RESUMO Alimentação adequada durante os primeiros anos de vida é fundamental para a saúde e tem repercussões em todos os ciclos da vida do indivíduo. Diversos trabalhos científicos associam efeitos nocivos à saúde com exposição aos agrotóxicos. Foram avaliados 312 agrotóxicos em alimentos comumente presentes na dieta infantil, selecionados a partir do cardápio do programa de alimentação escolar da educação infantil do município do Rio de Janeiro. A seleção dos alimentos baseou-se na frequência de consumo conforme os cardápios semanais da rede municipal de ensino. A análise multirresíduos por Cromatografia Líquida de Ultra Eficiência acoplada à Espectrometria de Massas sequencial em 145 amostras (leite, cereais infantis, banana, maçã, mamão, laranja, feijão e arroz) identificou 426 detecções de 53 agrotóxicos diferentes. Mais de 68% das amostras apresentaram múltiplos resíduos de agrotóxicos. Com os resultados, foi estimada a exposição da população infantil aos resíduos encontrados, indicando potencial risco à saúde das crianças, que precisa ser uma preocupação prioritária da saúde pública. É necessário verificar os impactos toxicológicos do uso de agrotóxicos sobre a saúde infantil, ampliar a aquisição de alimentos orgânicos pelo Programa Nacional de Alimentação Escolar e fortalecer a agroecologia com incentivos e políticas pública, buscando proteção e promoção da saúde coletiva.

ABSTRACT Adequate nutrition in the first years of life is a fundamental requirement for health and affects all life cycles of the individual. Several scientific studies associate exposure to pesticides with adverse effects to health. A total of 312 pesticides residues were evaluated in common foods from children’s diets, selected from the infancy school feeding program menu in the city of Rio de Janeiro. The selection of food was based on the frequency of consumption according to the weekly menus of the municipal school system. Multiresidue pesticide analysis by Ultra Performance Liquid Chromatography coupled to tandem Mass Spectrometry in 145 samples (milk, infant cereal, banana, apple, papaya, orange, beans and rice) identified 426 detections of 53 different pesticides. More than 68% of the samples had multiple pesticide residues. Based on the results, was estimated the exposure of children to residues that were detected, indicating a potential risk to children’s health, which needs to be a priority public health concern. It is necessary to verify the toxicological impacts of the use of pesticides on children’s health, to expand the acquisition of organic foods by the School Feeding National Program, and to strengthen agroecology with incentives and public policies, aiming at the protection and promotion of collective health.

RESUMO Alimentação adequada durante os primeiros anos de vida é fundamental para a saúde e tem repercussões em todos os ciclos da vida do indivíduo. Diversos trabalhos científicos associam efeitos nocivos à saúde com exposição aos agrotóxicos. Foram avaliados 312 agrotóxicos em alimentos comumente presentes na dieta infantil, selecionados a partir do cardápio do programa de alimentação escolar da educação infantil do município do Rio de Janeiro. A seleção dos alimentos baseou-se na frequência de consumo conforme os cardápios semanais da rede municipal de ensino. A análise multirresíduos por Cromatografia Líquida de Ultra Eficiência acoplada à Espectrometria de Massas sequencial em 145 amostras (leite, cereais infantis, banana, maçã, mamão, laranja, feijão e arroz) identificou 426 detecções de 53 agrotóxicos diferentes. Mais de 68% das amostras apresentaram múltiplos resíduos de agrotóxicos. Com os resultados, foi estimada a exposição da população infantil aos resíduos encontrados, indicando potencial risco à saúde das crianças, que precisa ser uma preocupação prioritária da saúde pública. É necessário verificar os impactos toxicológicos do uso de agrotóxicos sobre a saúde infantil, ampliar a aquisição de alimentos orgânicos pelo Programa Nacional de Alimentação Escolar e fortalecer a agroecologia com incentivos e políticas pública, buscando proteção e promoção da saúde coletiva.

ABSTRACT Adequate nutrition in the first years of life is a fundamental requirement for health and affects all life cycles of the individual. Several scientific studies associate exposure to pesticides with adverse effects to health. A total of 312 pesticides residues were evaluated in common foods from children’s diets, selected from the infancy school feeding program menu in the city of Rio de Janeiro. The selection of food was based on the frequency of consumption according to the weekly menus of the municipal school system. Multiresidue pesticide analysis by Ultra Performance Liquid Chromatography coupled to tandem Mass Spectrometry in 145 samples (milk, infant cereal, banana, apple, papaya, orange, beans and rice) identified 426 detections of 53 different pesticides. More than 68% of the samples had multiple pesticide residues. Based on the results, was estimated the exposure of children to residues that were detected, indicating a potential risk to children’s health, which needs to be a priority public health concern. It is necessary to verify the toxicological impacts of the use of pesticides on children’s health, to expand the acquisition of organic foods by the School Feeding National Program, and to strengthen agroecology with incentives and public policies, aiming at the protection and promotion of collective health.

Abstract An analytical method applying ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was validated for the determination of aflatoxins M2, M1, G2, G1, B2, B1, deoxynivalenol, ochratoxin A, fumonisins B1 and B2, hydrolyzed fumonisins B1 and B2, zearalenone and sterigmatocystin in crackers. The obtained recoveries (70 to 110%) and relative standard deviations (< 13%) were considered satisfactory. Method limits of quantification ranged from 0.20 µg kg-1 (sterigmatocystin) to 12.27 µg kg-1 (deoxynivalenol). The validated method was then applied for mycotoxin determination in 60 cracker samples (cream crackers and water and salt crackers) obtained from the metropolitan area of the state of Rio de Janeiro, RJ. Deoxynivalenol, zearalenone and fumonisin B1 were found, respectively, in 100, 50 and 28% of the analyzed samples. The maximum permissible limits established by Brazilian legislation for deoxynivalenol and zearalenone were not exceeded in the analyzed samples.

Samples of whole fluid pasteurized, UHT and powdered milk were analyzed for the presence of organophosphorus pesticide residues (OPR) using the QuEChERS method with detection by GC-FPD and confirmation by UPLC-MS/MS. A total of 23% of fluid milk samples and 27% of powdered milk samples contained at least one organophosphorus residue. The OPR found in the samples showed these can reach the milk and remain even after pasteurization, sterilization and drying processes. Some domestic sanitary residues were also present in the powdered milk samples. These residues have no LMR in Brazilian food legislation and are therefore not taken into account in food intake evaluations. There was an unidentified chromatographic peak in 30% of all the liquid and powdered milk samples, indicating the presence of some other contaminant.

This paper regards the implementation of the QuEChERS method for the analysis by GC-FPD of 53 different pesticides from the organophosphate class, in whole UHT and pasteurized milk. Selectivity, linearity, repeatability, recovery and limits of detection and quantification were evaluated. Of all pesticide recoveries, 51 were considered satisfactory since the values ranged from 70 to 120% with RSD < 20%. The quantification limits ranged from 0.005 to 0.4 mg kg-1. The QuEChERS method was suitable for determination of 52 pesticides, presenting several advantages - quick, cheap, easy, effective, rugged and safe - with regard to other traditional methodologies.

Neste trabalho são apresentados os resultados dos estudos de estabilidade referentes à produção de um material de referência certificado. Foram avaliados níveis residuais de concentração dos agrotóxicos γ-HCH, fenitrotiona, clorpirifós e procimidona em polpa de tomate. A pasteurização e a irradiação gama foram empregadas à polpa de tomate, visando manter a integridade da amostra candidata a material de referência. A polpa foi preparada e dividida em duas partes. Cada parte foi fortificada com os referidos agrotóxicos na faixa de concentração de 0,1 a 0,2 mg.kg-1. Uma das partes foi submetida à pasteurização a 90 °C por 4 minutos e a outra parte foi irradiada com dose de 2,0 kGy depois de homogeneizada. A estabilidade e a incerteza da amostra, correspondente ao período de tempo avaliado, foram determinadas através da análise de regressão em conjunto com a ANOVA. Os resultados indicaram que ambos os procedimentos de preparo da amostra são adequados para a conservação da polpa de tomate fortificada com os quatro agrotóxicos, com vantagem para o tratamento por irradiação com a dose de 2,0 kGy.

This research presents the results of stability studies regarding the production of certified reference materials. The residual concentration levels of four pesticides, namely γ-HCH, fenitrothion, chlorpyrifos, and procymidone were investigated. Pasteurization combined with gamma irradiation was used to maintain the integrity of the mixture tested as a reference material candidate. The pulp was prepared and split into two parts. Each part was then spiked with those pesticides in the concentration range of 0.1 to 0.2 mg.kg-1 in tomato pulp. One of them was submitted to pasteurization at 90 °C for 4 minutes after being homogenized, and the other was irradiated with a gamma dose of 2.0 kGy. The material stability and the corresponding uncertainty during the period of time evaluated were determined using regression analysis and ANOVA. The results indicated that the dose of 2.0 kGy was appropriated for the conservation of tomato pulp spiked with the four aforementioned pesticides.

Neste trabalho são apresentados os esforços para garantir a homogeneidade de um material de referência. Níveis residuais (mg.kg-1) de quatro agrotóxicos (γ-HCH, fenitrotiona, clorpirifós e procimidona) foram adicionados à polpa de tomate com o objetivo de se preparar um material de referência certificado. As propriedades mais importantes desses materiais são a homogeneidade e a estabilidade. Antes de serem enviados a outros laboratórios, os materiais de referência precisam ter sua homogeneidade verificada. Nas etapas prévias, amostras foram avaliadas de modo a prover dados sobre o tratamento mais adequado para minimizar a variabilidade analítica do lote preparado e garantir a qualidade da amostra candidata a material de referência certificado, tão bem como a estimativa da incerteza associada à homogeneidade. A análise de variância fornece informações sobre a variabilidade do lote preparado e o grau de invariabilidade da amostra fortificada. Depois da preparação, as amostras foram expostas à radiação gama na dose de 2 kGy e submetidas a um estudo interlaboratorial para certificação. As concentrações certificadas dos agrotóxicos após caracterização foram 0,191 ± 0,047 mg.kg-1; 0,192 ± 0,068 mg.kg-1; 0,225 ± 0,076 mg.kg-1e 0,177 ± 0,051 mg.kg-1 para o γ-HCH, a fenitrotiona, clorpirifós e procimidona respectivamente.

This study reports on the efforts to ensure homogeneity of certified reference materials. Residues of four pesticides (γ-HCH, fenitrothion, chlorpyrifos, and procymidone) were added to tomato pulp in order to produce reference materials. The two most important properties of such materials are known to be homogeneity and stability. Before being shipped to other laboratories, reference materials must have their homogeneity certified. As part of a preliminary study, hundreds of samples were investigated in order to provide data on the most suitable treatments to minimize analytical variability and ensure the quality of samples intended for use as reference materials as well as to yield estimates of the uncertainty associated to the homogeneity data. In addition, the variance analysis provided accurate information on the bulk variability and the degree of non-homogeneity of contaminated samples. After preparation, the samples were exposed to 2 kGy of gamma radiation and submitted to an interlaboratory certification study. The certified concentrations of γ-HCH, fenithrotion, chlorpyrifos, and procymidone were 0.191 ± 0.047 mg.kg-1; 0.192 ± 0.068 mg.kg-1; 0.225 ± 0.076 mg.kg-1 , and 0.177 ± 0.051 mg.kg-1, respectively.

Um modelo de procedimento para validação de método de ensaio para determinação de cinco agrotóxicos (γ - HCH, clorotalonil, fenitrotiona, clorpirifós e procimidona em matriz tomate) é demonstrado através da análise cromatográfica. A amostra processada é extraída com 30 mL de acetona e em seguida com 60 mL de uma mistura diclometano: éter de petróleo (1:1). O volume total é centrifugado e a alíquota orgânica é filtrada sob Na2SO4. Um mililitro de extrato orgânico é concentrado e dissolvido em um mililitro de iso-octano. Um microlitro do extrato é analisado no cromatógrafo a gás com detector por captura de elétrons - CG/DCE. Foram avaliados seletividade, linearidade, repetitividade, recuperação e limites de detecção e de quantificação. As recuperações obtidas variaram de 70 a 110%, considerando-se os níveis de adição de agrotóxicos/amostra de 0,02 a 2,50 mg.kg-1. Os limites de detecção do método variaram de 0,004 a 0,006 mg.kg-1 e os de quantificação entre 0,014 e 0,020 mg.kg-1.

A validation procedure model of a multiresidue method is presented for chromatographic analyses of five pesticides residues γ-HCH, chlorothalonil, fenitrothion, chlorpyrifos and procymidone applied on tomatoes. The tomatoes were processed and extracted by acetone plus a mixture of dichloromethane:petroleum benzine (1:1). The volume was centrifuged and was then filtered under Na2SO4. One milliliter of organic extract was concentrated then diluted in isooctane and one microliter was analyzed in the gas chromatograph with electron capture detector - GC/ECD. The parameters evaluated were selectivity, linearity, repeatability, recovery, and limits of detection and quantification. The recovery ranged from 70 to 110% in the concentration range of 0.02 to 2.50 mg.kg-1. The limits of detection ranged from 0.004 to 0.006 mg.kg-1 and the limits of quantification were between 0.014 to 0.02 mg.kg-1.

A proficiency assay of the determination of dithiocarbamate pesticide residues in banana was carried out. Fourteen laboratories participated in this study. Homogeneity and stability testing were performed by INCQS on the samples sent to the laboratories. Analytical results supplied by the pesticide residues laboratory of the VWA/KvW, Amsterdam, Holland, were used to define the designated value for the thiram concentration in the study samples. RESULTS: Fifty percent of the participating laboratories had satisfactory results. Efforts are needed to improve the precision of the analytical results and to decrease the number of false negative results observed.