Determinação de resíduos de agrotóxicos em mel de abelhas (Apis sp.) por cromatografia gasosa acoplada à espectrometria de massas

=== Among the problems concerning the quality of honey, are the physical and chemicalcharacteristics, the identification of the floral and geographical origin, the occurrence ofadulteration and contamination, especially with antibiotics and pesticides. The adequacy ofthese features to existing laws...

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Bibliographic Details
Main Author: Carla Martins Pittella
Other Authors: Leorges Moraes da Fonseca
Format: Others
Language:Portuguese
Published: Universidade Federal de Minas Gerais 2009
Online Access:http://hdl.handle.net/1843/SSLA-7UZJQ7
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Summary:=== Among the problems concerning the quality of honey, are the physical and chemicalcharacteristics, the identification of the floral and geographical origin, the occurrence ofadulteration and contamination, especially with antibiotics and pesticides. The adequacy ofthese features to existing laws in the country makes the product more competitive for the exportmarket. This work aims the development of a multi residue methodology for the determinationof pesticides in honey, as a contribution to the improvement of methodologies for the analysis ofcontaminants described in Normative Instruction No 9, March 30, 2007 to MAPA and itsapplication in samples of honey from different regions of Brazil. The technique used was gaschromatography coupled to mass spectrometry, using SIM acquisition mode, electron ionization(EI) at 70 eV. Three techniques of extraction - liquid-liquid extraction, solid phase extraction(C18) and dispersive solid phase extraction modified "QuEChERS" was evaluated. The resultsof the extraction procedures indicated the interference of the matrix in the chromatographicresponses when compared with the analytical curve obtained only in ethyl acetate. Best analyteresponses were obtained for the liquid-liquid extraction with ethyl acetate. A method usingliquid-liquid extraction and analytical curves obtained in the matrix extract resuspended in ethylacetate was developed and validated for the 20 pesticides from the classes of organochlorinepesticides, organophosphates, carbamates and pyrethroids. In this work the followingparameters were assessed for validation of the method. Linearity of analytical curves (7concentration levels and six injections each). Analytical curves were obtained to adjustment forquadratic regression and determination coefficients higher than 0.989. Limit of detection (LOD)calculated ranged from 0,4 to 13,4 ng mL-1 and limit of quantification (LOQ) performedbetween 1,4 and 60,8 ng mL-1. The precision for the study of repetibilibidade (% RSD between3,4 and 32,9%) and accuracy (recovery rate - 92% a 115%). The fortifications of the sampleswere taken at three concentration levels (1,0 ìg kg-1, 5,0 ìg kg-1, 10,0 ìg kg-1). Themethodology was applied to the analysis of 46 honey samples from different regions of Brazil.It was detected the presence of pesticides in 8 samples. In three of them, the compounds foundmay be related to the use of pesticides on crops in the neighborhood of apiaries === Entre as questoes relativas a qualidade do mel de abelhas, estao as caracteristicas fisicoquimicas, a identificacao da origem floral e geografica, a ocorrencia de adulteracoes e as contaminacoes, principalmente, com antibioticos e agrotoxicos. A adequacao dessascaracteristicas as legislacoes vigentes no pais torna o produto mais competitivo para o mercado de exportacao. O presente trabalho tem como objetivo o desenvolvimento de metodologia multirresiduo para a determinacao de agrotoxicos em mel de abelhas por cromatografia gasosa acoplada a espectrometria de massas, modo de aquisicao SIM usando ionizacao por eletrons (EI) a 70 eV.como contribuicao para o aprimoramento das metodologias de analise de contaminantes descritos na Instrucao Normativa no 9, de 30 de marco de 2007 do MAPA e sua aplicacao em amostras de mel de diferentes regioes do Brasil. Foram avaliadas tres tecnicas de extracao . extracao liquido-liquido, SPE - C18 e fase solida dispersiva "QuEChERS" modificado. Os resultados dos procedimentos de extracao indicaram a interferencia da matriznas respostas cromatograficas, quando comparadas com a curva analitica obtida apenas em acetato de etila. Maiores respostas para os analitos foram obtidas para a extracao liquido-liquido em acetato de etila. A metodologia utilizando extracao liquido-liquido e curvas analiticasobtidas no extrato da matriz ressuspendida em acetato de etila foi desenvolvida e validada para 20 agrotoxicos das classes dos organoclorados, organofosforados, carbamatos e piretroides.Neste trabalho, foram avaliados alguns parametros de validacao do metodo. A linearidade das curvas analiticas (sete niveis de concentracao e seis injecoes cada). Foram obtidas curvas analiticas com ajuste para regressao quadratica e coeficientes de determinacao superiores a0,989. Os limites de deteccao calculados variaram de 0,4 a 13,4 ng mL-1 e os limite de quantificacao apresentaram resultados entre 1,4 e 60,8 ng mL-1. A precisao pelo estudo de repetibilibidade (DPR entre 3,4 a 32,9%) e a exatidao pelo estudo dos indices de recuperacao(92% a 115%). As fortificacoes das amostras foram realizadas em tres niveis de concentracao (1,0 Êg kg-1, 5,0 Êg kg-1, 10,0 Êg kg-1). A metodologia foi aplicada em 46 amostras de mel oriundas de diferentes regioes do Brasil. Foi detectada a presenca de agrotoxicos em oitoamostras. Em tres delas, os compostos encontrados podem estar relacionados com o uso dos agrotoxicos nas culturas no entorno dos apiarios