subject.por.fl_str_mv |
Validação de metodologia GC-MS Análise multirresidual Análise de traços Química ambiental |
topic |
Validação de metodologia GC-MS Análise multirresidual Análise de traços Química ambiental CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The water resources contamination has caused great environmental impact worldwide. In Brazil, the Ministry of Health through the Law 518 defines potability parameters, between them, the maximum limits for a list of pesticides. In this work it was developed and validated a method for a pesticide determination in drinking water using gas chromatography coupled with mass spectrometry in selective ion monitoring mode (GC-MS-SIM). In the chromatographic separation a HP-5MS (30 m x 0.25 mm id x 0.25 μm) column was used, with a total analysis time below 30 min. In agreement of the concentration level demanded in the determination of some pesticides, in the ng L-1 order, a concentration factor of 400 times was necessary, carried through a solid phase extraction (SPE). After an initial evaluation with different sorbents and solvents, the cartridge Strata X® of 30 mg/3 mL and dichloromethane for the elution were selected. During the method development, optimizations were carried out through factorial models for evaluation of variable effects to the sensitivity and the extraction step. The method validation involved all the usual parameters of internal validation including detection and quantification limits, precision (instrumental precision, repeatability and intermediate precision), accuracy (recovery), linearity, selectivity, robustness, uncertainty of measurement, practical reporting limit and range of application. The gotten results had presented limits of instrumental quantification between 1 and 37 μg L-1 and method reporting limits between 0.003 and 0.093 μg L-1, attending the legislation limits. Only three compounds had presented recoveries below 50% (hexachlorobenzene, aldrin and permethrin). The others presented average recoveries between 51 and 116%. Although the differentiated chemical nature of the analyzed pesticides becomes difficult a good recovery for all the evaluated compounds, the intermediate precisions had guaranteed excellent results being well below of the Horwitz curve. Correlation factors between surrogate standards and pesticides allow the correction of recovery values in the samples, supplying more accurate results. In the robustness study, the method demonstrated to be consistent to external changes having to be taken a special attention to be solvent evaporation step before redissolution. Through the uncertainty estimate was possible to verify that the main sources are the repeatability, the evaporations and the sample turbidity. The analyses in real samples had satisfied the criteria of instrumental qualification and system suitability. The method selectivity has been considered in agreement and evaluated through the relative recovery of quantification and qualification ions. The method has been considered fitness for purpose and in compliance with the quality demanded by the ISO IEC 17025. |
publishDate |
2007 |
dc.date.issued.fl_str_mv |
2007-09-05 |
dc.date.accessioned.fl_str_mv |
2017-05-16 |
dc.date.available.fl_str_mv |
2017-05-16 |
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info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
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masterThesis |
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dc.identifier.citation.fl_str_mv |
SABIN, Guilherme Post. Development and validation of method using SPE AND GC-MS for the multiresidue determination of pesticides in drinking water. 2007. 166 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2007. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10430 |
identifier_str_mv |
SABIN, Guilherme Post. Development and validation of method using SPE AND GC-MS for the multiresidue determination of pesticides in drinking water. 2007. 166 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2007. |
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http://repositorio.ufsm.br/handle/1/10430 |
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