VI Jornada Nacional sobre estudios universitarios. II Taller de innovación educativa. Competencias: formación y evaluación

VI Jornada Nacional sobre Estudios Universitarios y II Taller de Innovación Educativa celebrados en la Universitat Jaume I los días 9 y 10 de noviembre de 2017

Application of Fast Gas Chromatography–Mass Spectrometry in Combination with the QuEChERS Method for the Determination of Pesticide Residues in Fruits and Vegetables

A fast gas chromatography–mass spectrometry method has been developed for multiresidue determination of up to 56 pesticides in fruits and vegetables in a chromatographic run time of <10 min, using a single quadrupole mass spectrometer operating in selected ion monitoring mode. The well-known acetate-buffering version of the QuEChERS method has been used for sample preparation. Programmable temperature vaporizer injection of 3 μL allowed reaching limits of detection between 0.15 and 15 μg/kg for most compounds in the sample matrices tested. The applicability of the method has been evaluated in apple, orange, carrot, and tomato. Recoveries at three fortification levels (0.01, 0.1 and 0.5 mg/kg) ranged from 70 to 120 % for most compounds, with relative standard deviations below 20 % in all cases. The developed method has been applied to fruit and vegetable samples from different Spanish provinces

Multiclass determination of 66 organic micropollutants in environmental water samples by fast gas chromatography–mass spectrometry

A multiresidue method has been developed for quantification and identification of 66 multiclass priority organic pollutants in water by fast gas chromatography (GC) coupled to mass spectrometry (MS). Capabilities and limitations of single quadrupole mass spectrometer as detector in fast GC were studied evaluating the chromatographic responses in terms of sensitivity and chromatographic peak shapes, as they were influenced by scan time. The number of monitored ions in a selected ion monitoring (SIM) group strongly conditioned the scan time and subsequently the number of data points per peak. A compromise between peak shape and scan time was adopted in order to reach the proper conditions for quantitative analysis. An average of 10–15 points per peak was attained for most compounds, involving scan times between 0.1 and 0.22 s. The method was validated for mineral, surface, and groundwater. A solid-phase extraction pre-concentration step using C18 cartridges was applied. Four isotopically labeled standards were added to the samples before extraction and used as surrogates to ensure a reliable quantification. Analyses were performed by GC–MS in electron ionization mode, monitoring the three most abundant and/or specific ions for each compound and using the intensity ratios as a confirmatory parameter. With a chromatographic run of less than 10 min, SIM mode provided excellent sensitivity and identification capability due to the monitoring of three ions and the evaluation of their intensity ratio. Limits of detection below 10 ng/L were reached for most of the 66 compounds in the three matrices studied. Accuracy and precision of the method were evaluated by means of recovery experiments at two fortification levels (10 and 100 ng/L), obtaining recoveries between 70% and 120% in most cases and relative standard deviations below 20%. The possibilities of a simultaneous SIM scan method have also been explored for non-target qualitative analysis. The developed method has been applied to the analysis of surface water samples collected from the Mediterranean region of Spain

Comparison of Simple and Rapid Extraction Procedures for the Determination of Pesticide Residues in Fruit Juices by Fast Gas Chromatography–Mass Spectrometry

Three sample treatment methods, based on QuEChERS, solid-phase extraction (SPE) and solid-phase microextraction (SPME), were compared and evaluated in order to obtain the best conditions to determine pesticide residues in fruit juice by fast gas chromatography–mass spectrometry (single quadrupole GC-MS). Analysis were performed under selected ion monitoring, acquiring the three most abundant and/or specific ions for each analyte and using their relative intensity ratios as a confirmatory parameter. The 3 methodologies (QuEChERS, SPE and SPME) were validated taking 15 selected pesticides as model compounds, using commercial apple juice. QuEChERS procedure was based on the AOAC Official Method 2007.01, using acetonitrile (containing 1 % acetic acid) as extraction solvent and primary–secondary amine during the dispersive solid-phase extraction. Oasis hydrophilic–lipophilic balance cartridges were used for SPE, and polyacrylate fibers were used for direct immersion SPME procedure. Three isotopically labeled standards were added to the samples before extraction and used as surrogate standards. Validation parameters as recoveries, limits of detection, and limits of quantification (LOQ), as well as matrix effects and sample throughput, were obtained and compared for the three extraction procedures. QuEChERS was considered faster and led to the best quantitative results. In this way, validation was extended to up to 56 pesticides by applying QuEChERS in multi-fruit juice samples, obtaining LOQs ranging from 2 to 20 μg/L for most compounds. Accuracy and precision were evaluated by means of recovery experiments at two concentration levels (10 and 100 μg/L), obtaining recoveries between 70 and 120 % in most cases and relative standard deviations below 15 %. Finally, the QuEChERS method was applied to the analysis of commercial juices, including mango–apple, pineapple, grapefruit and orange

V Jornada Nacional sobre Estudios Universitarios (5a. 2015. Castelló de la Plana). Estructura de títulos v3.2 y I Taller de motivación educativa, motivar para emprender, la asignatura pendiente

Jornada celebrada en Castellón de la Plana los días 12 y 13 de noviembre de 2015El principal objectiu d'aquesta jornada és facilitar que es compartisquen experiències i s'intercanvien opinions sobre dues tendències que marcaran els pròxims anys en la vida universitària espanyola: l'estructura de títols idònia i la necessitat de les universitats de contribuir a crear una cultura emprenedora. Amb aquestes jornades es pretén donar continuïtat a les celebrades en anys anteriors, en les quals acadèmics de diferents disciplines han debatut sobre els diferents factors que afecten a l'educació superior.El principal objetivo de esta jornada es facilitar que se compartan experiencias y se intercambien opiniones sobre dos tendencias que van a marcar los próximos años en la vida universitaria española: la estructura de títulos idónea y la necesidad de las universidades de contribuir a crear una cultura emprendedora. Con estas jornadas se pretende dar continuidad a las celebradas en años anteriores, en las que académicos de distintas disciplinas han debatido sobre los distintos factores que afectan a la educación superior

The role of GC-MS/MS with triple quadrupole in pesticide residue analysis in food and the environment

Gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) using a triple quadrupole (QqQ) analyzer has in the last few years become a powerful technique for the determination of pesticide residues due to its robustness, and excellent sensitivity and selectivity. This review gives an overview of currently published applications of GC-MS/MS with a QqQ analyzer for pesticide residue analysis of different food and environmental sample matrices. This technique allows the reliable quantification and identification of low pesticide concentrations for non-polar (semi) volatile compounds belonging to different chemical families. It has allowed a notable improvement of methods performance in comparison with the traditional GC methods with single stage quadrupole MS

Application of gas chromatography time-of-flight mass spectrometry for target and non-target analysis of pesticide residues in fruits and vegetables

In this work, the capability of gas chromatography coupled to time-of-flight mass spectrometry (GC–TOF MS) for quantitative analysis of pesticide residues has been evaluated. A multiclass method for rapid screening of pesticides (insecticides, acaricides, herbicides and fungicides) in fruit and vegetable matrices has been developed and validated, including detection, identification and quantification of the analytes. To this aim, several food matrices were selected: high water content (apples, tomatoes and carrots), high acid content (oranges) and high oil content (olives) samples. The well known QuEChERS procedure was applied for extraction of pesticides, and matrix-matched calibration using relative responses versus internal standard was used for quantification. The sample extracts were analyzed by GC–TOF MS. Up to five ions using narrow window (0.02 Da)-extracted ion chromatograms at the expected retention time were monitored using a target processing method. The most abundant ion was used for quantification while the remaining ones were used for confirmation of the analyte identity. Method validation was carried out for 55 analytes in the five sample matrices tested at three concentrations (0.01, 0.05 and 0.5 mg/kg). Most recoveries were between 70% and 120% with relative standard deviations (RSDs) lower than 20% at 0.05 and 0.5 mg/kg. At 0.01 mg/kg, roughly half of the pesticides could be satisfactorily validated due to sensitivity limitations of GC–TOF MS, which probably affected the ion ratios used for confirmation of identity. In the case of olive samples, results were not satisfactory due to the high complexity of the matrix. An advantage of TOF MS is the possibility to perform a non-target investigation in the samples by application of a deconvolution software, without any additional injection being required. Accurate-mass full-spectrum acquisition in TOF MS provides useful information for analytes identification, and has made feasible in this work the discovery of non-target imazalil, fluoranthene and pyrene in some of the samples analyzed

Simultaneous determination of dechloranes, polybrominated diphenyl ethers and novel brominated flame retardants in food and serum

A sensitive method for the simultaneous quantification of dechloranes, polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) has been developed for gas chromatography (GC) coupled to tandem mass spectrometry operating in electron capture negative ionization (ECNI) mode. The major advance has been achieved by combining selected ion monitoring (SIM) and multiple reaction monitoring (MRM) modes in well-defined time windows, to determine dechloranes, PBDEs and NBFRs at picogram per gram level in one single analysis in complex matrix biological samples. From the chromatographic point of view, efforts were devoted to study several injection modes using multimode inlet (MMI) in order to obtain low instrumental detection limits, necessary for trace compounds such as Dechlorane Plus (DP) isomers. Method performance was also evaluated: calibration curves were linear from 20 fg μL−1 to 100 pg μL−1 for the studied compounds, with method detection limits at levels of 50 fg g−1 for DPs. Repeatability and reproducibility, expressed as relative standard deviation, were better than 5% even in solvent vent mode for the injection of standards. The application to a wide range of complex samples (including food, human and animal serum samples) indicated a sensitive and reliable way to quantify at the picogram per gram level 4 halogenated norbornenes (HNs), Dechlorane Plus (anti-DP and syn-DP) and 2 of their homologues (Dechlorane-602 and Dechlorane-603), 11 PBDE congeners (no. 28, 47, 49, 66, 85, 99, 100, 153, 154, 183 and 209) and 5 novel BFRs, i.e. decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), hexabromobenzene (HBB), 2,3,4,5-tetrabromo-ethylhexyl-benzoate (TBB) and tetrabromophthalate (TBPH).The authors acknowledge the financial support of Universitat Jaume I (UJI-A2016-01) and Generalitat Valenciana (research group of excellence PROMETEO/2009/054 and PROMETEO II 2014/023 and Collaborative Research on Environment and Food-Safety (ISIC/2012/016)). Carlos Sales acknowledges the COST Action ES1307 for the STSM grant which made possible his stay at the Toxicological Centre of Antwerp. Dr. Giulia Poma and Dr. Govindan Malarvannan acknowledge the University of Antwerp for their postdoctoral fellowships

Optimization of electronic nose drift correction applied to tomato volatile profiling

This is a pre-print of an article published in Analytical and Bioanalytical Chemistry. The final authenticated version is available online at: https://doi.org/10.1007/s00216-021-03340-5E-noses can be routinely used to evaluate the volatile profile of tomato samples once the sensor drift and standardization issues are adequately solved. Short-term drift can be corrected using a strategy based on a multiplicative drift correction procedure coupled with a PLS adaptation of the component correction. It must be performed specifically for each sequence, using all sequence signals data. With this procedure, a drastic reduction of sensor signal %RSD can be obtained, ranging between 91.5 and 99.7% for long sequences and between 75.7 and 98.8% for short sequences. On the other hand, long-term drift can be fixed up using a synthetic reference standard mix (with a representation of main aroma volatiles of the species) to be included in each sequence that would enable sequence standardization. With this integral strategy, a high number of samples can be analyzed in different sequences, with a 94.4% success in the aggrupation of the same materials in PLS-DA two-dimensional graphical representations. Using this graphical interface, e-noses can be used to developed expandable maps of volatile profile similitudes, which will be useful to select the materials that most resemble breeding objectives or to analyze which preharvest and postharvest procedures have a lower impact on the volatile profile, avoiding the costs and sample limitations of gas chromatography

Quantification of prominent volatile compounds responsible for muskmelon and watermelon aroma by purge and trap extraction followed by gas chromatography–mass spectrometry determination

A dynamic headspace purge-and-trap (DHS-P&T) methodology for the determination and quantification of 61 volatile compounds responsible for muskmelon and watermelon aroma has been developed and validated. The methodology is based on the application of purge-and-trap extraction followed by gas chromatography coupled to (ion trap) mass spectrometry detection. For this purpose two different P&T sorbent cartridges have been evaluated. The influence of different extraction factors (sample weight, extraction time, and purge flow) on extraction efficiency has been studied and optimised using response surface methodology. Precision, expressed as repeatability, has been evaluated by analysing six replicates of real samples, showing relative standard deviations between 3% and 27%. Linearity has been studied in the range of 10–6130 ng mL−1 depending on the compound response, showing coefficients of correlation between 0.995 and 0.999. Detection limits ranged between 0.1 and 274 ng g−1. The methodology developed is well suited for analysis of large numbers of muskmelon and watermelon samples in plant breeding programs