Abstract The continuous increase in the use and release of pesticides is worrisome because water contamination can affect health and the environment. This study optimized and validated a multi-residue method in water. The method was developed using the QuEChERS method (Quick, Easy, Cheap, Effective, Rugged, and Safe) followed by ultrahigh- performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The validation was performed on the matrix (river water) regarding accuracy, precision, linearity, limits of detection (LODs) and limits of quantification (LOQs). LODs were below 3.03 µg L-1and LOQs were from 6.25 to 9.18 µg L-1. The accuracy (recoveries in the range of 80-117%) and for Inter-day precision, the coefficients of variation ranged from 0.35 to 15.71%, and for Intra-day precision were in the range of 0.48 to 7.02%. environment multiresidue multi residue Quick, Quick (Quick Easy Cheap Effective Rugged Safe ultrahigh UHPLCMS/MS. UHPLCMSMS UHPLC MS/MS . MS (UHPLC-MS/MS) river linearity (LODs LOQs. (LOQs) 303 3 03 3.0 L1and Land L 1and 625 6 25 6.2 918 9 18 9.1 L1. L1 1. 1 L-1 recoveries 80117% 80117 80 117% 117 80-117% Interday Inter day 035 0 35 0.3 1571 15 71 15.71% Intraday Intra 048 48 0.4 702 7 02 7.02% UHPLCMS UHPLCMS/MS MSMS (UHPLC-MS/MS (LOQs 30 3. 62 2 6. 91 9. L- 8011 8 11 80-117 0. 157 15.71 04 4 70 7.02 801 80-11 15.7 7.0 80-1 15. 7. 80-

Resumo O aumento contínuo do uso e liberação de agrotóxicos tem tornado o cenário preocupante, pois a contaminação das águas pode afetar a saúde e o meio ambiente. Neste estudo, um método multiresíduo em água foi otimizado e validado. O método foi desenvolvido utilizando o método QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) seguido de cromatografia líquida acoplada a espectrometria de massa (UHPLC-MS/MS). A validação foi realizada na matriz (água do rio) avaliando à exatidão, precisão, linearidade, limites de detecção (LODs) e limites de quantificação (LOQs). Os LODs ficaram abaixo de 3,03 µg L-1 e os LOQs variaram de 6,25 a 9,18 µg L-1. A exatidão apresentou recuperações de 80 a 117% e o coeficiente de variação para a repetibilidade foi de 0,35-15,71% e de 0,48-7,02% para a precisão intermediária. preocupante ambiente estudo validado Quick, Quick (Quick Easy Cheap Effective Rugged Safe UHPLCMS/MS. UHPLCMSMS UHPLC MS/MS . MS (UHPLC-MS/MS) rio linearidade (LODs LOQs. (LOQs) 303 3 03 3,0 L1 L 1 L- 625 6 25 6,2 918 9 18 9,1 L1. 1. 8 117 0,3515,71% 0351571 0,35 15,71% 0 35 15 71 0,35-15,71 0,487,02% 048702 0,48 7,02% 48 7 02 0,48-7,02 intermediária UHPLCMS UHPLCMS/MS MSMS (UHPLC-MS/MS (LOQs 30 3, 62 2 6, 91 9, 11 3515 0,3515,71 035157 035 0,3 1571 15,71 0,35-15,7 487 0,487,02 04870 048 0,4 702 7,02 4 0,48-7,0 351 0,3515,7 03515 0, 157 15,7 0,35-15, 0,487,0 0487 04 70 7,0 0,48-7, 0,3515, 0351 15, 0,35-15 0,487, 7, 0,48-7 0,3515 0,35-1 0,487 0,48- 0,351 0,35-

Given the extensive use of pesticides in modern times, residues are frequently detected in water samples. Therefore, this study developed and validated a method utilizing solid-phase extraction (SPE) with a polymeric sorbent for sample preparation in combination with ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The aim was to determine a variety of current-use pesticides (CUPs) in different types of water. The preconcentration step, employing the polymeric sorbent Oasis HLB (60 mg), combined with the high selectivity and sensitivity of the UHPLC-MS/MS analysis, enabled the multiclass determination of pesticide residues in water samples at very low concentrations. The proposed method underwent validation, demonstrating satisfactory linearity, precision, and accuracy. The accuracy results, determined through recovery assays at varying spike levels (0.04-0.4 μg L-1), ranged from 71 to 117%, with precision expressed as relative standard deviations consistently below 19%. The practical limits of detection and quantification for most compounds were 0.01 and 0.04 μg L-1, respectively. This method was effectively employed to analyze drinking water, artesian well water, dam water, and river water, leading to the detection of various pesticides at concentrations of up to 2.24 μg L-1. times Therefore solidphase solid phase SPE (SPE ultrahigh ultra UHPLCMS/MS. UHPLCMSMS UHPLC MS/MS . MS (UHPLC-MS/MS) currentuse current CUPs (CUPs step 60 (6 mg, mg , mg) UHPLCMS/MS analysis validation linearity results 0.040.4 00404 0.4 0 04 4 (0.04-0. L1, L1 L 1 L-1) 7 117 117% 19 19% 001 01 0.0 004 1, L-1 respectively 224 2 24 2.2 L1. 1. UHPLCMS MSMS (UHPLC-MS/MS 6 ( 040 0.040. 0040 0. (0.04-0 11 00 L- 22 2. 0.040 (0.04- (0.04 (0.0 (0. (0

Resumo O objetivo deste trabalho foi adaptar e validar um método multirresíduo para análise de agrotóxicos, para determinar a influência das atuais etapas de manejo pós-colheita sobre a degradação de resíduos de agrotóxicos em mamão. Mamões 'THB' do grupo Solo foram amostrados em cada etapa de manejo pós-colheita, em casa de beneficiamento. Para a validação da análise multirresíduos em mamão, a técnica de extração utilizada foi o método quick, easy, cheap, effective, rugged, and safe (QuEChERS), com modificações. A quantificação foi realizada com cromatógrafo líquido de ultraeficiência, acoplado a espectrômetro de massa triplo, quadrupolo, com ionização por eletrospray (UHPLC-MS/MS). Os frutos foram analisados antes e depois dos procedimentos de manuseio e avaliados após o amadurecimento. A metodologia utilizada foi validada com sucesso para detectar os pesticidas azoxistrobina, carbendazim, carbofuran, difenoconazol, imazalil, imidacloprid, flutriafol, prochloraz, piraclostrobina, tebuconazol, tiabendazol e thiacloprid em mamão. A lavagem dos frutos reduz os níveis de resíduos de azoxistrobina e difenoconazol em 78 a 90% e em 47 a 90% na superfície dos frutos, respectivamente. Embora as etapas de manejo pós-colheita sejam ineficazes para a redução dos níveis do tiabendazol, se este fungicida for utilizado na dose adequada, os níveis de resíduos permanecerão abaixo dos limites permitidos por lei. póscolheita pós colheita mamão THB 'THB póscolheita, colheita, beneficiamento quick easy cheap effective rugged QuEChERS, QuEChERS , (QuEChERS) modificações ultraeficiência triplo quadrupolo UHPLCMS/MS. UHPLCMSMS UHPLC MS/MS . MS (UHPLC-MS/MS) amadurecimento carbendazim carbofuran imazalil imidacloprid flutriafol prochloraz piraclostrobina tebuconazol 7 90 4 respectivamente adequada lei (QuEChERS UHPLCMS UHPLCMS/MS MSMS (UHPLC-MS/MS 9

Abstract The objective of this work was to adapt and validate a multiresidue method for pesticide analysis, to determine the influence of the current postharvest handling steps on the degradation of pesticide residues in papaya. 'THB' papaya of the Solo group were sampled at each postharvest handling step in the packinghouse. For the validation of the multiresidue analysis in papaya, the technique used for extraction was the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, with modifications. Pesticide quantification was carried out using an ultra-high performance liquid chromatograph coupled to a triple quadrupole mass spectrometer with electrospray ionization (UHPLC-MS/MS). Fruit were analyzed before and after the handling procedures and were evaluated after ripening. The used methodology was successfully validated to detect the azoxystrobin, carbendazim, carbofuran, difenoconazole, imazalil, imidacloprid, flutriafol, prochloraz, pyraclostrobin, tebuconazole, thiabendazole, and thiacloprid pesticides in papaya. Fruit washing reduces azoxystrobin and difenoconazole residue levels in 78 to 90% and in 47 to 90% on fruit surface, respectively. Although the postharvest handling steps are ineffective in reducing the levels of thiabendazole, if this fungicide is applied at the appropriate rate, the residue levels will remain below the limits permitted by law. THB 'THB packinghouse quick easy cheap effective rugged QuEChERS (QuEChERS modifications ultrahigh ultra high UHPLCMS/MS. UHPLCMSMS UHPLC MS/MS . MS (UHPLC-MS/MS) ripening carbendazim carbofuran imazalil imidacloprid flutriafol prochloraz pyraclostrobin tebuconazole thiabendazole 7 90 4 surface respectively rate law UHPLCMS UHPLCMS/MS MSMS (UHPLC-MS/MS 9

The growing awareness of health and well-being has led to increased consumption of healthy foods, such as exotic fruits, owing to their high nutritional value and global availability. However, the production and trade of exotic fruit presents significant challenges, particularly with regard to increasing supply and ensuring food safety concerning pesticide residues. This review examines modern analytical strategies employed to determine pesticide residues in exotic fruits. It is evident from the literature that ultra-high performance liquid chromatography and gas chromatography techniques, coupled with tandem mass spectrometry, remain the methods of choice for determining pesticide residues. For sample preparation, the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method, renowned for its simplicity and efficiency, is extensively utilized in its original form as well as in acetate, citrate, and other modified versions to enhance its effectiveness. Developing these analytical methods is crucial for ensuring the safety of exotic fruits, protecting consumer health, and facilitating exports to global markets. Further advancements in this field are essential to overcome the challenges posed by producing and trading exotic fruits, thereby promoting food safety and public health. This review also discusses the occurrence of pesticides in exotic fruits. wellbeing being foods fruits availability However ultrahigh ultra techniques spectrometry preparation Quick, Quick (Quick Easy Cheap Effective Rugged Safe method efficiency acetate citrate effectiveness markets

The tomato (Solanum lycopersicon L.) crop has great economic relevance, being one of the most processed agricultural products worldwide. Some pesticides are chemically stable and can remain in food even after processing. In this context, the objective of this work was to analyze food products derived from tomatoes (extract, sauce and ketchup), regarding the levels of pesticide residues. Fifteen samples were acquired from Vale do Jaguaribe, Ceará, Brazil. Six pesticides (bifenthrin, chlorothalonil, chlorpyrifos, cyfluthrin, pyriproxyfen, trifluralin) authorized by Agência Nacional de Vigilância Sanitária (Anvisa) for tomato cultivation were selected for the study. QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction and gas chromatography coupled to mass spectrometry (GC-MS) were used in method validation, according to the recommendations of SANTE 11312/2021 guidelines. Statistical analyses of linearity showed that the six pesticides studied were classified as heterocesdastic. Limits of detection (LOD) and quantification (LOQ) values (0.01-0.03 and 0.03-0.10 mg kg-1, respectively) were below the established maximum residue limits (MRLs) for tomatoes. Accuracy and precision (78-121 and 2.3-16.7%, respectively) were satisfactory. The results indicated that among the 15 analyzed samples, one active ingredient was detected (0.05 mg kg-1) in a tomato sauce sample, lower than MRLs (Anvisa 0.15 mg kg-1 and FAO 0.3 mg kg-1). The results show the relevance of monitoring pesticide residues in tomato-derived products and the validation of new methodologies for food control. Solanum L. L worldwide processing context extract, extract (extract ketchup, ketchup , ketchup) Jaguaribe Ceará Brazil bifenthrin, bifenthrin (bifenthrin chlorothalonil chlorpyrifos cyfluthrin pyriproxyfen trifluralin Anvisa study quick, quick (quick easy cheap effective rugged safe GCMS GC MS (GC-MS 113122021 11312 2021 11312/202 guidelines heterocesdastic LOD (LOD LOQ (LOQ 0.010.03 001003 0.01 0.03 0 01 03 (0.01-0.0 0.030.10 003010 0.10 10 0.03-0.1 kg1, kg1 kg 1, 1 respectively (MRLs 78121 78 121 (78-12 2.316.7%, 23167 2.3 16.7%, 2 3 16 7 2.3-16.7% satisfactory 0.05 005 05 (0.0 sample 015 0.1 kg- 0. kg1. . tomatoderived control 11312202 1131 202 11312/20 010 0.010.0 00100 001 0.0 003 (0.01-0. 030 0.030.1 00301 0.03-0. 7812 12 (78-1 316 2.316.7% 2316 23 2. 167 16.7% 2.3-16.7 00 (0. 1131220 113 20 11312/2 0.010. 0010 (0.01-0 0.030. 0030 0.03-0 781 (78- 31 2.316.7 231 16.7 2.3-16. (0 113122 11 11312/ 0.010 (0.01- 0.030 0.03- (78 2.316. 16. 2.3-16 ( (0.01 (7 2.316 2.3-1 2.31 2.3-

RESUMO: A frequente presença do morango entre os alimentos com resíduos de agrotóxicos acima do limite máximo ou não autorizados gera uma série de questionamentos em relação aos riscos envolvidos no seu consumo. Nos processos de avaliação do riscopodemserutilizadosmétodosdeterminísticos e probabilísticosdependendo dos dados disponíveis. O objetivodestetrabalhofoiconduzirumaavaliaçãodeterminística e probabilística do risco de ingestão de agrotóxicosatravés do consumo de morangos. Para tanto, 62 amostras de morangosforamanalisadasatravés do método de multiresíduos entre osanos de 2018 e 2019. Osresultados de concentração dos ingredientesativosforamorganizados e utilizados para oscálculos de estimativa da ingestão. No métododeterminísticoaingestãofoicalculada com base nos dados de concentração dos ingredientesativos das amostras de morangos, dados de consumoprovenientes de um questionário online e pesos corporais entre 5 e 70 kg. No métodoprobabilísticoforamutilizadosos dados de concentração dos ingredientesativos das amostras e peso corporal de 60 kg noscenários um e dois, onde, no primeiro, os dados de consumoutilizadosforamos dados do questionário e no segundoos dados de consumo de morangoprovenientes da Pesquisa de OrçamentosFamiliares. Nas 62 amostras de morangoanalisadasforamdetectados 38 ingredientesativos, sendo 25 amostrasconsideradassatisfatórias, e 37 insatisfatórias. Entre osingredientesativosdetectados, 40% nãotêmseuusoautorizado para a cultura. Na avaliaçãodeterminística, 23% dos ingredientesativosapresentaramingestãocalculada superior a ingestãodiáriaaceitávelempelomenos um cenário, estando o riscoconcentradonos pesos corporais entre 5 e 30 kg, sendo o riscobaixoquandoconsiderado o peso corporal de 60 kg. Todososingredientesativostestados no primeirocenário da avaliaçãoprobabilísticaapresentaramalgumapossibilidade de aingestãoser superior a ingestãodiáriaaceitável, enquanto que para o segundocenárioapenas o ingredienteativoprocimidonasuperou a ingestãodiáriaaceitável. Entre osmodelosestudados, o primeirocenário da avaliaçãoprobabilísticafoi o que apresentou a maiorprobabilidade de provocarintoxicação e procimidonafoi o ingredienteativomaisfrequentementedetectadonasamostras, e que apresentou as maiores chances de oferecerrisco à saúde.

ABSTRACT: Repeated presence of strawberries amongst produce with pesticide residues results in questionings related to the risks involved by its consumption. Deterministic and probabilistic risk assessment methods might be used depending on the available data. In the present study, both methods were used to estimate risks of pesticide intake by strawberry consumption. Strawberry samples along two years were analyzed via the multiresidue method. Results of active ingredients (a.i.) concentrations were organized and used for calculations for intake estimates. On the deterministic method, intake was calculated based on the data of a.i. concentration and consumption data coming from an online questionnaire and body weight between 5 and 70 kg. On the probabilistic method, the concentrations of a.i. and body weight of 60 kg were evaluated in two scenarios: a) consumption data from an online questionnaire or b) consumption data retrieved from Family Budget Survey of the Brazilian Institute of Geography and Statistics. In the 62 strawberry samples, 38 a.i. were quantified and in 25 samples the residue analyses were considered satisfactory and 37 had an unsatisfactory outcome. In the deterministic approach, 23% of the a.i. had a calculated intake higher than the acceptable daily intake (ADI) and risk concentrated in body weights between 5 and 30 kg. The risk is low when considering a body weight of 60 kg. All a.i. tested in the first scenario of the probabilistic method pointed towards some possibility of intake being higher than the ADI. In the second scenario, only the a.i. procymidone exceeded the ADI.

Grapes are among the most widely cultivated fruits in the world, with the majority of Brazilian production focusing on natural grape juice. In this work, a total of 40 samples of 2 types of natural grape juice were analyzed for the presence of 86 pesticide residues, with multiresidue extraction based on modified QuEChERS, by liquid chromatography with high-resolution mass spectrometry (LC-HRMS). Limits of detection and quantification were below 6 µg L-1 and 20 µg L-1, RSD < 20%, R2 > 0.99 and recovery ranged from 80 and 120%. Thus, the developed method was validated and good performance characteristics such as linearity, trueness, repeatability and inter-day precision were obtained. As results, 7 pesticides were detected in real samples (azoxystrobin, benalaxyl, carbendazim, tebuconazol, thiophanate-methyl, pyriproxiphen and pyrimethanil). The method was successfully validated for simultaneous evaluation of 86 multiclass pesticides residues levels, which was applied in 40 natural white and red grape juice market samples. The limits of quantification (LOQs) were low enough and the method was tested on samples showing its applicability, and therefore, this method can be used in routine analysis. Also, this work therefore also serves as an alert regarding the contamination of processed products. world 4 8 QuEChERS highresolution high resolution LCHRMS. LCHRMS LC HRMS . (LC-HRMS) L1 L 1 L- L1, 1, 20% R 099 0 99 0.9 120 120% Thus linearity trueness interday inter day obtained results azoxystrobin, azoxystrobin (azoxystrobin benalaxyl carbendazim tebuconazol thiophanatemethyl, thiophanatemethyl thiophanate methyl, methyl thiophanate-methyl pyrimethanil. pyrimethanil pyrimethanil) levels LOQs (LOQs applicability analysis Also products (LC-HRMS 09 9 0. 12

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.

This work focuses on the validation and application of solid phase extraction followed by high-performance liquid chromatography (SPE-HPLC) analysis of important endocrine disruptors compounds (EDC) from different classes in highly complex wastewater matrix. The endocrine disruptors investigated included three different categories: pharmaceuticals (sulfamethoxazole (SMZ), trimethoprim (TMP) and diclofenac (DCF)), hormones (estrone (E1), 17α-ethinylestradiol (EE2) and 17β-estradiol (E2)) and plastic materials (bisphenol A (BPA)). The method involves pre-concentration by SPE using Strata-X extraction cartridges followed by HPLC coupled with diode array detector (DAD). As the assumption of homoscedasticity was met for analytical data, ordinary linear regression procedure was applied to the data. The method was considered validated for 7 EDC after consistent evaluation of the key analytical parameters. Recoveries were ranged from 52.3 to 179.6%. Limits of quantification were in the range 6.0-0.4 µg L−1. The described method was applied to evaluate the occurrence and removal efficiency of EDC in two biological sewage treatment plants (STPs). The influent mean concentrations of E1, E2 and EE2 hormones were 79.54; 175.09 and 102.19 µg L−1, respectively, while for SMZ, TMP, DCF and BPA were 215.17; 187.01; 218.97 and 87.12 µg L−1 for STP A, respectively. The efficiencies for the removal of EDCs ranged from 0 to 79.4%.

Abstract: The pesticides intake causes health problems; therefore, food must not exceed the maximum allowable limits. The aim of this work was the evaluation of a multi-residue method for the determination of eleven pesticides in tropical fruits of Yucatan, Mexico. Pesticide extraction was carried out with acetonitrile and clean-up by dispersive solid phase extraction (QuEChERS method). The extracts were analyzed by GC/MS. The quantification was performed by the external standard matrix match calibration. Most of the quantification limits were below 10 ng?g-1. In 70% of the cases, the relative standard deviation was lower than 15%. The pesticide recoveries ranged from 67.74% to 138.57%. The method allowed the quantification of pesticides in papaya, melon, dragon fruit and sugar apple.

Resumen: La ingesta de plaguicidas causa problemas de salud; por lo tanto, los alimentos no deben exceeder los límites máximos permitidos. El objetivo de este trabajo fue evaluar un método multiresíduo para la determinación de once plaguicidas en frutas tropicales del estado de Yucatán, México. La extracción de plaguicicas se realizó con acetonitrilo y la limpieza por extracción por fase sólida dispersiva (método QuEChERS). Los extractos se analizaron por GC/MS. La cuantificación se realizó por calibración externa utilizando la misma matriz de los extractos. La mayoría de los límites de cuantificación estuvieron por debajo de 10 10 ng?g-1. En el 70% de los casos la desviación estándar relativa fue menor al 15%. Las recuperaciones de los plaguicidas estuvieron entre 67.74% y 138.57%. El método permitió la cuantificación de plaguicidas en papaya, melón, pitaya y saramuyo.

A multiresidue method was developed to estimate community drug use during two weekends of the 2014 Soccer World Cup via wastewater analyses. Five of the 16 investigated substances were detected in all eight samples. Benzoilecgonine (BE), the major cocaine metabolite, was the most abundant substance (1.9 ± 0.3 to 4.2 ± 0.2 μg L-1) followed by anhydroecgonine (AE) (1.5 ± 0.2 to 2.6 ± 0.2 μg L-1), phenacetin (PHE) (0.62 ± 0.06 to 1.3 ± 0.1 μg L-1), levamisole (LEV) (0.5 ± 0.2 to 1.23 ± 0.09 μg L-1), and cocaine (COC) (0.46 ± 0.07 to 0.8 ± 0.1 μg L-1). COC and BE levels suggested a human consumption origin for the investigated drugs. AE/BE ratios revealed a significant use of smoked crack/free base cocaine. Relationships between the adulterants PHE and LEV evidenced a higher use of crack cocaine in the South-Wing WWTP region. An estimative for cocaine use revealed slightly higher drug consumption during the Soccer World Cup weekends in comparison with a typical weekend in 2012.

Resumen Se desarrolló un método para la determinación de residuos de plaguicidas en miel de abejas mediante cromatografía líquida ultra rápida acoplada a espectrometría de masas(cuádruplo sencillo). Se partió del método QuEChERS, evaluando las siguientes variables: (i) cantidad de muestra, (ii) tipo de sal para el control de pH, (iii) valor de pH del buffer y (iv) mezclas de limpieza. Adicionalmente y con el propósito de demostrar la confiabilidad del método, se evaluaron diferentes parámetros como exactitud, límites de detección y cuantificación, linealidad y selectividad. Los resultados mostraron que, mediante las modificaciones realizadas, se logró obtener un método más selectivo y se mejoró la exactitud de 19 plaguicidas respecto al método QuEChERS original. Por otro lado, mediante el proceso de validación, se encontró que el método es apto para el análisis de 50 plaguicidas (de 56 que se emplearon). Se obtuvieron porcentajes de recuperación entre el 70 y 120% y coeficientes de variación inferiores al 15%

Abstract A method for the determination of pesticide residues in honey by ultra fast liquid chromatography coupled with mass spectrometry was developed. For this purpose, different variations of the QuECHERS method were performed: (i) amount of sample, (ii) type of salt to control pH, (iii) buffer pH, and (iv) different mixtures for cleaning-up. In addition, to demonstrate that the method is reliable, different validation parameters were studied: accuracy, limits of detection and quantification, linearity, and selectivity. The results showed that by means of the changes introduced it was possible to get a more selective method that improves the accuracy of about 19 pesticides selected from the original method. It was found that the method is suitable for the analysis of 50 pesticides, out of 56. Furthermore, with the developed method recoveries between 70 and 120% and relative standard deviation below 15% were found.

Resumo Foi desenvolvido um método para a determinação de resíduos de pesticidas no mel por cromatografia líquida ultrarrápida acoplada à espectrometría de massa. Para este efeito, foram realizadas diferentes variações do método QuEChERS: (i) quantidade de amostra, (ii) tipo de sal para o controle do pH, (iii) valor do pH do tampão, (iv) diferentes misturas de limpeza. Além disso, a fim de demonstrar que o método é confiável, diferentes parâmetros foram validados como: precisão, limite de detecção e quantificação, linearidade e seletividade. Os resultados mostraram que, por meio das modificações é possível obter um método mais seletivo que melhora a precisão de cerca de 19 pesticidas selecionados, respeito ao método original. Adicionalmente, foi determinado que a validação do método estabeleceu que este é adequado para a análise de 50 pesticidas (56 foram utilizados). Foram obtidos percentagens de recuperação entre 70 e 120% e coeficientes de variação menores ao 15%.

This work involved the validation of a multiresidue method according to the Normative Instruction 24/2009-MAPA for determining 25 analytes, among fluoroquinolones, sulfonamides and trimethoprim in samples of poultry and porcine kidney. The extraction procedure was based on a QuEChERS approach. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed using the selected reaction monitoring mode (SRM) and ESI+ ionization. All of the validated figures of merit were evaluated as satisfactory. Accuracy was assessed by recovery studies, varying from 82.7 to 115.5% for porcine kidney and from 91.5 to 110.4% for poultry kidney. Relative standard deviations were lower than 25.5% for porcine kidney, and 29.8% for poultry kidney. Decision limits (CCα) comprised values from 10.37 to 3298.43 µg kg-1 for porcine kidney and 10.08 to 3176.59 µg kg-1 for poultry kidney. Detection capabilities (CCβ) varied from 10.73 to 3396.86 µg kg-1 for porcine kidney and 10.67 to 3253.19 µg kg-1 for poultry kidney. The developed method has been successfully employed in the routine analysis of incurred samples.

An effective analytical method for pesticides multiresidue determination in grape samples was developed and validated. A modified quick, easy, cheap, effective, robust and safe (QuEChERS) method was used to extract the target compounds. Several sorbent materials were tested for the clean-up step using dispersive solid phase extraction (d-SPE) and Florisil® was selected. Samples extracts were evaporated before injection in the gas chromatography with mass spectrometry (GC-MS) system in order to improve detectability. Recoveries from blank samples spiked at 0.04, 0.3 and 1.0 mg kg−1 ranged from 95 to 102% with relative standard deviation (RSD) from 1.3 to 19.7%. Method limits of detection (LODm) and quantification (LOQm) ranged from 0.006 to 0.012 and 0.02 to 0.04 mg kg−1, respectively. The positive matrix effect caused an increase in the peak areas of all compounds and matrix matched calibration curve linearity (coefficient of determination, r2) was higher than 0.98 for all target analytes. The validated method was successfully applied for the determination of 19 pesticides in grape samples.