Osmar D. Prestes

Simultaneous determination of pesticides, biopesticides and mycotoxins in organic products applying a quick, easy, cheap, effective, rugged and safe extraction procedure and ultra-high performance liquid chromatography–tandem mass spectrometry

A method for the simultaneous determination of pesticides, biopesticides and mycotoxins from organic products was developed. Extraction of more than 90 compounds was evaluated and performed by using a modified QuEChERS-based (acronym of Quick, Easy, Cheap, Effective, Rugged, and Safe) sample preparation procedure. The method was based on a single extraction with acidified acetonitrile, followed by partitioning with salts, avoiding any clean-up step prior the determination by ultra-high performance liquid chromatography/tandem quadrupole mass spectrometry (UHPLC-MS/MS). Validation studies were carried out in wheat, cucumber and red wine as representative matrixes. Recoveries of the spiked samples were in the range between 70 and 120% (with intra-day precision, expressed as relative standard deviation, lower than 20%) for most of the analysed compounds, except picloram and quinmerac. Inter-day precision, expressed as relative standard deviation, was lower than 24%. Limits of quantification were lower than 10μg kg⁻¹ and the developed method was successfully applied to the analysis of organic food products, detecting analytes belonging to the three types of compounds.

QuEChERS: a modern sample preparation method for pesticide multiresidue determination in food by chromatographic methods coupled to mass spectrometry

This review attempts to provide an updated overview of the Quick, Easy, Cheap, Effective, Ruged and Safe (QuEChERS) multiresidue extraction method, that involves initial extraction in acetonitrile, an extraction/partition step after the addition of salt, and a cleanup step utilizing dispersive solid phase extraction. QuEChERS method is nowadays the most applied extraction method for the determination of pesticide residues in food samples, providing acceptable recoveries for acidic, neutral and basic pesticides. Several applications for various food matrices (fruits, vegetables, cereals and others) in combination with chromatographic mass spectrometry analysis were presented.

Method validation and comparison of acetonitrile and acetone extraction for the analysis of 169 pesticides in soya grain by liquid chromatography-tandem mass spectrometry.

An acetonitrile-based extraction method for the analysis of 169 pesticides in soya grain, using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the positive and negative electrospray ionization (ESI) mode, has been optimized and validated. This method has been compared with our earlier published acetone-based extraction method, as part of a comprehensive study of both extraction methods, in combination with various gas chromatography-(tandem) mass spectrometry [GC-MS(/MS)] and LC-MS/MS techniques, using different detection modes. Linearity of calibration curves, instrument limits of detection (LODs) and matrix effects were evaluated by preparing standards in solvent and in the two soya matrix extracts from acetone and acetonitrile extractions, at seven levels, with six replicate injections per level. Limits of detection were calculated based on practically realized repeatability relative standard deviations (RSDs), rather than based on (extrapolated) signal/noise ratios. Accuracies (as % recoveries), precision (as repeatability of recovery experiments) and method limits of quantification (LOQs) were compared. The acetonitrile method consists of the extraction of a 2-g sample with 20 mL of acetonitrile (containing 1% acetic acid), followed by a partitioning step with magnesium sulphate and a subsequent buffering step with sodium acetate. After mixing an aliquot with methanol, the extract can be injected directly into the LC-MS/MS system, without any cleanup. Cleanup hardly improved selectivity and appeared to have minor changes of the matrix effect, as was earlier noticed for the acetone method. Good linearity of the calibration curves was obtained over the range from 0.1 or 0.25 to 10 ng mL(-1), with r(2)>or=0.99. Instrument LOD values generally varied from 0.1 to 0.25 ng mL(-1), for both methods. Matrix effects were not significant or negligible for nearly all pesticides. Recoveries were in the range 70-120%, with RSD<or=20%. If not, they were still mostly in the 50-70% range, with good precision (RSD<or=20%). The method LOQ values were most often 10 microg kg(-1) for almost all pesticides, with good repeatability RSDs. Apart from some minor pros and cons, both compared methods are fast, efficient and robust, with good method performances. The two methods were applied successfully in a routine analysis environment, during surveys in 2007 and 2008.

Optimization of a QuEChERS based method by means of central composite design for pesticide multiresidue determination in orange juice by UHPLC-MS/MS.

In this study, different extraction procedures based on the QuEChERS method were compared for the multiresidue determination of pesticides in orange juice by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). After choosing preliminary conditions, an experimental design was carried out with the variables C18, PSA, NaOH and CH3COONa to optimize the sample preparation step. The validation results of the validation were satisfactory, since the method presented recoveries between 70% and 118%, with RSD lower than 19% for spike levels between 10 and 100 μg L(-1). The method limit of detection (LOD) and limit of quantification (LOQ) ranged from 3.0 to 7.6 μg L(-1) and from 4.9 to 26 μg L(-1), respectively. The method developed was adequate for the determination of 74 pesticide residues in orange juice.

Evaluation of alternative sorbents for dispersive solid‐phase extraction clean‐up in the QuEChERS method for the determination of pesticide residues in rice by liquid chromatography with tandem mass spectrometry

Many compounds are used for pest control during the production and storage of rice, making it necessary to employ multiclass methods for pesticide residues determination. For this purpose, QuEChERS-based methods are very efficient, fast and accurate, and improvements in the clean-up step are important, especially for complex matrices, like cereals. In this work, different sorbents such as chitosan, florisil(®) , alumina, diatomaceous earth, graphitized carbon black, besides the commonly used primary secondary amine and octadecylsilane, were evaluated for dispersive solid-phase extraction clean-up in acetate-buffered QuEChERS method for the determination of residues of 20 representative pesticides and one metabolite in rice by liquid chromatography coupled to tandem mass spectrometry. The sorbent C18 presented the best results, however, chitosan showed similar results, and the best performance among the unconventional sorbents evaluated. The method limit of quantification, attending accuracy (70-120% recovery) and precision (RSD ≤20%) criteria, ranged from 5 to 20 μg/kg. Results showed that chitosan is an effective alternative to reduce analysis costs, maintaining the method reliability and accuracy.

Multiresidue determination of pesticides in drinking water by gas chromatography-mass spectrometry after solid-phase extraction

Neste trabalho, um metodo usando extracao em fase solida e cromatografia a gas acoplada a espectrometria de massas no modo de monitoramento seletivo de ions, foi desenvolvido e validado para a determinacao multiclasse de 20 pesticidas regulados pela legislacao brasileira para agua potavel. Como estes pesticidas devem ser determinados em baixas concentracoes, um elevado fator da pre-concentracao associado a sensibilidade elevada da analise cromatografica foi necessario. O metodo apresentou limites de quantificacao entre 0,003 e 0,093 µg L-1. A maioria dos compostos apresentou recuperacoes medias entre 51 e 116%. Embora a natureza quimica distinta dos pesticidas analisados dificulte a obtencao de boa recuperacao para todos os compostos avaliados, a precisao dos resultados foi excelente. A seletividade do metodo foi avaliada atraves da intensidade relativa dos ions de quantificacao e de qualificacao, sendo considerada adequada. A analise em amostras reais cumpriu os criterios para a qualificacao instrumental e a avaliacao da conformidade do sistema.

Principais técnicas de preparo de amostra para a determinação de resíduos de agrotóxicos em água por cromatografia líquida com detecção por arranjo de diodos e por espectrometria de massas

The determination of pesticide residues in water samples by Liquid Chromatography require sample preparation for extraction and enrichment of the analytes with the minimization of interferences to achieve adequate detection limits. The Solid Phase Extraction (SPE), Solid Phase Microextraction (SPME), Stir Bar Sorptive Extraction (SBSE) and Dispersive Liquid-Liquid Microextraction (DLLME) techniques have been widely used for extraction of pesticides in water. In this review, the principles of these sample preparation techniques associated with the analysis by Liquid Chromatography with Diode Array Detection (LC-DAD) or Mass Spectrometry (LC-MS) are described and an overview of several applications were presented and discussed.

Comparison of several extraction procedures for the determination of biopesticides in soil samples by ultrahigh pressure LC-MS/MS

A new procedure has been proposed for the determination of biopesticides (nicotine, sabadine, veratridine, rotenone, azadirachtin, cevadine, deguelin, spynosad D, and pyrethrins) and piperonyl butoxide in agricultural soils. Several extraction procedures such as solid-liquid extraction using mechanical shaking, sonication, pressurized liquid extraction, and modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) have been tested, obtaining better results when QuEChERS procedure without further cleanup steps was applied. The determination of the compounds was carried out by ultra high pressure liquid chromatography coupled to tandem mass spectrometry, using methanol and aqueous solution of ammonium formate 5 mM as mobile phase. The method was validated for all compounds at concentrations ranging from 10 to 100 μg/kg and recoveries ranged from 68 to 116%, except for nicotine and sabadine, with recoveries lower than 50%. Precision was estimated through intra- and inter-day studies, obtaining intra-day precision lower than 20% for most of the compounds, and inter-day precision was lower than 25%. Limits of detection and quantification were also estimated, obtaining limits of quantification equal or lower than 10 μg/kg. Finally, the method was applied to the analysis of 20 real agricultural soil samples and no biopesticide residues were found over the limit of quantification.

Determination of pesticides and related compounds in water by dispersive liquid–liquid microextraction and gas chromatography-triple quadrupole mass spectrometry

The declining quality of drinking water supplies due to industrial waste is the result of highly diverse industrial processes. In this context, the establishment of analytical methods focused on monitoring organic compounds related to environmental and health problems is very important. In this study, a quick and effective method based on dispersive liquid–liquid microextraction (DLLME) and gas chromatography coupled with triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) was developed and validated for the simultaneous determination of pesticide residues and related compounds in water. The proposed DLLME method uses water sample aliquots of 5 mL, 2 mL of acetone as a dispersive solvent and 50 μL of carbon tetrachloride as an extraction solvent at low temperature. This method was successfully applied for the determination of pesticide residues and related compounds in water at quantification limits between 0.03 and 0.10 μg L−1. The method showed a linear range from 0.05 to 10.0 μg L−1 with r2 > 0.998. Recovery assays presented mean recoveries between 70 and 120% for most of the compounds with good precision, despite different chemical natures of the compounds analyzed.

O estado da arte na determinação de resíduos de medicamentos veterinários em alimentos de origem animal empregando técnicas cromatográficas acopladas à espectrometria de massas

The determination of veterinary drug residues in foods of animal origin is an important issue because of the risk these compounds pose to human health in addition to their persistence and tendency to bioaccumulate. In recent years, significant progress has been made in the area and this review presents the state of the art in sample preparation procedures associated with chromatographic techniques coupled to mass spectrometry for multiresidue determination of veterinary drugs in food of animal origin at concentration levels suitable for the control of residues and contaminants in food.