Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz

Detalhes bibliográficos
Ano de defesa: 2018
Autor(a) principal: Rosa, Francisco Cunha da lattes
Orientador(a): Dressler, Valderi Luiz lattes
Banca de defesa: Pozebon, Dirce lattes, Santos, Clarissa Marques Moreira dos lattes, Bizzi, Cezar Augusto lattes, Prestes, Osmar Damian lattes
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/1/15656
Resumo: From the discovery of intolerances related to bovine milk and wheat, there is a growing demand for derived products from rice, such as milk, beer, sake, vinegar, among others. However, these products are potential holders of high arsenic concentrations, since many studies report that rice has large amounts of this element when compared to other foods. In this sense, the laws regulating these products are restricted to setting only limits for total As content, without considering the fact that there are large differences in toxicity among the known species of this element. The inorganic forms, As (III) and As (V), are up to 100 times more toxic than organics, such as DMA and MMA, commonly detected in rice. Faced with this, the simple determination of total As may not be enough, putting many humans at risk. It is therefore very important to provide more complete information on the As species concentration present in these derived products, which can be obtained from the speciation analysis. However, for this purpose the species must be kept in their original form, which requires great attention in terms of sample preparation. Therefore, it is necessary to employ milder methods, such as extractions, which are relatively time consuming and error prone by the number of steps involved. Thus, in order to meet this demand, we proposed the development of simpler and organic solvent-free methods, aiming the As speciation analysis by LC-ICP-MS in rice milk, beer, sake and rice vinegar. In this way, we evaluated the simple dilution of the samples, the heating for evaporation of the sample matrix, the samples freeze-drying to remove the matrix and a new technique called electromembrane extraction (EME). Also, parameters such as salt type, concentration, flow rate and pH of mobile phase were evaluated, aiming at the most appropriate conditions for determining the species As(III), As(V), MMA and DMA. The results were obtained from a comprehensive chromatographic condition and demonstrated that the simple dilution of the samples is satisfactory for As speciation analysis with a good accuracy level, from 80 to 120%, according to the recovery tests, and by comparison of the species sum with the total As concentration (t-test, with confidence interval greater than 95%) obtained by ICP-MS, after microwave assisted wet digestion (MAD). The rice milks and sake were those with the highest concentrations of total As (above 10 μg L-1). There was a predominance of inorganic species (approximately 50%), with exception of sake, where DMA predominates.
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spelling 2019-02-15T13:08:03Z2019-02-15T13:08:03Z2018-12-14http://repositorio.ufsm.br/handle/1/15656From the discovery of intolerances related to bovine milk and wheat, there is a growing demand for derived products from rice, such as milk, beer, sake, vinegar, among others. However, these products are potential holders of high arsenic concentrations, since many studies report that rice has large amounts of this element when compared to other foods. In this sense, the laws regulating these products are restricted to setting only limits for total As content, without considering the fact that there are large differences in toxicity among the known species of this element. The inorganic forms, As (III) and As (V), are up to 100 times more toxic than organics, such as DMA and MMA, commonly detected in rice. Faced with this, the simple determination of total As may not be enough, putting many humans at risk. It is therefore very important to provide more complete information on the As species concentration present in these derived products, which can be obtained from the speciation analysis. However, for this purpose the species must be kept in their original form, which requires great attention in terms of sample preparation. Therefore, it is necessary to employ milder methods, such as extractions, which are relatively time consuming and error prone by the number of steps involved. Thus, in order to meet this demand, we proposed the development of simpler and organic solvent-free methods, aiming the As speciation analysis by LC-ICP-MS in rice milk, beer, sake and rice vinegar. In this way, we evaluated the simple dilution of the samples, the heating for evaporation of the sample matrix, the samples freeze-drying to remove the matrix and a new technique called electromembrane extraction (EME). Also, parameters such as salt type, concentration, flow rate and pH of mobile phase were evaluated, aiming at the most appropriate conditions for determining the species As(III), As(V), MMA and DMA. The results were obtained from a comprehensive chromatographic condition and demonstrated that the simple dilution of the samples is satisfactory for As speciation analysis with a good accuracy level, from 80 to 120%, according to the recovery tests, and by comparison of the species sum with the total As concentration (t-test, with confidence interval greater than 95%) obtained by ICP-MS, after microwave assisted wet digestion (MAD). The rice milks and sake were those with the highest concentrations of total As (above 10 μg L-1). There was a predominance of inorganic species (approximately 50%), with exception of sake, where DMA predominates.Em função da descoberta de intolerâncias relacionadas ao leite bovino e ao trigo, há uma demanda crescente por produtos derivados do arroz, tais como bebida de arroz (ou “leite de arroz”), cerveja, saquê, vinagre, entre outras. No entanto, esses produtos são potenciais detentores de concentrações elevadas de arsênio (As), uma vez que muitos estudos relatam que o arroz possui grandes quantidades deste elemento, quando comparado a outros alimentos. Nesse sentido, a legislação que regulamenta esses produtos restringe-se a estabelecer apenas limites para As total, sem considerar o fato de que há grandes diferenças de toxicidade entre as espécies conhecidas desse elemento. As formas inorgânicas, As(III) e As(V), são até 100 vezes mais tóxicas que as orgânicas, como o dimetilarsênio (DMA) e o monometiarsênio (MMA), sendo essas quatro espécies comumente detectadas no arroz. Diante disso, a determinação de As total não é suficiente, submetendo a maiores riscos os consumidores destes produtos. Por isso, é muito importante que se tenha informações mais completas sobre a concentração das espécies de As presentes nesses produtos derivados do arroz, o que pode ser obtido a partir da análise de especiação de As. Entretanto, para isso, as espécies devem ser mantidas em sua forma original, o que requer grande atenção ao preparo das amostras. Portanto, é necessário o emprego de métodos mais brandos, tais como extrações, que são relativamente morosas e susceptíveis a erros pelas etapas envolvidas. Sendo assim, buscando-se contornar alternativas morosas de preparo das amostras, neste trabalho foi proposto o desenvolvimento de métodos mais simples e livres de solventes orgânicos, visando a análise de especiação de As por cromatografia à líquido de alta eficiência por troca de íons acoplada a espectrometria de massa com plasma indutivamente acoplado (LC-ICP-MS) em bebida, cerveja, saquê e vinagre de arroz. Nesse sentido, avaliou-se a simples diluição das amostras, o aquecimento para evaporação da matriz das amostras, a liofilização das amostras para remoção da matriz e a eletroextração através de membrana (EME). Além disso, parâmetros cromatográficos como tipo de fase móvel, concentração, vazão e pH da fase móvel foram avaliados, visando-se a condição mais para a separação de As(III), As(V), DMA e MMA. Os resultados foram obtidos a partir de uma condição cromatográfica abrangente e demonstraram que a simples diluição das amostras é satisfatória para a análise de especiação de As com bom nível de exatidão, na faixa de 80 a 120%, conforme os ensaios de recuperação, e pela comparação do somatório das espécies com a concentração de As total (teste t, com intervalo de confiança superior a 95%) obtida por ICP-MS, após decomposição via úmida assistida por micro-ondas (MAD). As amostras de bebidas de arroz e saquê foram as que apresentaram concentrações mais elevadas de As total (acima de 10 μg L-1). Houve predomínio das espécies inorgânicas (aproximadamente 50%), com exceção do saquê, em que predomina o DMA.porUniversidade 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/openAccessArsênioAnálise de especiaçãoDerivados de arrozArsenicSpeciation analysisRice derivativesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICADesenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arrozDevelopment of method for arsenic speciation analysis in rice liquid derivativesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisDressler, Valderi Luizhttp://lattes.cnpq.br/4054740296547580Pozebon, Dircehttp://lattes.cnpq.br/1962782589609789Santos, Clarissa Marques Moreira doshttp://lattes.cnpq.br/5084194130501067Bizzi, Cezar Augustohttp://lattes.cnpq.br/2975070149037006Prestes, Osmar Damianhttp://lattes.cnpq.br/9632234955509028http://lattes.cnpq.br/9375431470174481Rosa, Francisco Cunha da10060000000060029c59cfe-a489-425c-88a5-18fdf7cbf25837e9f95f-123a-4e53-8596-d6e852653dc0a10aee69-497f-4257-96b7-c8a42f2d968374155d13-8098-4ad4-864e-a334be1e29ac4f68e2ef-8a41-454c-95f8-e24b79255a5d0496cf79-48da-4fcf-a75e-441d41336dd9reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGQUIMICA_2018_ROSA_FRANCISCO.pdfTES_PPGQUIMICA_2018_ROSA_FRANCISCO.pdfTese de Doutoradoapplication/pdf3519304http://repositorio.ufsm.br/bitstream/1/15656/1/TES_PPGQUIMICA_2018_ROSA_FRANCISCO.pdf75df2612231bce7de4b74e82c952a721MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz
dc.title.alternative.eng.fl_str_mv Development of method for arsenic speciation analysis in rice liquid derivatives
title Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz
spellingShingle Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz
Rosa, Francisco Cunha da
Arsênio
Análise de especiação
Derivados de arroz
Arsenic
Speciation analysis
Rice derivatives
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz
title_full Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz
title_fullStr Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz
title_full_unstemmed Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz
title_sort Desenvolvimento de método para análise de especiação de arsênio em derivados líquidos de arroz
author Rosa, Francisco Cunha da
author_facet Rosa, Francisco Cunha da
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.referee1.fl_str_mv Pozebon, Dirce
dc.contributor.referee1Lattes.fl_str_mv http://lattes.cnpq.br/1962782589609789
dc.contributor.referee2.fl_str_mv Santos, Clarissa Marques Moreira dos
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/5084194130501067
dc.contributor.referee3.fl_str_mv Bizzi, Cezar Augusto
dc.contributor.referee3Lattes.fl_str_mv http://lattes.cnpq.br/2975070149037006
dc.contributor.referee4.fl_str_mv Prestes, Osmar Damian
dc.contributor.referee4Lattes.fl_str_mv http://lattes.cnpq.br/9632234955509028
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/9375431470174481
dc.contributor.author.fl_str_mv Rosa, Francisco Cunha da
contributor_str_mv Dressler, Valderi Luiz
Pozebon, Dirce
Santos, Clarissa Marques Moreira dos
Bizzi, Cezar Augusto
Prestes, Osmar Damian
dc.subject.por.fl_str_mv Arsênio
Análise de especiação
Derivados de arroz
topic Arsênio
Análise de especiação
Derivados de arroz
Arsenic
Speciation analysis
Rice derivatives
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.eng.fl_str_mv Arsenic
Speciation analysis
Rice derivatives
dc.subject.cnpq.fl_str_mv CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description From the discovery of intolerances related to bovine milk and wheat, there is a growing demand for derived products from rice, such as milk, beer, sake, vinegar, among others. However, these products are potential holders of high arsenic concentrations, since many studies report that rice has large amounts of this element when compared to other foods. In this sense, the laws regulating these products are restricted to setting only limits for total As content, without considering the fact that there are large differences in toxicity among the known species of this element. The inorganic forms, As (III) and As (V), are up to 100 times more toxic than organics, such as DMA and MMA, commonly detected in rice. Faced with this, the simple determination of total As may not be enough, putting many humans at risk. It is therefore very important to provide more complete information on the As species concentration present in these derived products, which can be obtained from the speciation analysis. However, for this purpose the species must be kept in their original form, which requires great attention in terms of sample preparation. Therefore, it is necessary to employ milder methods, such as extractions, which are relatively time consuming and error prone by the number of steps involved. Thus, in order to meet this demand, we proposed the development of simpler and organic solvent-free methods, aiming the As speciation analysis by LC-ICP-MS in rice milk, beer, sake and rice vinegar. In this way, we evaluated the simple dilution of the samples, the heating for evaporation of the sample matrix, the samples freeze-drying to remove the matrix and a new technique called electromembrane extraction (EME). Also, parameters such as salt type, concentration, flow rate and pH of mobile phase were evaluated, aiming at the most appropriate conditions for determining the species As(III), As(V), MMA and DMA. The results were obtained from a comprehensive chromatographic condition and demonstrated that the simple dilution of the samples is satisfactory for As speciation analysis with a good accuracy level, from 80 to 120%, according to the recovery tests, and by comparison of the species sum with the total As concentration (t-test, with confidence interval greater than 95%) obtained by ICP-MS, after microwave assisted wet digestion (MAD). The rice milks and sake were those with the highest concentrations of total As (above 10 μg L-1). There was a predominance of inorganic species (approximately 50%), with exception of sake, where DMA predominates.
publishDate 2018
dc.date.issued.fl_str_mv 2018-12-14
dc.date.accessioned.fl_str_mv 2019-02-15T13:08:03Z
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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
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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
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